Sulfonium salts, chemically amplified resist compositions, and pattern forming processes

Abstract

The present invention relates to a sulfonium salt, a chemically amplified resist composition, and a pattern forming method. The present invention provides a sulfonium salt used in a chemically amplified resist composition which is excellent in resolution, and which can suppress collapse of a resist pattern, and a chemically amplified resist composition containing the sulfonium salt as a quencher, and a pattern forming method using the chemically amplified resist composition, in optical lithography using a high-energy ray. The means for solving the problem is a sulfonium salt represented by the following formula (1). In the formula, Z ‑ is an aromatic carboxylic acid anion which can also have a substituent.

Description

Technical Field

[0001] This invention relates to matte salts, chemically amplified resist compositions, and methods for pattern formation. Background Technology

[0002] With the increasing integration and speed of LSI (Lithium-ion Sensors), the miniaturization of patterning is also progressing rapidly. This is due to the widespread adoption of high-speed 5G communication and artificial intelligence (AI), which necessitates high-performance devices to handle these technologies. Regarding the most advanced miniaturization technology, mass production of 5nm node devices using 13.5nm extreme ultraviolet (EUV) lithography is already underway. Furthermore, discussions are underway regarding the use of EUV lithography in next-generation 3nm and the next-next-generation 2nm node devices.

[0003] As miniaturization progresses, image blurring caused by acid diffusion becomes a problem. To ensure the resolution of fine patterns below 45 nm, in addition to the previously proposed improvement of dissolution contrast, it has been suggested that controlling acid diffusion is crucial (Non-Patent Literature 1). However, chemically amplified resist compositions utilize acid diffusion to improve sensitivity and contrast; therefore, if the post-exposure baking (PEB) temperature is lowered or the time is shortened to suppress acid diffusion to the limit, sensitivity and contrast will be significantly reduced.

[0004] This demonstrates a triangular trade-off between sensitivity, resolution, and linewidth roughness (LWR). To improve resolution, acid diffusion needs to be suppressed, but shortening the acid diffusion distance will reduce sensitivity.

[0005] Adding acid-generating agents that produce bulky acids is effective in suppressing acid diffusion. Therefore, it has been proposed to include repeating units from onium salts with polymerizable unsaturated bonds in the polymer. In this case, the polymer also functions as an acid-generating agent (polymer-bonded acid-generating agent). Patent Document 1 proposes sulfonium salts and sulfonium salts with polymerizable unsaturated bonds that produce specific sulfonic acids. Patent Document 2 proposes sulfonium salts where the sulfonic acid is directly bonded to the main chain.

[0006] The acid-indestabilized groups in the (meth)acrylate polymers used in ArF resist compositions undergo deprotection reactions using acid-generating agents that produce sulfonic acids with α-position fluorine atom substitution. However, if the acid-generating agent does not produce sulfonic or carboxylic acids with α-position unsubstituted fluorine atom substitution, the deprotection reaction will not occur. When a sulfonium or ferrophosphate salt that produces sulfonic acids with α-position fluorine atom substitution is mixed with a sulfonium or ferrophosphate salt that produces sulfonic acids with α-position unsubstituted fluorine atom substitution, the sulfonium or ferrophosphate salt that produces sulfonic acids with α-position fluorine atom substitution will undergo ion exchange with the sulfonic acid with α-position fluorine atom substitution. The sulfonic acid with α-position fluorine atom substitution generated by light will reverse back to the sulfonium or ferrophosphate salt through ion exchange; therefore, the sulfonium or ferrophosphate salt of sulfonic or carboxylic acids with α-position unsubstituted fluorine atom substitution functions as a quencher. Some have proposed using matte or ferrous salts that produce carboxylic acids as quenching agents in resist compositions (Patent Document 3).

[0007] Some researchers have proposed sulfonate salt-type quenchers that produce carboxylic acids. Examples include sulfonates of salicylic acid, β-hydroxycarboxylic acid (Patent Document 4), salicylic acid derivatives (Patent Documents 5 and 6), fluorosalicylic acid (Patent Document 7), hydroxynaphthoic acid (Patent Document 8), salicylic acid with iodine-containing aromatic substituents (Patent Document 9), and salicylic acid with a cyclic acetal structure (Patent Document 10). Salicylic acid, in particular, exhibits a high degree of acid diffusion inhibition due to the intramolecular hydrogen bonding between the carboxyl and hydroxyl groups.

[0008] It has been pointed out that the dimensional uniformity (CDU) of the resist pattern decreases due to the aggregation of the quencher. The aim is to improve the dimensional uniformity of the developed pattern by preventing the aggregation of the quencher in the resist film and by homogenizing its distribution.

[0009] For further miniaturization requirements, especially during alkaline development in positive resists, swelling caused by the developer and pattern collapse during the formation of fine patterns have become a challenge. To address this miniaturization challenge, the development of novel materials for resist compositions is important, and it is desirable to develop onium salt-type quenchers with good sensitivity, well-controlled acid diffusion, excellent solvent solubility, and effective suppression of pattern collapse.

[0010] Existing technical documents

[0011] Patent documents

[0012] [Patent Document 1] Japanese Patent Application Publication No. 2006-45311

[0013] [Patent Document 2] Japanese Patent Application Publication No. 2006-178317

[0014] [Patent Document 3] Japanese Patent Application Publication No. 2007-114431

[0015] [Patent Document 4] International Publication No. 2018 / 159560

[0016] [Patent Document 5] Japanese Patent Application Publication No. 2020-203984

[0017] [Patent Document 6] Japanese Patent Application Publication No. 2020-91404

[0018] [Patent Document 7] Japanese Patent Application Publication No. 2020-91312

[0019] [Patent Document 8] Japanese Patent Application Publication No. 2019-120760

[0020] [Patent Document 9] Japanese Patent Application Publication No. 2022-77505

[0021] [Patent Document 10] International Publication No. 2023 / 189502

[0022] Non-patent literature

[0023] [Non-Patent Literature 1] SPIE Vol. 6520 65203L-1 (2007) Summary of the Invention

[0024] [The problem that the invention aims to solve]

[0025] To meet the high-resolution requirements of resist patterns in recent years, resist compositions using known sulfonate-type acid generators and quenchers cannot adequately suppress acid diffusion, resulting in degradation of lithographic performance such as contrast, LWR, CDU, exposure latitude (EL), and depth of focus (DOF). Furthermore, there is a problem of pattern collapse due to swelling during the formation of fine patterns.

[0026] The present invention was made in view of the foregoing circumstances, and aims to provide a sulfonium salt used in a chemically amplified resist composition for improving the lithography performance of LWR, CDU, EL, DOF, etc., with high sensitivity and excellent resolution, and suppressing the collapse of resist patterns in optical lithography using high-energy rays such as far-ultraviolet light, electron beam (EB), and EUV; a chemically amplified resist composition containing the sulfonium salt as a quencher; and a pattern formation method using the chemically amplified resist composition.

[0027] [Methods for solving the problem]

[0028] The inventors of this application, through repeated and in-depth exploration to achieve the aforementioned objectives, have obtained the following insights, and thus completed this invention: a sulfonium salt composed of an aromatic carboxylic acid anion and a sulfonium cation having an acid-unstable group having a nitro group and a tertiary / secondary ether structure, a tertiary / secondary ester structure, a tertiary / secondary carbonate structure, or an acetal structure on the same aromatic ring has excellent solvent solubility. The chemically amplified resist composition using it as a quenching agent has high sensitivity and high contrast, and excellent photolithography performance such as LWR, CDU, EL, and DOF. It is extremely effective in suppressing pattern collapse during the formation of fine patterns, and also contributes to suppressing defects during the development of patterns using alkaline developers.

[0029] That is, the present invention provides the following matte salt, chemically amplified resist composition and pattern formation method.

[0030] 1. A sulfonium salt, represented by the following formula (1).

[0031] [Chemistry 1]

[0032]

[0033] 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.

[0034] R 1 R 2 and R 3 Each R can be independently a halogen atom, cyano 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] Z - It can also be an aromatic carboxylic acid anion with substituents.

[0039] 2. Such as the sulfite salt in 1, which is represented by the following formula (1A).

[0040] [Chemistry 2]

[0041]

[0042] 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.

[0043] 3. A sulfonium salt as in 1 or 2, wherein the aforementioned acid-unstable group is represented by the formula (AL-1) or (AL-2).

[0044] [Chemistry 3]

[0045]

[0046] In the formula, p1 and p2 are independently 0 or 1, respectively. q1 and q2 are independently 0, 1, 2, 3 or 4, respectively.

[0047] 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 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.

[0048] 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 heterocycle can also be replaced by -O- or -S-.

[0049] L 4 It can be either -O- or -S-.

[0050] R La ~R Ld Hydrocarbon groups consisting of 1 to 20 carbon atoms, each independently composed of hydrogen atoms, or may contain heteroatoms.

[0051] * indicates L 1 L 2 and L 3 Atomic bonds.

[0052] 4. A sulfonium salt such as any one of 1.~3, where Z - Z represents the anion.

[0053] [Chemistry 4]

[0054]

[0055] In the formula, n21 is 0 or 1. n22 is 0, 1, 2, 3 or 4. n23 is 0, 1 or 2. n24 is 0, 1, 2, 3 or 4. However, when n21 is 0, 2 ≤ n22 + n23 + n24 ≤ 5, and when n21 is 1, 2 ≤ n22 + n23 + n24 ≤ 7.

[0056] L A It can be a single bond, -O-, -S-, ester bond, or carbonate bond.

[0057] R 11 In L A When the bond is a single hydrogen atom, it may also contain a hydrocarbon group with 1 to 20 carbon atoms and heteroatoms, in L A When the bond is -O-, -S-, ester bond or carbonate bond, it is a hydrogen atom, or it may contain a hydrocarbon group with 1 to 40 carbon atoms (but exclude acid-instable groups) or acid-instable groups.

[0058] R 12 It can be a halogen atom other than iodine, a nitro group, a cyano group, a pentafluorothio group, a 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 n24 is 2, 3, or 4, multiple R... 12 They can also bond to each other and form a ring structure together with the carbon atoms on the aromatic rings they are bonded to, and part of the -CH2- of the ring can be replaced by -O- or -S-.

[0059] 5. Sulfonium salts as in 4, wherein Z - Let (Z1) be the expression.

[0060] [Chemistry 5]

[0061]

[0062] In the formula, n22~n24, L A R 11 and R 12 Same as above.

[0063] 6. Sulfonium salts such as 4. or 5, wherein L A It is either -O- or an ester bond.

[0064] 7. Sulfonium salts such as those in 4 or 5, wherein L A For -O-, -S-, ester or carbonate bonds, R 11 It is an acid-labile group.

[0065] 8. A matte salt as described in any of 4.~7, wherein R 11 The acid-unstable group is represented by the following formula (AL-3) or (AL-4).

[0066]

[0067] In the formula, p1 and p2 are independently 0 or 1, respectively. q1 and q2 are independently 0, 1, 2, 3 or 4, respectively.

[0068] R L11 and R L12 Each is an independent hydrocarbon group having 1 to 12 carbon atoms. R L13 It consists of a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R L11 R L12 and R L13 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 L11 and R L12 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 L13 When R is a hydrogen atom L11 and R L12 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.

[0069] R L14 and R L15 Each can be independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R L16 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 L15 and R L16 They can also bond to each other and to the carbon atoms and L atoms they are bonded to. B Together they form a heterocyclic group with 3 to 20 carbon atoms, and part of the -CH2- of the heterocycle can also be replaced by -O- or -S-.

[0070] L B It can be either -O- or -S-.

[0071] R La ~R Ld Hydrocarbon groups consisting of 1 to 20 carbon atoms, each independently composed of hydrogen atoms, or may contain heteroatoms.

[0072] * indicates L A Atomic bonds.

[0073] 9. A quenching agent comprising a sulfonium salt of any one of 1. to 8.

[0074] 10. A chemically amplified resist composition containing a quencher such as 9.

[0075] 11. The chemically amplified resist composition of 10 further comprises a base polymer containing at least one of a repeating unit selected from the repeating units represented by formula (a1), formula (a2), and formula (a3).

[0076] [Chemistry 6]

[0077]

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

[0079] X 1 Single bond, 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, or a saturated hydrocarbon 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.

[0080] X 2 For single bonds, *-C(=O)-O- or *-C(=O)-N(H)-X 11 -

[0081] * indicates an atomic bond with a carbon atom in the main chain.

[0082] 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 oxy 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 oxy group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxy 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.

[0083] AL 1 and AL 2Each is an acid-labile group.

[0084] a1 can be 0, 1, 2, 3 or 4.

[0085] [Chemistry 7]

[0086]

[0087] 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.

[0088] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0089] X 3 It represents a single bond, *-C(=O)-O-, or *-C(=O)-N(H)-. * indicates an atomic bond with a carbon atom in the main chain.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxycarbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group or -N(R) group with 1 to 20 carbon atoms. 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 of the aromatic rings they are bonded to.

[0094] 12. A chemically amplified resist composition as described in 11, wherein the aforementioned polymer contains repeating units represented by formula (b1) or (b2).

[0095] [Chemistry 8]

[0096]

[0097] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0098] Y 1 Single bond, 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, or a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom. 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.

[0099] Y 2 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain.

[0100] 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)-).

[0101] 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 oxy 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 oxy group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxy 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.

[0102] c1 can be 1, 2, 3, or 4. c2 can be 0, 1, 2, 3, or 4. However, 1 ≤ c1 + c2 ≤ 5.

[0103] 13. A chemically amplified resist composition as described in 11 or 12, wherein the polymer contains at least one repeating unit selected from the following formula (c1), the following formula (c2), the following formula (c3), the following formula (c4), and the following formula (c5).

[0104] [Chemistry 9]

[0105]

[0106] In the formula, d1 and d2 are 0, 1, 2 or 3 independently, respectively.

[0107] e1 is 0 or 1. e2 is 0, 1, 2, 3 or 4. e3 is 0, 1, 2, 3 or 4. However, when e1 is 0, 0 ≤ e2 + e3 ≤ 4, and when e1 is 1, 0 ≤ e2 + e3 ≤ 6.

[0108] R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0109] Z 1 It is a single bond or may have substituents.

[0110] Z 2 For single bonds, **-C(=O)-OZ 21 -、**-C(=O)-N(H)-Z 21 -or**-OZ 21 -. Z 21 It is an aliphatic alkylene group, phenylene group, or a divalent group obtained by combining them, which has 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups.

[0111] Z 3 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0112] Z 4 It is a single bond, or an aliphatic alkylene group with 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups.

[0113] Z 5 Each can be a single bond, or a phenylene group with substituents, or a naphthylene group with substituents, or *-C(=O)-OZ. 51 -or *-C(=O)-N(R)-Z 51 -. Z 51It is an aliphatic hydrocarbon group, phenylene, or naphthylene with 1 to 10 carbon atoms, and the aliphatic hydrocarbon group may also contain a halogen atom, a hydroxyl group, an ether bond, an ester bond, or an lactone ring. R is a hydrogen atom, or may also contain a hydrocarbon group with 1 to 10 carbon atoms.

[0114] Z 6 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0115] Z 7 Each is independently a single bond, ***-Z 71 -C(=O)-O-、***-C(=O)-N(R)-Z 71 -or ***-OZ 71 -. Z 71 It can also be a hydrocarbon group with 1 to 20 carbon atoms and containing heteroatoms. R is the same as described above.

[0116] Z 8 Each is independently a single bond, ****-Z 81 -C(=O)-O-、****-C(=O)-N(R)-Z 81 -or ****-OZ 81 -. Z 81 It can also be a hydrocarbon group with 1 to 20 carbon atoms and containing heteroatoms. R is the same as described above.

[0117] Z 9 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, *-C(=O)-OZ 91 -、*-C(=O)-N(R)-Z 91 -or *-OZ 91 -. Z 91 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group. R is the same as described above.

[0118] * indicates an atomic bond with a carbon atom in the main chain. ** indicates an atomic bond with Z. 1 The atomic bonds. *** indicates the relationship between Z and 6 Atomic bonds. **** represents the bond between Z and Z. 7 Atomic bonds.

[0119] L 11 It can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, sulfonamide bond, carbonate bond or carbamate bond.

[0120] Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms.

[0121] 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.

[0122] Rf 5 and Rf 6 Each can be independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. However, all Rf 5 and Rf 6 It cannot be both hydrogen atoms at the same time.

[0123] Rf 7 It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl thio group having 1 to 6 carbon atoms, or a pentafluorothio group. When e2 is 2, 3, or 4, each Rf 7 They can be the same or different.

[0124] R 41 and R 42 Each can be independently a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms. Also, R 41 and R 42 They can also bond to each other and form rings together with the sulfur atoms they are bonded to.

[0125] R 43 It is a halogen atom other than fluorine, or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms. When e3 is 2, 3, or 4, each R 43 They can be the same or different, and there are multiple Rs. 43 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0126] M - It is a non-nucleophilic relative ion.

[0127] A + It is a ium cation.

[0128] 14. Any chemically amplified resist composition as described in any of 10 to 13 also contains an organic solvent.

[0129] 15. Any chemically amplified resist composition, such as any one of 10. to 14, also contains a photoacid generator that produces strong acid.

[0130] 16. A chemically amplified resist composition, such as any one of 10 to 15, further contains a quencher other than the quencher in 9.

[0131] 17. Any chemically amplified resist composition as described in any of 10 to 16, further contains a surfactant.

[0132] 18. A method for forming a pattern, comprising the following steps:

[0133] A resist film is formed on a substrate using a chemically amplified resist composition such as any one of 10. to 17.

[0134] The aforementioned resist film was exposed to high-energy radiation, and

[0135] The previously exposed resist film was developed using a developer.

[0136] 19. The pattern forming method of 18, wherein the aforementioned high-energy rays are KrF excimer lasers, ArF excimer lasers, EB, or EUV with a wavelength of 3 to 15 nm.

[0137] [The effects of the invention]

[0138] When patterning is performed using a chemically amplified resist composition containing the matte salt of the present invention as a quencher, a resist pattern with high contrast and good sensitivity, excellent photolithography performance such as LWR, CDU, EL, and DOF, and suppression of development defects can be formed. Detailed Implementation

[0139] [Sulfate]

[0140] The sulfite salt of the present invention is represented by the following formula (1).

[0141] [Chemistry 10]

[0142]

[0143] In formula (1), 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, it is preferable to have a benzene ring with n1 = 0. 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 being 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.

[0144] In formula (1), 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, it is preferable to have a benzene ring with n5 of 0. 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.

[0145] In formula (1), 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, it is preferable to have a benzene ring with n9 of 0. 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.

[0146] In equation (1), 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.

[0147] In equation (1), R 1 R 2 and R 3 Each group can be independently composed of a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms; a hydrocarbon oxygen 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, hydrocarbon oxygen group, and hydrocarbon thio 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, 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.

[0148] 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.

[0149] In equation (1), 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.

[0150] In equation (1), 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.

[0151] The aforementioned acid-unstable groups should preferably be represented by the following formula (AL-1) or (AL-2).

[0152] [Chemistry 11]

[0153]

[0154] In the formula, * represents the sum of L. 1 L 2 and L 3 Atomic bonds.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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 rings formed in this way 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.

[0159] 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 example applies to hydrocarbon groups with 1 to 10 carbon atoms.

[0160] 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 heterocycle can also be replaced by -O- or -S-.

[0161] In equation (AL-2), L 4 It can be either -O- or -S-.

[0162] In equations (AL-1) and (AL-2), R La ~R Ld Each of the above is a hydrocarbon group consisting of 1 to 20 carbon atoms, which may also contain heteroatoms. These hydrocarbon groups with 1 to 20 carbon atoms 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.

[0163] 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 the group with L... 1 L 2 and L 3 Atomic bonds.

[0164] [Chemistry 12]

[0165]

[0166] [Chemistry 13]

[0167]

[0168] [Chemistry 14]

[0169]

[0170] [Chemistry 15]

[0171]

[0172] [Chemistry 16]

[0173]

[0174] [Chemistry 17]

[0175]

[0176] [Chemistry 18]

[0177]

[0178] [Chemistry 19]

[0179]

[0180] [Chemistry 20]

[0181]

[0182] [Chemistry 21]

[0183]

[0184] [Chemistry 22]

[0185]

[0186] [Chemistry 23]

[0187]

[0188] [Chemistry 24]

[0189]

[0190] [Chemistry 25]

[0191]

[0192] [Chemistry 26]

[0193]

[0194] [Chemistry 27]

[0195]

[0196] [Chemistry 28]

[0197]

[0198] [Chemistry 29]

[0199]

[0200] [Chemistry 30]

[0201]

[0202] [Chemistry 31]

[0203]

[0204] [Chemistry 32]

[0205]

[0206] [Chemistry 33]

[0207]

[0208] 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 the group with L... 1 L 2 and L 3 Atomic bonds.

[0209] [Chemistry 34]

[0210]

[0211] [Chemistry 35]

[0212]

[0213] [Chemistry 36]

[0214]

[0215] In formula (1), nitro and -L 1 -R AL1 They should bond to adjacent carbon atoms. This proximity improves the -R group due to the electron-withdrawing property of the nitro group. AL1 It reduces the acidity of phenols and carboxylic acids generated during deprotection and improves solubility contrast.

[0216] In formula (1), nitro and -L 2 -R AL2 They should bond to adjacent carbon atoms. This proximity improves the -R group due to the electron-withdrawing property of the nitro group. AL2 It reduces the acidity of phenols and carboxylic acids generated during deprotection and improves solubility contrast.

[0217] In formula (1), nitro and -L 3 -R AL3 They should bond to adjacent carbon atoms. This proximity improves the -R group due to the electron-withdrawing property of the nitro group. AL3 It reduces the acidity of phenols and carboxylic acids generated during deprotection and improves solubility contrast.

[0218] 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.

[0219] [Chemistry 37]

[0220]

[0221] In the formula, the dashed lines represent atomic bonds.

[0222] The sulfite represented by formula (1) should preferably be represented by the following formula (1A).

[0223] [Chemistry 38]

[0224]

[0225] 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.

[0226] Specific examples of cations of sulfonium salts represented by formula (1) are shown below, but are not limited thereto. In addition, Me is a methyl group in the following formula.

[0227] [Chemistry 39]

[0228]

[0229] [Chemistry 40]

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[0231] [Chemistry 41]

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[0621] In equations (1) and (1A), Z - It can also be an aromatic carboxylic acid anion with substituents. The aforementioned aromatic carboxylic acid anion is preferably represented by the following formula (Z).

[0622] [Chemistry 236]

[0623]

[0624] In formula (Z), n21 is 0 or 1. When n21 is 0, it represents a benzene ring; when n21 is 1, it represents a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with n21 = 0. n22 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, it is preferable to have 0, 1, 2, or 3. Considering solvent solubility, 0, 1, or 2 is more preferred. n23 is 0, 1, or 2. n24 is 0, 1, 2, 3, or 4. However, when n21 is 0, 2 ≤ n22 + n23 + n24 ≤ 5; when n21 is 1, 2 ≤ n22 + n23 + n24 ≤ 7. Considering the availability of raw materials, n24 is preferable to have 0, 1, 2, or 3, with 0, 1, or 2 being more preferred.

[0625] In formula (Z), L A It can be a single bond, -O-, -S-, ester bond, or carbonate bond. (R will be discussed later.) 11 When L is a hydrogen atom A It should be -O-. Also, R will be discussed later. 11 When L is an acid-labile group, A It is preferable to use -O-, ester or carbonate bonds, with -O- or ester bonds being even better.

[0626] In formula (Z), R 11 In L AA hydrocarbon group with 1 to 20 carbon atoms, which may be a hydrogen atom when it is a single bond, or may contain heteroatoms. The aforementioned hydrocarbon groups with 1 to 20 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 20 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 20 carbon atoms, such as dodecyl; alkenyl groups with 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, pentenyl, and hexenyl; alkynyl groups with 2 to 20 carbon atoms, such as ethynyl, propynyl, butynyl, pentynyl, and hexynyl; cyclic unsaturated aliphatic hydrocarbon groups with 3 to 20 carbon atoms, such as cyclopentenyl and cyclohexenyl; aryl groups with 6 to 20 carbon atoms, such as phenyl, naphthyl, and dihydroindenyl; aralkyl groups with 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these. Furthermore, the aforementioned hydrocarbon groups may also contain heteroatoms, specifically halogen atoms, oxygen atoms, sulfur atoms, etc.]

[0627] R 11 In L A When the bond is -O-, -S-, ester bond, or carbonate bond, it is a hydrogen atom, or a hydrocarbon group with 1 to 20 carbon atoms (excluding acid-labile groups) or an acid-labile group. The aforementioned hydrocarbon groups can be any of the aforementioned groups other than acid-labile groups.

[0628] R 11 The unstable acid group should preferably be represented by the following formula (AL-3) or (AL-4).

[0629] [Chemistry 237]

[0630]

[0631] In the formula, * represents the sum of L. A Atomic bonds.

[0632] In equations (AL-3) and (AL-4), 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.

[0633] In equation (AL-3), R L11 and R L12 Each is an independent hydrocarbon group having 1 to 12 carbon atoms. R L13 It consists of a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R L11 R L12 and R L13 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.

[0634] R L11 R L12 and R L13 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.

[0635] Also, R L11 and R L12 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 rings formed in this way 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... L13 When R is a hydrogen atom L11 and R L12 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 this alicyclic ring can be replaced by halogen atoms.

[0636] In equation (AL-4), R L14 and R L15 Each can be independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R L14 and R L15 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. L11 R L12 and R L13 The same example applies to hydrocarbon groups with 1 to 10 carbon atoms.

[0637] In equation (AL-4), R L16 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] L15 and R L16They can also bond to each other and to the carbon atoms and L atoms they are bonded to. B Together they form a heterocyclic group with 3 to 20 carbon atoms, and part of the -CH2- of the heterocycle can also be replaced by -O- or -S-.

[0638] In equation (AL-4), L B It can be either -O- or -S-.

[0639] In equations (AL-3) and (AL-4), R La ~R Ld Each of the above is a hydrocarbon group consisting of 1 to 20 carbon atoms, which may also contain heteroatoms. These hydrocarbon groups with 1 to 20 carbon atoms 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.

[0640] Specific examples of acid-indestructible groups represented by formula (AL-3) can be listed and illustrated as similar examples as acid-indestructible groups represented by formula (AL-1), but are not limited thereto.

[0641] Specific examples of acid-indestructible groups represented by formula (AL-4) can be listed and illustrated as similar examples as acid-indestructible groups represented by formula (AL-2), but are not limited thereto.

[0642] In formula (Z), R 12 The halogen atom other than iodine, nitro, cyano, pentafluorothio, 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. Examples of halogen atoms other than iodine include fluorine, chlorine, and bromine, with fluorine being preferred. The aforementioned hydrocarbon groups with 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 11 The same example applies to hydrocarbon groups. Furthermore, the aforementioned hydrocarbon groups may also contain heteroatoms; specifically, they may contain halogen atoms, oxygen atoms, sulfur atoms, etc.

[0643] Furthermore, when n24 is 2, 3, or 4, multiple R 12 They can also bond to each other and form ring structures together with the carbon atoms on the aromatic rings they are bonded to, and part of the -CH2- in this ring can be replaced by -O- or -S-. Specific examples of rings formed in this way 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-.

[0644] The aromatic carboxylic acid anion represented by formula (Z) should preferably be represented by formula (Z1).

[0645] [Chemistry 238]

[0646]

[0647] In the formula, n22~n24, L A R 11 and R 12 Same as above.

[0648] Specific examples of aromatic carboxylic acid anions represented by formula (Z) are listed below, but are not limited thereto.

[0649] [Chemistry 239]

[0650]

[0651] [Chemistry 240]

[0652]

[0653] [Chemistry 241]

[0654]

[0655] [Chemistry 242]

[0656]

[0657] [Chemistry 243]

[0658]

[0659] [Chemistry 244]

[0660]

[0661] [Chemistry 245]

[0662]

[0663] [Chemistry 246]

[0664]

[0665] [Chemistry 247]

[0666]

[0667] [Chemistry 248]

[0668]

[0669] [Chemistry 249]

[0670]

[0671] [Chemistry 250]

[0672]

[0673] [Chemistry 251]

[0674]

[0675] [Chemistry 252]

[0676]

[0677] [Chemistry 253]

[0678]

[0679] [Chemistry 254]

[0680]

[0681] [Chemistry 255]

[0682]

[0683] [Chemistry 256]

[0684]

[0685] [Chemistry 257]

[0686]

[0687] [Chemistry 258]

[0688]

[0689] [Chemistry 259]

[0690]

[0691] [Chemistry 260]

[0692]

[0693] [Chemistry 261]

[0694]

[0695] [Chemistry 262]

[0696]

[0697] [Chemistry 263]

[0698]

[0699] [Chemistry 264]

[0700]

[0701] [Chemistry 265]

[0702]

[0703] [Chemistry 266]

[0704]

[0705] [Chemistry 267]

[0706]

[0707] [Chemistry 268]

[0708]

[0709] [Chemistry 269]

[0710]

[0711] [Chemistry 270]

[0712]

[0713] [Chemistry 271]

[0714]

[0715] [Chemistry 272]

[0716]

[0717] [Chemistry 273]

[0718]

[0719] [Chemistry 274]

[0720]

[0721] [Chemistry 275]

[0722]

[0723] [Chemistry 276]

[0724]

[0725] [Chemistry 277]

[0726]

[0727] [Chemistry 278]

[0728]

[0729] [Chemistry 279]

[0730]

[0731] [Chemistry 280]

[0732]

[0733] [Chemistry 281]

[0734]

[0735] [Chemistry 282]

[0736]

[0737] [Chemistry 283]

[0738]

[0739] [Chemistry 284]

[0740]

[0741] [Chemistry 285]

[0742]

[0743] [Chemistry 286]

[0744]

[0745] [Chemistry 287]

[0746]

[0747] [Chemistry 288]

[0748]

[0749] [Chemistry 289]

[0750]

[0751] [Chemistry 290]

[0752]

[0753] [Chemistry 291]

[0754]

[0755] [Chemistry 292]

[0756]

[0757] [Chemistry 293]

[0758]

[0759] [Chemistry 294]

[0760]

[0761] [Chemistry 295]

[0762]

[0763] [Chemistry 296]

[0764]

[0765] [Chemistry 297]

[0766]

[0767] [Chemistry 298]

[0768]

[0769] [Chemistry 299]

[0770]

[0771] [Chemical 300]

[0772]

[0773] [Chemical Engineering 301]

[0774]

[0775] [Chemical 302]

[0776]

[0777] [Chemical 303]

[0778]

[0779] [Chemical 304]

[0780]

[0781] [Chemical 305]

[0782]

[0783] [Chemical 306]

[0784]

[0785] [Chemical 307]

[0786]

[0787] [Chemical 308]

[0788]

[0789] [Chemical 309]

[0790]

[0791] [Chemical 310]

[0792]

[0793] [Chemistry 311]

[0794]

[0795] [Chemistry 312]

[0796]

[0797] [Chemistry 313]

[0798]

[0799] [Chemical 314]

[0800]

[0801] [Chemical 315]

[0802]

[0803] [Chemistry 316]

[0804]

[0805] [Chemistry 317]

[0806]

[0807] [Chemistry 318]

[0808]

[0809] [Chemistry 319]

[0810]

[0811] [Chemistry 320]

[0812]

[0813] [Chemistry 321]

[0814]

[0815] [Chemistry 322]

[0816]

[0817] [Chemistry 323]

[0818]

[0819] [Chemistry 324]

[0820]

[0821] [Chemistry 325]

[0822]

[0823] [Chemistry 326]

[0824]

[0825] [Chemistry 327]

[0826]

[0827] [Chemistry 328]

[0828]

[0829] [Chemistry 329]

[0830]

[0831] [Chemistry 330]

[0832]

[0833] [Chemistry 331]

[0834]

[0835] [Chemistry 332]

[0836]

[0837] [Chemistry 333]

[0838]

[0839] [Chemistry 334]

[0840]

[0841] [Chemistry 335]

[0842]

[0843] [Chemistry 336]

[0844]

[0845] [Chemistry 337]

[0846]

[0847] [Chemistry 338]

[0848]

[0849] Other specific examples of aromatic carboxylic acid anions represented by formula (Z) can be listed as follows: paragraphs

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

[0231] to

[0233] and

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

[0240] to

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

[0203] to

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

[0282] to

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

[0013] to

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

[0022] ~

[0024] of the report, 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. 20 Paragraphs from Japanese Patent Application Publication No. 24-074268

[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 Japanese Patent Application Publication No. 2024-102839

[0027] ~

[0028] , Paragraphs

[0035] ~

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

[0256] ~

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

[0266] of Japanese Patent Application Publication No. 2025-010082, Paragraphs

[0022] ~

[0024] of Japanese Patent Application Publication No. 2025-027484, Paragraphs

[0299] of Japanese Patent Application Publication No. 7611887, Paragraphs

[0190] ~

[0198] The subjects described in paragraphs

[0285] to

[0290] of Japanese Patent No. 7614747 and paragraphs

[0201] to

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

[0850] Specific examples of the matte salt of the present invention can be listed as any combination of the aforementioned anions and cations.

[0851] The matte salt of the present invention can be synthesized, for example, using the same method as that described in Japanese Patent Application Publication No. 2020-91312 for onium salts, but is not limited thereto.

[0852] The structural features of the sulfonium salt of the present invention can be exemplified by a triarylsulfonium cation having an acid-labile group having a nitro group and an aromatic carboxylic acid anion 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 which may also have substituents. The substituent of the aromatic carboxylic acid anion is preferably an iodine atom. Aromatic carboxylic acid anions containing iodine atoms exhibit very high EUV absorption, especially in EUV lithography at a wavelength of 13.5 nm, thus generating secondary electrons from the iodine atom during exposure. Furthermore, the iodine atom has appropriate solubility-inhibiting ability, especially in suppressing pattern collapse in unexposed areas with alkaline developers. It is known that the nitro group of the aromatic ring bonded to the sulfonium cation is a strong electron-withdrawing group. Therefore, it is believed that the energy level of the lowest unoccupied molecular orbital (LOMO) in frontier molecular orbital theory will be lowered. Thus, it becomes easier to accept secondary electrons generated from the iodine atom in the anion and promote the decomposition of the cation, thereby efficiently generating acid. Furthermore, since the nitro group has a resonance structure with a positive charge on its nitrogen atom and a negative charge on its oxygen atom, it is expected that the negative charge on the oxygen atom will interact with the protons of the generated acid and function as an acid diffusion inhibitor group. Because of this charge, it also has a high affinity for alkaline developers, and the residues after cation decomposition can be efficiently removed relative to the alkaline developer, thus reducing the risk of development defects in the exposed areas.

[0853] The aforementioned acid-instable groups with tertiary / secondary ether, tertiary / secondary ester, tertiary / secondary carbonate, or acetal structures undergo deprotection reactions due to acids generated during exposure, producing corresponding phenols or carboxylic acids. The structure transforms from lipophilic to hydrophilic, thereby improving the contrast between the exposed and unexposed areas. Furthermore, the nitro group, by bonding to a carbon atom adjacent to a phenolic hydroxyl group formed during deprotection or to a carboxyl group, increases the acidity of the phenol or carboxylic acid due to the electron-withdrawing property of the nitro group. When the exposed area where the deprotection reaction has occurred is developed with an alkaline developer, the increased acidity of the phenol improves its solubility in the alkaline developer, thereby suppressing development residue. Additionally, fluorine atoms or substituents containing fluorine atoms are preferable to the other aromatic rings in the triarylsulfonium cation. It is believed that the strong electron-withdrawing property of fluorine atoms or substituents containing fluorine atoms lowers the energy level of the lowest unoccupied molecular orbital in the frontier molecular orbital theory of the triarylsulfonium cation. Therefore, it readily accepts secondary electrons generated from iodine atoms in both cations and anions, promoting the decomposition of cations and efficiently generating acids. Furthermore, when the anion also possesses acid-instable groups, the deprotection reaction of these unstable groups in the generated acid proceeds, leading to anticipated improvements in contrast and increased sensitivity due to further changes in solubility. In the exposed portion of a positive resist, the higher the affinity for alkaline developers, the lower the risk of development defects. Moreover, the matte salt of this invention contains aromatic carboxylic acid anions, thus exhibiting strong alkalinity and effectively capturing strong acids generated by photoacid generators. Through these synergistic effects, the matte salt of this invention can form patterns with high dissolution contrast, excellent lithographic performance (LWR for line patterns, CDU for hole patterns), and strong resistance to pattern collapse, making it suitable as a material for positive resist compositions.

[0854] The matte salt of the present invention can be ideally used as a quencher. Furthermore, in the present invention, the quencher is a material used to prevent the strong acid generated from the photoacid generator from diffusing into the unexposed area and to form a desired pattern by capturing it. The photoacid generator is a compound that generates a strong acid due to high-energy radiation; a strong acid is defined as a compound with sufficient acidity to induce a deprotection reaction of the unstable acid groups. The aforementioned aromatic carboxylic acids, when the unstable acid groups are tertiary esters or tertiary ethers, do not possess sufficient acidity to induce a deprotection reaction. Therefore, as described later, in order to induce a deprotection reaction of the unstable acid groups, it is effective to add a photoacid generator that generates an α-fluorinated sulfonic acid, imide acid, or methylated acid that produces a strong acid at the α-position. Furthermore, the photoacid generator that generates an α-fluorinated sulfonic acid, imide acid, or methylated acid can be additive or polymerically bonded to a base polymer.

[0855] When a sulfonate salt that produces the aforementioned aromatic carboxylic acid and a photoacid generator that produces a perfluoroalkyl sulfonic acid are mixed and then exposed to light, aromatic carboxylic acids and perfluoroalkyl sulfonic acids will be produced. Since the photoacid generator does not completely decompose, undecomposed photoacid generators will remain nearby. In this case, if the sulfonate salt that produces aromatic carboxylic acids and the perfluoroalkyl sulfonic acid coexist, initially the perfluoroalkyl sulfonic acid will undergo ion exchange with the sulfonate salt that produces aromatic carboxylic acids, producing a perfluoroalkyl sulfonate sulfonate and releasing the aromatic carboxylic acid. This is because perfluoroalkyl sulfonates, which have high acid strength, are more stable. On the other hand, even if a perfluoroalkyl sulfonate sulfonate and an aromatic carboxylic acid coexist, ion exchange will not occur. Not only perfluoroalkyl sulfonic acids can cause ion exchange, but aromatic sulfonic acids, alkyl sulfonic acids, imide acids, methylated acids, etc., which have higher acid strength than the aromatic carboxylic acids produced from the sulfonate salt of this invention, will also undergo the same ion exchange.

[0856] [Chemical amplification resist composition]

[0857] [(A) Quenching agent]

[0858] The chemically amplified resist composition of the present invention contains a quencher composed of a sulfonium salt represented by formula (1) as an essential component.

[0859] In the chemically amplified resist composition of the present invention, the content of (A) quencher relative to 80 parts by weight of the base polymer described later is preferably 0.1 to 40 parts by weight, and more preferably 0.5 to 30 parts by weight. If the content of (A) quencher is within the aforementioned range, the sensitivity and resolution are good, and there is no concern about the generation of foreign matter after development or stripping of the resist film, which is therefore ideal. (A) Quencher can be used alone or in combination of two or more types.

[0860] [(B) Basic Polymer]

[0861] The chemically amplified resist composition of the present invention may also contain a base polymer as component (B). The base polymer (B) is preferably a repeating unit containing an acid-indestructible group. The aforementioned repeating unit containing an acid-indestructible group may be used alone or in combination of two or more.

[0862] Specific examples of the repeating units containing acid-instable groups mentioned above can be listed as follows: the repeating unit represented by the following formula (a1) (hereinafter also referred to as repeating unit a1) and the repeating unit represented by the following formula (a2) (hereinafter also referred to as repeating unit a2).

[0863] [Chemistry 339]

[0864]

[0865] In equations (a1) and (a2), R AEach can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0866] In equation (a1), X 1 Single bond, 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, or a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom. X 11 It is a saturated alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0867] In equation (a2), X 2 For single bonds, *-C(=O)-O- or *-C(=O)-N(H)-X 11 -. * indicates an atomic bond with a carbon atom 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 oxy 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 oxy group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxy 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.

[0868] 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.

[0869] For representativeness, specific examples of the aforementioned acid-instable groups can be exemplified by any of the formulas (AL-5) to (AL-7).

[0870] [Transformation 340]

[0871]

[0872] In the formula, the dashed lines represent atomic bonds.

[0873] In equations (AL-5) and (AL-6), R L21 and R L22Each 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.

[0874] In formula (AL-5), a2 is an integer from 0 to 10, preferably 1, 2, 3, 4 or 5.

[0875] In equation (AL-6), R L23 and R L24 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... L22 R L23 and R L24 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 atoms and oxygen atoms. The aforementioned rings are preferably rings with 4 to 16 carbon atoms, and alicyclic rings are particularly preferred.

[0876] In equation (AL-7), R L25 R L26 and R L27 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... L25 R L26 and R L27 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.

[0877] 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 an acid leaving reaction.

[0878] 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.

[0879] [Chemistry 341]

[0880]

[0881] [Chemistry 342]

[0882]

[0883] [Chemistry 343]

[0884]

[0885] [Chemistry 344]

[0886]

[0887] [Chemistry 345]

[0888]

[0889] [Chemistry 346]

[0890]

[0891] [Chemistry 347]

[0892]

[0893] 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.

[0894] [Chemistry 348]

[0895]

[0896] [Chemistry 349]

[0897]

[0898] [Chemical 350]

[0899]

[0900] Other specific examples of the aforementioned repeating units containing acid-labile groups can be listed as repeating units represented by the following formula (a3) ​​(hereinafter also referred to as repeating unit a3).

[0901] [Chemistry 351]

[0902]

[0903] 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, it is preferable to have a benzene ring with b1 = 0. 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 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more desirable.

[0904] In equation (a3), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R A It is preferable to have a hydrogen atom or a methyl group, with a hydrogen atom being better.

[0905] In equation (a3), X 3 The bonds are single bonds, *-C(=O)-O-, or *-C(=O)-N(H)-. * indicates an atomic bond with a carbon atom in the main chain. Among these, single bonds and *-C(=O)-O- are preferred, with single bonds being even better.

[0906] 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 group formed after the reaction, a single bond or a carbonyl group is even better.

[0907] 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.

[0908] 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.

[0909] 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.

[0910] 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 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxycarbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group or -N(R) group with 1 to 20 carbon atoms. 24A (R) 24B R24A and 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 oxy group, hydrocarbon oxycarbonyl 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.

[0911] 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.

[0912] 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.

[0913] [Chemistry 352]

[0914]

[0915] [Chemistry 353]

[0916]

[0917] [Chemistry 354]

[0918]

[0919] [Chemical Formula 355]

[0920]

[0921] [Chemical Formula 356]

[0922]

[0923] [Chemical Formula 357]

[0924]

[0925] [Chemical Formula 358]

[0926]

[0927] [Chemical Formula 359]

[0928]

[0929] [Chemical Formula 360]

[0930]

[0931] [Chemical Formula 361]

[0932]

[0933] [Chemical Formula 362]

[0934]

[0935] [Chemical Formula 363]

[0936]

[0937] [Chemical Formula 364]

[0938]

[0939] [Chemical Formula 365]

[0940]

[0941] [Chemical Formula 366]

[0942]

[0943] [Chemical Formula 367]

[0944]

[0945] [Chemical Formula 368]

[0946]

[0947] [Chemistry 369]

[0948]

[0949] [Transformation 370]

[0950]

[0951] [Chemistry 371]

[0952]

[0953] [Chemistry 372]

[0954]

[0955] [Chemistry 373]

[0956]

[0957] [Chemistry 374]

[0958]

[0959] [Chemistry 375]

[0960]

[0961] [Chemistry 376]

[0962]

[0963] [Chemistry 377]

[0964]

[0965] [Chemistry 378]

[0966]

[0967] [Chemistry 379]

[0968]

[0969] [Chemistry 380]

[0970]

[0971] [Chemistry 381]

[0972]

[0973] [Chemistry 382]

[0974]

[0975] [Chemistry 383]

[0976]

[0977] [Chem. 384]

[0978]

[0979] [Chem.385]

[0980]

[0981] [Chemistry 386]

[0982]

[0983] [Chemistry 387]

[0984]

[0985] [Chem.388]

[0986]

[0987] [Chemistry 389]

[0988]

[0989] [Chemistry 390]

[0990]

[0991] [Chemistry 391]

[0992]

[0993] [Chemistry 392]

[0994]

[0995] [Chemistry 393]

[0996]

[0997] [Chem. 394]

[0998]

[0999] [Chemistry 395]

[1000]

[1001] [Chemistry 396]

[1002]

[1003] [Chemistry 397]

[1004]

[1005] [Chemistry 398]

[1006]

[1007] [Chemistry 399]

[1008]

[1009] [Chemical 400]

[1010]

[1011] [Chemical Engineering 401]

[1012]

[1013] 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).

[1014] [Chemical 402]

[1015]

[1016] 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 Single bond, 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, or a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom. 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 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom 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, carbonyl group, carboxyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulcinolone ring, and carboxylic anhydride (-C(=O)-OC(=O)-). R 32It 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 oxy 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 oxy group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxy 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.

[1017] 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.

[1018] [Chemical 403]

[1019]

[1020] [Chemical 404]

[1021]

[1022] [Chemical 405]

[1023]

[1024] [Chemical 406]

[1025]

[1026] [Chemical 407]

[1027]

[1028] [Chemical 408]

[1029]

[1030] [Chemical 409]

[1031]

[1032] [Chemical 410]

[1033]

[1034] [Chemistry 411]

[1035]

[1036] [Chemistry 412]

[1037]

[1038] [Chemistry 413]

[1039]

[1040] [Chemistry 414]

[1041]

[1042] [Chemical 415]

[1043]

[1044] [Chemistry 416]

[1045]

[1046] [Chemistry 417]

[1047]

[1048] [Chemistry 418]

[1049]

[1050] [Chemistry 419]

[1051]

[1052] [Chem.420]

[1053]

[1054] [Chemistry 421]

[1055]

[1056] [Chemistry 422]

[1057]

[1058] 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.

[1059] [Chemistry 423]

[1060]

[1061] [Chemistry 424]

[1062]

[1063] [Chemical 425]

[1064]

[1065] [Chemistry 426]

[1066]

[1067] [Chemistry 427]

[1068]

[1069] 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.

[1070] The aforementioned polymer may also contain at least one of the repeating units represented by formula (c1) (hereinafter also referred to as repeating unit c1), the repeating unit represented by formula (c2) (hereinafter also referred to as repeating unit c2), the repeating unit represented by formula (c3) (hereinafter also referred to as repeating unit c3), the repeating unit represented by formula (c4) (hereinafter also referred to as repeating unit c4), and the repeating unit represented by formula (c5) (hereinafter also referred to as repeating unit c5).

[1071] [Chemistry 428]

[1072]

[1073] In equations (c1) to (c5), R A Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It is a single bond or may have substituents. Z 2 For single bonds, **-C(=O)-OZ 21 -、**-C(=O)-N(H)-Z 21 -or**-OZ 21 -. Z 21 It is a divalent group consisting of an aliphatic hydrocarbon group, a phenylene group, or a combination thereof, having 1 to 6 carbon atoms, and may also contain a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 3 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. 4 It is a single bond, or an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may also contain a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 5 Each can be a single bond, or a phenylene group with substituents, or a naphthylene group with substituents, or *-C(=O)-OZ. 51 -or *-C(=O)-N(R)-Z 51 -. Z 51It is an aliphatic hydrocarbon group, phenylene, or naphthylene with 1 to 10 carbon atoms, and the aliphatic hydrocarbon group may also contain a halogen atom, a hydroxyl group, an ether bond, an ester bond, or an lactone ring. R is a hydrogen atom, or may also contain a hydrocarbon group with 1 to 10 carbon atoms.

[1074] Z 6 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. 7 Each is independently a single bond, ***-Z 71 -C(=O)-O-、***-C(=O)-N(R)-Z 71 -or ***-OZ 71 -. Z 71 It can also be a hydrocarbon group with 1 to 20 carbon atoms and containing heteroatoms. R is the same as described above. Z 8 Each is independently a single bond, ****-Z 81 -C(=O)-O-、****-C(=O)-N(R)-Z 81 -or ****-OZ 81 -. Z 81 It can also be a hydrocarbon group with 1 to 20 carbon atoms and containing heteroatoms. R is the same as described above. Z 9 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, *-C(=O)-OZ 91 -、*-C(=O)-N(R)-Z 91 -or *-OZ 91 -. Z 91 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group. R is the same as above. * indicates an atomic bond with a carbon atom in the main chain. ** indicates a bond with Z. 1 The atomic bonds. *** indicates the relationship between Z and 6 Atomic bonds. **** represents the bond between Z and Z. 7 Atomic bonds.

[1075] Z 21 Z 51 and Z 91The 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.

[1076] Z 71 and Z 81 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.

[1077] [Chemistry 429]

[1078]

[1079] In the formula, the dashed lines represent atomic bonds.

[1080] In equation (c1), R 41 and R 42 Each of the above-mentioned hydrocarbon groups can be independently a hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 20 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclohexenyl; aryl groups with 6 to 20 carbon atoms such as phenyl, naphthyl, and thiophene; aralkyl groups with 7 to 20 carbon atoms such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them, which are preferably aryl groups. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can 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 can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1081] Also, R 41 and R 42 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. Specific examples of the aforementioned rings can be shown in the following formulas, etc.

[1082] [Chemistry 430]

[1083]

[1084] In the formula, the dashed line represents Z. 4 Atomic bonds.

[1085] Specific examples of the cation in repeating unit c1 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1086] [Chemistry 431]

[1087]

[1088] [Chemistry 432]

[1089]

[1090] [Chemistry 433]

[1091]

[1092] [Chemistry 434]

[1093]

[1094] [Chemistry 435]

[1095]

[1096] [Chemistry 436]

[1097]

[1098] [Chemistry 437]

[1099]

[1100] [Chemistry 438]

[1101]

[1102] [Chemistry 439]

[1103]

[1104] [Chemistry 440]

[1105]

[1106] In equation (c1), M - These are non-nucleophilic relative ions. The aforementioned non-nucleophilic relative ions are preferably halide ions, sulfonic acid anions, imide acid anions, and methylated acid anions. Specific examples of the aforementioned halide ions include chloride ions and bromide ions. Specific examples of the aforementioned sulfonic acid anions (sulfonate ions) include trifluoromethanesulfonate ions, 1,1,1-trifluoroethanesulfonate ions, nonafluorobutanesulfonate ions, and other fluoroalkyl sulfonate ions; toluenesulfonate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, 1,2,3,4,5-pentafluorobenzenesulfonate ions, and other aryl sulfonate ions; methanesulfonate ions, butanesulfonate ions, and other alkyl sulfonate ions, etc. Specific examples of the aforementioned imide acid anions (imide ions) include bis(trifluoromethylsulfonyl)imide ions, bis(perfluoroethylsulfonyl)imide ions, bis(perfluorobutylsulfonyl)imide ions, etc. Specific examples of the aforementioned methylated acid anions (methylated ions) include: tris(trifluoromethylsulfonyl) methylated ion, tris(perfluoroethylsulfonyl) methylated ion, etc.

[1107] Other examples of the aforementioned non-nucleophilic relative ions can be listed as anions represented by any of the following formulas (c1-1) to (c1-4).

[1108] [Chemistry 441]

[1109]

[1110] In equation (c1-1), R fa The hydrocarbon group consists of fluorine atoms, or may contain heteroatoms, and has 1 to 40 carbon atoms. 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 (c1-1-1). 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.

[1111] The anion represented by formula (c1-1) should preferably be represented by the following formula (c1-1-1).

[1112] [Chemistry 442]

[1113]

[1114] In equation (c1-1-1), Q 1 and Q 2 Each of the following components 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 components is preferably trifluoromethyl. m can be 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.

[1115] 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-ethylenebridged-9,10-dihydroanthrayl and 6,13-ethylenebridged-6,13-dihydropentaphenyl; hydrocarbon groups with 17 to 40 carbons having a steroid skeleton; and groups obtained by combining them.

[1116] 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.

[1117] In equation (c1-1-1), L a1 The bonds can be single bonds, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, or carbamate bonds. From a synthetic point of view, ether bonds or ester bonds are preferred, with ester bonds being even better.

[1118] Specific examples of anions represented by equation (c1-1) are shown below, but are not limited to these. Additionally, in the following equation, Q... 1 As mentioned above, Ac is an acetyl group.

[1119] [Chemistry 443]

[1120]

[1121] [Chemistry 444]

[1122]

[1123] [Chemistry 445]

[1124]

[1125] [Chemistry 446]

[1126]

[1127] [Chemistry 447]

[1128]

[1129] [Chemistry 448]

[1130]

[1131] [Chemistry 449]

[1132]

[1133] [Chemistry 450]

[1134]

[1135] [Chemistry 451]

[1136]

[1137] [Chemistry 452]

[1138]

[1139] [Chemistry 453]

[1140]

[1141] [Chemistry 454]

[1142]

[1143] [Chemistry 455]

[1144]

[1145] Other specific examples of anions represented by formula (c1-1) 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.

[1146] In equation (c1-2), 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 (c1-1-1). 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.

[1147] In equation (c1-3), 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 (c1-1-1). 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.

[1148] In equation (c1-4), 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 (c1-1-1). 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.

[1149] Specific examples of anions represented by formula (c1-4) are listed below, but are not limited to these.

[1150] [Chemistry 456]

[1151]

[1152] [Chemistry 457]

[1153]

[1154] [Chemistry 458]

[1155]

[1156] Other specific examples of anions represented by formula (c1-4) can be listed, such as those described in paragraphs

[0050] to

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

[1157] The examples of the aforementioned non-nucleophilic relative ions can be further illustrated by anions having aromatic rings substituted with iodine or bromine atoms. Specific examples of such anions can be exemplified by those represented by the following formula (c1-5).

[1158] [Chemistry 459]

[1159]

[1160] In equation (c1-5), x1 is 1, 2, or 3. y1 is 1, 2, 3, 4, or 5. z1 is 0, 1, 2, or 3. However, 1 ≤ y1 + z1 ≤ 5. y1 should preferably be 1, 2, or 3, with 2 or 3 being even better. z1 should preferably be 0, 1, or 2.

[1161] In equation (c1-5), X BI It consists of iodine or bromine atoms. When x1 and / or y1 are 2 or more, each X BI They can be the same or different.

[1162] In equation (c1-5), L 11 It can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond, carbamate bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms, and part of the -CH2- of the hydrocarbon group can also be replaced by an ether bond or ester bond. The aforementioned saturated hydrocarbon group can be any of the following: linear, branched, or cyclic.

[1163] In equation (c1-5), L 12 When x1 is 1, it is a single bond or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms. When x1 is 2 or 3, it is a (x1+1) valence hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms.

[1164] 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-ethene-bridged-9,10-dihydroanthracenediyl and 6,13-ethene-bridged-6,13-dihydropentaphenyl; and groups obtained by combining them, etc.] 12 The (x1+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.

[1165] Furthermore, some or all of the hydrogen atoms in the aforementioned alkylene groups and (x1+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 (x1+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.

[1166] In equation (c1-5), L 13 It can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond.

[1167] In equation (c1-5), R fe It can be a hydroxyl group, carboxyl group, fluorine atom, chlorine atom, bromine atom, amino group, hydrocarbon group with 1 to 20 carbon atoms, hydrocarbon oxy group with 1 to 20 carbon atoms, hydrocarbon sulfonyl 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 oxycarbonyl group, hydrocarbon carbonyloxy group, and hydrocarbon sulfonyloxy group may also contain at least one selected from fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, amino group, ester bond, and ether bond. feA and R feB Each 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 group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms. R feD It 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 hydrocarbon oxy group with 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group with 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl oxy group with 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group can be saturated or unsaturated, and can be straight-chain, branched, or cyclic. The aforementioned hydrocarbon group, hydrocarbon oxy group, hydrocarbon carbonyl group, hydrocarbon oxycarbonyl group, hydrocarbon carbonyl oxy group, and hydrocarbon sulfonyl oxy group can be straight-chain, branched, or cyclic. When x1 and / or z1 are 2 or more, each R fe They can be the same or different.

[1168] 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.

[1169] In equation (c1-5), Rf 11 ~Rf 14 Each 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. Rf 13 and Rf 14 All of them are fluorine atoms, which is of excellent quality.

[1170] Specific examples of anions represented by equation (c1-5) are shown below, but are not limited to these. Additionally, in the following equation, X... BI Same as above.

[1171] [Chemistry 460]

[1172]

[1173] [Chemistry 461]

[1174]

[1175] [Chemistry 462]

[1176]

[1177] [Chemistry 463]

[1178]

[1179] [Chemistry 464]

[1180]

[1181] [Chemistry 465]

[1182]

[1183] [Chemistry 466]

[1184]

[1185] [Chemistry 467]

[1186]

[1187] [Chemistry 468]

[1188]

[1189] [Chemistry 469]

[1190]

[1191] [Chemistry 470]

[1192]

[1193] [Chemistry 471]

[1194]

[1195] [Chemistry 472]

[1196]

[1197] [Chemistry 473]

[1198]

[1199] [Chemistry 474]

[1200]

[1201] [Chemistry 475]

[1202]

[1203] [Chemistry 476]

[1204]

[1205] [Chemistry 477]

[1206]

[1207] [Chemistry 478]

[1208]

[1209] [Chemistry 479]

[1210]

[1211] [Chemistry 480]

[1212]

[1213] [Chemistry 481]

[1214]

[1215] [Chemistry 482]

[1216]

[1217] [Chemistry 483]

[1218]

[1219] M -Other examples of anions represented include: paragraphs

[0076] and

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

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

[0253] to

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

[0044] to

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

[0205] to

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

[0170] to

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

[0026] to

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

[0022] to

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

[0026] to

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

[0028] to

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

[0026] to

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

[0028] to

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

[0028] to

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

[0031] to

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

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

[0023] ~

[0025] , paragraphs

[0026] ~

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

[0020] ~

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

[0140] ~

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

[0023] ~

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

[0028] ~

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

[0030] ~

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

[0028] ~

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

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

[0030] ~

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

[0025] ~

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

[0033] ~

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

[0021] ~

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

[0169] ~

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

[0178] ~

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

[0040] ~

[0143] ,The paragraphs

[0030] to

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

[0157] to

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

[0227] to

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

[0253] to

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

[0309] to

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

[1220] Other examples of the aforementioned non-nucleophilic relative ions can be further listed as follows: 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. 609 The fluorine-free aromatic sulfonic acid anions and alkyl sulfonic acid anions described in paragraphs

[0034] to

[0037] of Japanese Patent Application Publication No. 0585, 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.

[1221] The aforementioned non-nucleophilic relative ions may also be the anions of disulfonic acid described in Japanese Patent Application Publication No. 2015-206932, the anions of sulfonic acid on one side and sulfonamide or sulfonylimide on the other side as described in International Publication No. 2020 / 158366, and the anions of sulfonic acid on one side and carboxylic acid on the other side as described in Japanese Patent Application Publication No. 2015-24989.

[1222] In equations (c2) and (c3), d1 and d2 are independently 0, 1, 2 or 3, and should preferably be 1.

[1223] In equation (c4), e1 is 0 or 1. e2 is 0, 1, 2, 3 or 4. e3 is 0, 1, 2, 3 or 4. However, when e1 is 0, 0 ≤ e2 + e3 ≤ 4, and when e1 is 1, 0 ≤ e2 + e3 ≤ 6.

[1224] In equations (c2), (c3) and (c4), L 1 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.

[1225] In equation (c2), Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among them, Rf 1 and Rf 2 To increase the acid strength of the produced acid, it is preferable that all atoms be fluorine 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. Among them, Rf is used to improve solvent solubility. 3 and Rf 4 At least one of them should preferably be trifluoromethyl.

[1226] In equation (c3), Rf 5 and Rf 6 Each can be independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. However, all Rf 5 and Rf 6 They cannot all be hydrogen atoms simultaneously. Among them, Rf is used to improve solvent solubility. 5 and Rf 6 At least one of them should preferably be trifluoromethyl.

[1227] In equation (c4), Rf 7 It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated alkyl thio group having 1 to 6 carbon atoms. Rf 7 It is preferable to have a fluorine atom, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, or difluoromethylthio, with fluorine, trifluoromethyl, or trifluoromethoxy being more preferred. When e2 is 2, 3, or 4, each Rf 7 They can be the same or different.

[1228] In equation (c4), R 43 It is a halogen atom other than fluorine, or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated in the description of formula (1) as R. 1and R 2 Examples of hydrocarbon groups are similar, but not limited to these. Also, when e3 is 2, 3, or 4, each R... 43 They can be the same or different.

[1229] Furthermore, when e3 is 2, 3, or 4, multiple R... 43 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.

[1230] Specific examples of the anion in repeating unit c2 can be listed below, but are not limited to these. Additionally, in the following formula, R... A As mentioned above, Me is a methyl group.

[1231] [Chemistry 484]

[1232]

[1233] [Chemistry 485]

[1234]

[1235] [Chemistry 486]

[1236]

[1237] [Chemistry 487]

[1238]

[1239] [Chemistry 488]

[1240]

[1241] [Chemistry 489]

[1242]

[1243] [Chemistry 490]

[1244]

[1245] [Chemistry 491]

[1246]

[1247] [Chemistry 492]

[1248]

[1249] [Chemistry 493]

[1250]

[1251] [Chemistry 494]

[1252]

[1253] [Chemistry 495]

[1254]

[1255] [Chemistry 496]

[1256]

[1257] Other specific examples of repeating unit c2 can be listed as follows: paragraphs

[0043] ~

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

[0067] ~

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

[0057] ~

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

[0020] ~

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

[0067] to

[0070] of Japanese Patent No. 0703, the paragraphs

[0075] to

[0084] of Japanese Patent No. 7520258, the paragraphs

[0032] to

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

[0385] to

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

[0062] to

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

[1258] Specific examples of the anion in repeating unit c3 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1259] [Chemistry 497]

[1260]

[1261] [Chemistry 498]

[1262]

[1263] [Chemistry 499]

[1264]

[1265] [Chemical 500]

[1266]

[1267] [Chemical 501]

[1268]

[1269] [Chemical 502]

[1270]

[1271] [Chemical 503]

[1272]

[1273] [Chemical 504]

[1274]

[1275] [Chemical 505]

[1276]

[1277] [Chemical 506]

[1278]

[1279] [Chem. 507]

[1280]

[1281] Specific examples of the anion in repeating unit c4 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1282] [Chemical 508]

[1283]

[1284] [Chemical 509]

[1285]

[1286] [Chem.510]

[1287]

[1288] [Chem.511]

[1289]

[1290] [Chem.512]

[1291]

[1292] [Chem.513]

[1293]

[1294] [Chem.514]

[1295]

[1296] [Chem.515]

[1297]

[1298] [Chem.516]

[1299]

[1300] [Chem.517]

[1301]

[1302] [Chem.518]

[1303]

[1304] [Chem.519]

[1305]

[1306] [Chem.520]

[1307]

[1308] [Chem.521]

[1309]

[1310] [Chem.522]

[1311]

[1312] [Chem.523]

[1313]

[1314] [Chem.524]

[1315]

[1316] Other specific examples of the anion of repeating unit c4 can be listed as follows: paragraphs

[0023] to

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

[0419] to

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

[1317] Specific examples of the anion in repeating unit c5 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1318] [Chem.525]

[1319]

[1320] In equations (c2) to (c5), A + The cation is a sulfonium cation. Examples of the aforementioned sulfonium cations include: sulfonium cations, monium cations, ammonium cations, etc., and sulfonium cations and monium cations are preferred. Specific examples of the aforementioned sulfonium cations include: specific examples of cations that are sulfonium salts represented by formula (1), 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, and those described in paragraphs

[0035] to

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

[1321] Furthermore, the aforementioned sulfonium cation should also be a sulfonium cation represented by the following formula (sulfo-1).

[1322] [Chem.526]

[1323]

[1324] In formula (sulfo-1), f1 is 0 or 1. When f1 is 0, it is a benzene ring; when f1 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with f1 = 0. f2 is 0 or 1. When f2 is 0, it is a benzene ring; when f2 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with f2 = 0. f3 is 0 or 1. When f3 is 0, it is a benzene ring; when f3 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with f3 = 0.

[1325] In formula (sulfo-1), f4 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption of EUV, but there are concerns that it will become less solvent-soluble and precipitate in the resist composition. Therefore, f4 should preferably be 0, 1, 2, or 3, with 0, 1, or 2 being more preferred.

[1326] In formula (sulfo-1), f5 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, f5 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred. f is 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, f6 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred. f7 is 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, f7 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred.

[1327] In formula (sulfo-1), f8 is 0, 1, or 2. From the perspective of raw material availability, f8 should preferably be 0 or 1. f9 is 0, 1, or 2. From the perspective of raw material availability, f9 should preferably be 0 or 1. f10 is 0, 1, or 2. From the perspective of raw material availability, f10 should preferably be 0 or 1.

[1328] In formula (sulfo-1), f11 is 0 or 1. When f11 is 0, it is a benzene ring; when f11 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with f11 of 0.

[1329] In formula (sulfo-1), f12 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption of EUV, but there are concerns that it will become less solvent-soluble and precipitate in the resist composition. Therefore, f12 should preferably be 0, 1, 2, or 3, with 0, 1, or 2 being more preferred.

[1330] In formula (sulfo-1), f13 is 0, 1, or 2. From the perspective of raw material availability, f13 is preferably 0 or 1. f14 is 0, 1, or 2. From a synthetic perspective, f14 is preferably 0 or 1.

[1331] However, when f1 is 0, 0 ≤ f6 + f9 ≤ 4; when f1 is 1, 0 ≤ f6 + f9 ≤ 6. When f2 is 0, 0 ≤ f7 + f10 ≤ 4; when f2 is 1, 0 ≤ f7 + f10 ≤ 6. When f3 is 0, 1 ≤ f4 + f5 + f8 + f14 ≤ 4; when f3 is 1, 1 ≤ f4 + f5 + f8 + f14 ≤ 6. When f11 is 0, 0 ≤ f12 + f13 ≤ 4; when f11 is 1, 0 ≤ f12 + f13 ≤ 6. Also, f4 + f12 ≥ 1.

[1332] 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 f5 is 2, 3, or 4, each R... F1 They can be the same or different. When f6 is 2, 3, 4, 5 or 6, each R... F2They can be the same or different. When f7 is 2, 3, 4, 5 or 6, each R... F3 They can be the same or different.

[1333] In formula (sulfo-1), R ct1 ~R ct4 The hydroxyl 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 that may contain heteroatoms, a hydrocarbon oxygen 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. 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 listed and illustrated in the description of formula (1) as R. 1 and R 2 The same example applies to the hydrocarbon group. Furthermore, some or all of the hydrogen atoms in the hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon sulfide group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. 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, it may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1334] Also, when f8 is 2, there are 2 Rs. ct1 They can be the same or different, and there are 2 Rs. ct1 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When f9 is 2, there are 2 R atoms. ct2 They can be the same or different, and there are 2 Rs. ct2 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When f10 is 2, there are 2 R atoms. ct3 They can be the same or different, and there are 2 Rs. ct3 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When f13 is 2, there are 2 R atoms. ct4 They can be the same or different, and there are 2 Rs. ct4They 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.

[1335] 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.

[1336] [Chem.527]

[1337]

[1338] In the formula, the dashed lines represent atomic bonds.

[1339] In formula (sulfo-1), L C and L D 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... C The bonds should ideally be single bonds, ether bonds, ester bonds, or sulfonate bonds, with ester bonds or sulfonate bonds being preferred. D It is preferable to have a single bond, ether bond, or ester bond, with a single bond being better.

[1340] In formula (sulfo-1), X L It is a single bond, or may contain heteroatoms, of carbon atoms ranging from 1 to 40. The aforementioned alkylene group can be linear, branched, or cyclic; specific examples include alkyldiyl, cyclic saturated alkylene groups, and arylene groups. Specific examples of the aforementioned heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms.

[1341] X L Examples of hydrocarbon groups containing 1 to 40 carbon atoms and also representing heteroatoms are shown below, but are not limited to these. Additionally, in the following formula, * indicates the combination with L... E and L F Atomic bonds.

[1342] [Chem.528]

[1343]

[1344] [Chem. 529]

[1345]

[1346] [Chem.530]

[1347]

[1348] [Chemistry 531]

[1349]

[1350] 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.

[1351] The sulfonium cation represented by formula (sulfo-1) should preferably be represented by the following formula (sulfo-1-1).

[1352] [Chemistry 532]

[1353]

[1354] In the formula, f4~f10, f12~f14, R F1 ~R F3 R ct1 ~R ct4 L C L D and X L Same as above.

[1355] The sulfonium cation represented by formula (sulfo-1-1) should preferably be represented by formula (sulfo-1-2).

[1356] [Chem.533]

[1357]

[1358] In the formula, f4~f10, R F1 ~R F3 and R ct1 ~R ct3 Same as above.

[1359] 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.

[1360] [Chemistry 534]

[1361]

[1362] [Chem.535]

[1363]

[1364] [Chemistry 536]

[1365]

[1366] [Chem.537]

[1367]

[1368] [Chem.538]

[1369]

[1370] [Chemistry 539]

[1371]

[1372] [Chemistry 540]

[1373]

[1374] [Chemistry 541]

[1375]

[1376] [Chemistry 542]

[1377]

[1378] [Chemistry 543]

[1379]

[1380] [Chemistry 544]

[1381]

[1382] [Chem.545]

[1383]

[1384] [Chemistry 546]

[1385]

[1386] [Chemistry 547]

[1387]

[1388] [Chem.548]

[1389]

[1390] [Chemical Formula 549]

[1391]

[1392] [Chemical Formula 550]

[1393]

[1394] [Chemical Formula 551]

[1395]

[1396] [Chemical Formula 552]

[1397]

[1398] [Chemical Formula 553]

[1399]

[1400] [Chemical Formula 554]

[1401]

[1402] [Chemical Formula 555]

[1403]

[1404] [Chemical Formula 556]

[1405]

[1406] [Chemical Formula 557]

[1407]

[1408] [Chemical Formula 558]

[1409]

[1410] [Chemical Formula 559]

[1411]

[1412] [Chemical Formula 560]

[1413]

[1414] [Chemical Formula 561]

[1415]

[1416] 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.

[1417] Specific examples of the aforementioned ammonium cations can be listed as those represented by the formula (am-1).

[1418] [Chem.562]

[1419]

[1420] In equation (am-1), R ct5 ~R ct8 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R ct5 and R ct6 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to. Specific examples of the aforementioned hydrocarbon groups can be listed and illustrated in the description of formula (1) as R. 1 and R 2 The same example represents hydrocarbon groups.

[1421] Specific examples of ammonium cations represented by formula (am-1) are listed below, but are not limited thereto.

[1422] [Chem.563]

[1423]

[1424] The specific structures of repeating units c1 to c5 can be listed as any combination of the aforementioned anions and cations.

[1425] Among the repeating units c1 to c5, considering the control of acid diffusion, repeating units c2 to c5 are preferable; considering the acid strength of the generated acid, repeating units c2, c4, and c5 are even better; and considering the solvent solubility, repeating unit c2 is even better.

[1426] The aforementioned polymer may also contain repeating units (hereinafter also referred to as repeating units d) with a structure in which hydroxyl groups are protected by acid-indestructible groups. If the repeating unit d has one or more hydroxyl groups protected, and the protecting group decomposes and generates hydroxyl groups due to the action of acid, there are no particular restrictions, and it is preferable to be represented by the following formula (d1).

[1427] [Chem.564]

[1428]

[1429] In equation (d1), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 51 It can also contain a (g+1) valence hydrocarbon group with 1 to 30 carbon atoms, which may also contain heteroatoms. R 52is an acid-labile group. g is 1, 2, 3 or 4.

[1430] In formula (d1), R 52 The acid-labile group represented by is not particularly limited as long as it is deprotected by the action of an acid to generate a hydroxyl group. R 52 The structure of is not particularly limited, and is preferably an acetal structure, a ketal structure, a hydrocarbyloxycarbonyl group, a hydrocarbyloxymethyl group represented by the following formula (d2), etc., and a hydrocarbyloxymethyl group represented by the following formula (d2) is particularly preferred.

[1431] [Chemical 565]

[1432]

[1433] In the formula, * denotes an atomic bond. R 53 is a hydrocarbyl group having 1 to 15 carbon atoms.

[1434] R 52 Specific examples of the acid-labile group represented by, the hydrocarbyloxymethyl group represented by formula (d2), and the repeating unit d include the same examples as those exemplified in the description of the repeating unit d described in Japanese Patent Laid-Open No. 2020-111564.

[1435] The aforementioned polymer may further contain a repeating unit e derived from indene, benzofuran, benzothiophene, acenaphthene, chromone, coumarin, norbornadiene, or a derivative thereof. Specific examples of the monomer that provides the repeating unit e include the following, but are not limited thereto.

[1436] [Chemical 566]

[1437]

[1438] The aforementioned polymer may further contain a repeating unit f derived from indane, vinylpyridine, or vinylcarbazole.

[1439] In the aforementioned polymer, the content ratios of repeating units a1, a2, a3, b1, b2, c1, c2, c3, c4, c5, d, e, and f should preferably be 0 ≤ a1 ≤ 0.8, 0 ≤ a2 ≤ 0.8, 0 ≤ a3 ≤ 0.6, 0 ≤ b1 ≤ 0.8, 0 ≤ b2 ≤ 0.5, 0 ≤ c1 ≤ 0.4, 0 ≤ c2 ≤ 0.4, 0 ≤ c3 ≤ 0.4, 0 ≤ c4 ≤ 0.4, and 0 ≤ c5 ≤ 0.4. The following are better values: 0≤d≤0.3, 0≤e≤0.3, and 0≤f≤0.3. However, 0≤a1≤0.7, 0≤a2≤0.7, 0≤a3≤0.5, 0≤b1≤0.7, 0≤b2≤0.4, 0≤c1≤0.3, 0≤c2≤0.3, 0≤c3≤0.3, 0≤c4≤0.3, 0≤c5≤0.3, 0≤d≤0.2, 0≤e≤0.2, and 0≤f≤0.2. But, a1+a2+a3+b1+b2+c1+c2+c3+c4+d+e+f≤1.0.

[1440] The weight-average molecular weight (Mw) of the aforementioned polymer is preferably between 1,000 and 500,000, and more preferably between 3,000 and 100,000. If Mw is within this range, sufficient etch resistance can be obtained, and there is no concern about a decrease in resolution due to the difference in dissolution rates before and after exposure. Furthermore, in this invention, Mw is a polystyrene equivalent value determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as solvents.

[1441] Regarding the aforementioned polymer molecular weight distribution (Mw / Mn), the influence of Mw / Mn tends to increase as the pattern becomes more regular and refined. Therefore, in order to obtain a resist composition that can be ideally used for fine pattern sizes, Mw / Mn should preferably be a narrow dispersion of 1.0 to 2.0. If it is within the aforementioned range, there will be fewer low-molecular-weight and high-molecular-weight polymers, and there will be no concern about foreign matter being observed on the pattern after exposure or the pattern shape deteriorating.

[1442] Examples of methods for synthesizing the aforementioned polymers include: polymerizing a monomer that provides the aforementioned repeating unit in an organic solvent by adding a free radical polymerization initiator and heating it.

[1443] 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.

[1444] 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 free radicals generated from the initiator may lead to polymerization and the formation of ultra-high molecular weight polymers during the standby 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%.

[1445] 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.

[1446] 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.

[1447] 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.

[1448] 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.

[1449] 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 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.

[1450] 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, and 1-ethoxy-2-propanol; and propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, and propylene glycol dimethyl ether. Ethers such as diethylene glycol dimethyl ether; esters such as PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as GBL; alcohols such as diacetone alcohol (DAA); high-boiling-point alcohol solvents such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, and 1,3-butanediol; and their mixed solvents.

[1451] In the aforementioned polymer solution, the polymer concentration is preferably 0.01~30% by mass, and more preferably 0.1~20% by mass.

[1452] The aforementioned reaction solutions and polymer solutions should be filtered. Filtering removes foreign matter and gels that could cause defects, effectively stabilizing the quality.

[1453] 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.

[1454] (B) The base polymer may be used alone or in combination with two or more polymers having different composition ratios, Mw and / or Mw / Mn. Furthermore, (B) in addition to the aforementioned polymers, the base polymer may also contain hydrides of ring-opening metathesis polymers, for which the polymers described in Japanese Patent Application Publication No. 2003-66612 may be used.

[1455] [(C) Organic solvent]

[1456] The chemically amplified resist composition of the present invention may also contain an organic solvent as component (C). There are no particular limitations on whether the organic solvent in (C) 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.

[1457] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, ethyl lactate, DAA, and their mixed solvents are particularly suitable for dissolving the base polymer of component (B).

[1458] In the chemically amplified resist composition of the present invention, the content of (C) organic solvent relative to 80 parts by mass of (B) base polymer is preferably 200-5000 parts by mass, and more preferably 400-3500 parts by mass. (C) organic solvent may be used alone or in combination of two or more.

[1459] [(D) Photoacid generator]

[1460] The chemically amplified resist composition of the present invention may also contain a photoacid generator as component (D). There are no particular limitations on whether the aforementioned photoacid generator is a compound that produces a strong acid upon irradiation with high-energy rays.

[1461] Ideal photoacid generators can be represented by formulas (2) or (3).

[1462] [Chem.567]

[1463]

[1464] In equation (2), 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 them can also bond to each other and form a ring together with the sulfur atoms they are bonded to. Specific examples of the aforementioned hydrocarbon groups can be listed and illustrated in the description of formula (1) as R. 1 and R 2 The same example represents hydrocarbon groups.

[1465] Specific examples of sulfonium salt cations represented by formula (2) can be listed, including those exemplified as sulfonium salt cations represented by formula (1), 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 those exemplified as sulfonium cations represented by formula (sulfo-1), etc., but are not limited thereto. Specific examples of ferrous salt cations represented by formula (3) can be listed, including those described in paragraph

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

[1466] In equations (2) and (3), Xa - It is an anion of a strong acid. Specific examples of the aforementioned strong acid anions can be listed as examples represented by any of formulas (c1-1) to (c1-5). Furthermore, fluorine-containing aromatic sulfonic acid anions described in paragraphs

[0029] to

[0034] of Japanese Patent No. 6648726, paragraphs

[0264] to

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

[0040] to

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

[1467] Furthermore, the photoacid generator of component (D) should also be represented by the following formula (4).

[1468] [Chem.568]

[1469]

[1470] In equation (4), 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 203Any two of them can also bond to each other and form a ring together with the sulfur atoms they are bonded to.

[1471] 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.]

[1472] 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.

[1473] In equation (4), 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.

[1474] In equation (4), 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.

[1475] The photoacid generator represented by formula (4) should preferably be represented by the following formula (4').

[1476] [Chem.569]

[1477]

[1478] In equation (4'), 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. 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 (c1-1-1). fa1 The same example represents hydrocarbon groups. x2 and y2 are independently 0, 1, 2, 3, 4 or 5, and z2 is 0, 1, 2, 3 or 4.

[1479] Specific examples of photoacid generators represented by formula (4) 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).

[1480] Among the aforementioned photoacid generators, those containing anions represented by formula (c1-1-1) or (c1-4) exhibit low acid diffusion and excellent solvent solubility, making them particularly ideal. Furthermore, those represented by formula (4') exhibit extremely low acid diffusion, making them particularly ideal.

[1481] 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 (B) 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.

[1482] [(E) Other quenching agents]

[1483] The chemically amplified resist composition of the present invention may also contain a quencher other than component (A) (hereinafter also referred to as other quenchers) as component (E).

[1484] (E) Other quenching agents can be listed as onion salts represented by formula (5) or (6).

[1485] [Chemistry 570]

[1486]

[1487] In equation (5), R q1It 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 (6), R q2 Hydrocarbon groups consisting of 1 to 40 carbon atoms, which may also contain heteroatoms.

[1488] 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.]

[1489] 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.

[1490] Specific examples of the anions of onium salts represented by equation (5) are listed below, but are not limited thereto.

[1491] [Chemistry 571]

[1492]

[1493] [Chemistry 572]

[1494]

[1495] [Chem.573]

[1496]

[1497] [Chemistry 574]

[1498]

[1499] [Chemistry 575]

[1500]

[1501] Other specific examples of the onium salt anion represented by formula (5) 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.

[1502] Specific examples of onium salt anions represented by equation (6) are listed below, but are not limited thereto.

[1503] [Chemistry 576]

[1504]

[1505] [Chemistry 577]

[1506]

[1507] [Chem.578]

[1508]

[1509] [Chemistry 579]

[1510]

[1511] [Chem.580]

[1512]

[1513] Other specific examples of onium salt anions represented by formula (6) 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.

[1514] In equations (5) and (6), Mq + The cation is a sulfonium cation. Examples of sulfonium cations include: sulfonium cations, monium cations, ammonium cations, etc. Specific examples of sulfonium cations include: examples of cations that are sulfonium salts represented by formula (1), 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 to these examples. Specific examples of monium cations include: those described in paragraph

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

[1515] Specific examples of onium salts represented by formulas (5) and (6) 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.

[1516] The onium salts represented by formulas (5) and (6) 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 formulas (5) and (6) function as quenchers when used in combination with onium salt-type photoacid generators that have conjugate bases of strong acids such as sulfonic acids as relative anions. That is, when onium salts that produce strong acids such as sulfonic acids are mixed with onium salts that produce weak acids such as carboxylic acids, if the strong acid generated from the photoacid generator due to high-energy ray irradiation collides with the unreacted onium salt with weak acid anions, the weak acid will be released through salt exchange, and onium salts with strong acid anions will be generated. During this process, strong acids are exchanged for weak acids with low catalytic activity, thus the acid appears to be deactivated and acid diffusion can be controlled.

[1517] Furthermore, (E) other quenching agents may be onium salts having sulfonium cations and benzene oxide anions within the same molecule as described in Japanese Patent No. 6848776, and onium salts having sulfonium cations and carboxylate anions within the same molecule as described in Japanese Patent No. 6583136, Japanese Patent Application Publication No. 2020-200311, and onium salts having uranium cations and carboxylate anions within the same molecule as described in Japanese Patent No. 6274755.

[1518] 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.

[1519] When the chemically amplified resist composition of the present invention contains an onium salt represented by formula (5) or (6) as another quencher in (E), its content relative to 80 parts by mass of the base polymer in (B) 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 the sensitivity will not be significantly reduced, which is ideal. The onium salt represented by formula (5) or (6) can be used alone or in combination of two or more.

[1520] The chemically amplified resist composition of the present invention may also contain nitrogen-containing compounds as (E) other quenchers. Specific examples of the aforementioned nitrogen-containing compounds include: first-, second-, or third-order amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103, and in particular, amine compounds having hydroxyl groups, ether bonds, ester bonds, lactone rings, cyano groups, or sulfonate bonds. Furthermore, compounds formed by protecting a first- or second-order 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, sulfonolactone ring, lactam ring, or sulfonamide ring coexisting with an acid-instable group, as described in Japanese Patent Publication No. 7615989, may also be cited.

[1521] 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.

[1522] When the chemically amplified resist composition of the present invention contains a nitrogen-containing compound as (E) other quenching agents, its content relative to 80 parts by mass of the (B) base polymer 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.

[1523] [(F) Surfactant]

[1524] The chemically amplified resist composition of the present invention may also contain a surfactant as component (F). The surfactant (F) 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.

[1525] 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).

[1526] [Chem.581]

[1527]

[1528] 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.

[1529] [Chem.582]

[1530]

[1531] In the formula, the dashed lines represent atomic bonds, which are partial structures derived from glycerol, trimethylolethane, trimethylolpropane, and neopentyl tertrol, respectively.

[1532] Among them, 1,4-butylene, 2,2-dimethyl-1,3-propylene, etc. are preferred.

[1533] 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 based on partially fluorinated oxyheterocyclic butane ring-opening polymer systems, please refer to the specification of US Patent No. 5,650,483, etc.

[1534] 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 as foreign substances that can be dissolved in alkaline aqueous solutions after exposure or post-exposure baking (PEB) and are 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.

[1535] Specific examples of such polymeric surfactants may include at least one of the following: repeating unit represented by formula (7A) (hereinafter also called repeating unit 7A), repeating unit represented by formula (7B) (hereinafter also called repeating unit 7B), repeating unit represented by formula (7C) (hereinafter also called repeating unit 7C), repeating unit represented by formula (7D) (hereinafter also called repeating unit 7D), and repeating unit represented by formula (7E) (hereinafter also called repeating unit 7E).

[1536] [Chem.583]

[1537]

[1538] In equations (7A) to (7E), 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 s4It is a (u+1) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 20 carbon atoms. u can be 1, 2, or 3. R s5 Each 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 it may also insert an ether bond or a carbonyl group between carbon bonds.

[1539] R s1 The 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.

[1540] 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.

[1541] 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 given as R. s1 In addition to those representing hydrocarbon groups, other examples include: undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc. R 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.

[1542] 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.

[1543] 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.

[1544] R sa The fluorinated hydrocarbon group represented is preferably saturated, and may be linear, branched, or cyclic. Specific examples thereof include groups 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.

[1545] Specific examples of the repeating units 7A to 7E include the groups shown below, but are not limited thereto. In addition, in the following formulae, R B is the same as described above.

[1546] [Chem. 584]

[1547]

[1548] [Chem. 585]

[1549]

[1550] [Chem. 586]

[1551]

[1552] [Chem. 587]

[1553]

[1554] [Chem. 588]

[1555]

[1556] [Chem. 589]

[1557]

[1558] The aforementioned polymeric surfactant may further contain other repeating units besides the repeating units 7A to 7E. 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 7A to 7E in all repeating units is preferably 20 mol% or more, more preferably 60 mol% or more, and even more preferably 100 mol%.

[1559] 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.

[1560] Methods for synthesizing the aforementioned polymeric surfactants include: polymerizing monomers containing unsaturated bonds, selected from at least one repeating unit 7A-7E and other repeating units as needed, in an organic solvent by adding a free radical initiator and heating. Examples of organic solvents used in polymerization include toluene, benzene, THF, diethyl ether, and dioxane. Examples of polymerization initiators include AIBN, 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2-azobis(2-methylpropionic acid), benzoyl peroxide, and lauroyl peroxide. 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.

[1561] 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%.

[1562] When the chemically amplified resist composition of the present invention contains surfactant (F), its content relative to 80 parts by weight of the base polymer (B) is preferably 0.1 to 50 parts by weight, and more preferably 0.5 to 10 parts by weight. If the content of surfactant (F) 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 (F) can be used alone or in combination of two or more.

[1563] [(G) Other ingredients]

[1564] 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 (G). 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 (B) is preferably 0 to 5 parts by mass, 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.

[1565] [Pattern Formation Method]

[1566] The pattern forming method of the present invention includes the following steps: forming a resist film on a substrate using the aforementioned chemically amplified resist composition, exposing the aforementioned resist film to high-energy rays, and developing the aforementioned exposed resist film using a developing solution.

[1567] 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.).

[1568] 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.

[1569] 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.

[1570] 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.

[1571] The aforementioned water-insoluble protective film, used to prevent leaching from the resist film and improve the hydrophobicity of the film surface, 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. Materials can also be prepared by dissolving the aforementioned water-insoluble but alkaline developing solution-soluble surfactants in alcohol solvents with 4 or more carbon atoms, ether solvents with 8 to 12 carbon atoms, or mixtures thereof.

[1572] 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.

[1573] 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.

[1574] 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.

[1575] 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.

[1576] 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.

[1577] 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.

[1578] Example

[1579] 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.

[1580] MALDI TOF-MS: S3000 manufactured by Nippon Electronics Co., Ltd.

[1581] [1] Synthesis of sulfonium salts

[1582] [Example 1-1] Synthesis of Sulfonium Salt PDQ-1

[1583] [Transformation 590]

[1584]

[1585] (1) Synthesis of sulfonium salt PDQ-1

[1586] Under nitrogen atmosphere, compound SM-1 (4.0 g), sodium bicarbonate (1.0 g), and water (20 g) were mixed in a reaction vessel and stirred at an internal temperature of 45 °C for 1 hour. The reaction mixture was then cooled to room temperature, and starting material SM-2 (5.3 g) and methyl isobutyl ketone (30 g) were added. The mixture was stirred at room temperature for 30 minutes. After stirring, the organic layer was separated and washed with water, followed by concentration under reduced pressure. The concentrate was purified by silica gel chromatography to obtain 8.3 g of the target compound, sulfonium salt PDQ-1 (93% yield), as an oil.

[1587] The TOF-MS results for PDQ-1 are shown below.

[1588] MALDI TOF-MS: POSITIVE M + 492 (equivalent to C) 25 H 22 F4NO3S + )

[1589] NEGATIVE M - 403 (equivalent to C8H5I2O3) - )

[1590] [Examples 1-2~1-7] Synthesis of Sulfonium Salts PDQ-2~PDQ-7

[1591] Using the corresponding raw materials and known organic chemical reactions, the sulfonium salts PDQ-2 to PDQ-7 represented by the following formulas were synthesized.

[1592] [Chem.591]

[1593]

[1594] [2] Synthesis of basic polymers

[1595] [Synthetic Example] Synthesis of basic polymers (polymers P-1 to P-5)

[1596] The monomers were combined and copolymerized in MEK as a solvent. The reaction solution was then placed in hexane, and the precipitated solid was washed with hexane, separated, and dried to obtain the base polymers (polymers P-1 to P-5) with the compositions shown below. The composition of the obtained base polymers was utilized... 1 The results were confirmed by H-NMR, and Mw and Mw / Mn were confirmed using GPC (solvent: DMF, standard: polystyrene).

[1597] [Chem. 592]

[1598]

[1599] [3] Preparation of chemically amplified resist composition

[1600] [Examples 2-1 to 2-30, Comparative Examples 1-1 to 1-20]

[1601] The quenchers of the present invention (PDQ-1 to PDQ-7), comparative quenchers (PDQ-A to PDQ-D), photoacid generators (PAG-X, PAG-Y, PAG-Z), base polymers (P-1 to P-5), and other quenchers (AQ-1, AQ-2) were dissolved in a solvent containing 0.01% by mass of surfactant A (OMNOVA) to prepare a solution. The solution was filtered through a 0.2 μm Teflon (registered trademark) type filter to obtain chemically amplified resist compositions (R-1 to R-30 and CR-1 to CR-20).

[1602] [Table 1]

[1603]

[1604] [Table 2]

[1605]

[1606] In Tables 1 and 2, the solvents, photoacid generators PAG-X, PAG-Y, PAG-Z, comparative quenchers PDQ-A to PDQ-D, other quenchers AQ-1 and AQ-2, and surfactant A are described below.

[1607] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[1608] EL (ethyl lactate)

[1609] DAA (diacetone alcohol)

[1610] Photoacid generators: PAG-X, PAG-Y, PAG-Z

[1611] [Chem.593]

[1612]

[1613] Comparison of quenching agents: PDQ-A to PDQ-D

[1614] [Chem. 594]

[1615]

[1616] Other quenching agents: AQ-1, AQ-2

[1617] [Chem.595]

[1618]

[1619] Surfactant A: 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane·tetrahydrofuran·2,2-dimethyl-1,3-propanediol copolymer (manufactured by OMNOVA).

[1620] [Chem.596]

[1621]

[1622] a : (b + b') : (c + c') = 1 : 4~7 : 0.01~1 (molar ratio)

[1623] Mw=1500

[1624] [4] Evaluation of EUV lithography (1)

[1625] [Examples 3-1 to 3-30, Comparative Examples 2-1 to 2-20]

[1626] Each chemically amplified resist composition (R-1~R-30, CR-1~CR-20) was spin-coated onto a Si substrate containing a silicon-containing spin-coating hard mask SHB-A940 (43% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd., with a film 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 dose and focus (exposure interval: 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 3 and 4 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.

[1627] The LS pattern obtained was observed using a Hitachi Advanced Technology Co., Ltd. (HIT) CG6300 measuring SEM, and the sensitivity, EL, LWR, depth of focus (DOF), and collapse limit were evaluated according to the following methods. Furthermore, the development defects of the obtained LS pattern were evaluated. The results are shown in Tables 3 and 4.

[1628] [Sensitivity Evaluation]

[1629] Find the optimal exposure E for obtaining an LS pattern with a linewidth of 18 nm and a pitch of 36 nm. op (mJ / cm 2 ), and let it be the sensitivity. The smaller the value, the higher the sensitivity.

[1630] [EL Review]

[1631] The exposure amount formed within ±10% (16.2~19.8nm) of the 18nm spacing width in the aforementioned LS pattern is used to calculate the EL (unit: %) using the following formula. The larger this value, the better the performance.

[1632] EL(%)=(|E1-E2| / E op )×100

[1633] E1: Provides optimal exposure for LS patterns with a linewidth of 16.2nm and a pitch of 36nm.

[1634] E2: Provides optimal exposure for LS patterns with a linewidth of 19.8nm and a pitch of 36nm.

[1635] E op Provides optimal exposure for LS patterns with a linewidth of 18nm and a pitch of 36nm.

[1636] [LWR Evaluation]

[1637] The length direction of the line is determined by E op The dimensions at 10 points of the LS pattern obtained by irradiation are used to calculate the LWR, which is three times the standard deviation (σ). The smaller this value, the more uniform the linewidth and roughness of the pattern can be obtained.

[1638] [DOF Rating]

[1639] The focal depth is evaluated by determining the focal range formed within ±10% (16.2~19.8nm) of the 18nm dimension in the aforementioned LS pattern. The larger this value, the wider the focal depth.

[1640] [Collapse Limit Assessment of Line Patterns]

[1641] 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 that could be obtained without collapse was taken as the collapse limit dimension. The smaller this value, the better the collapse limit.

[1642] [Evaluation of Development Defects]

[1643] 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 ​​below 0.5 are rated A, values ​​above 0.5 but below 1.0 are rated B, values ​​above 1.0 but below 5.0 are rated C, and values ​​above 5.0 are rated D. Lower values ​​indicate better performance.

[1644] [Table 3]

[1645]

[1646] [Table 4]

[1647]

[1648] As shown in Tables 3 and 4, the chemically amplified resist composition containing the photoacid generator of the present invention exhibits good sensitivity and excellent EL, LWR, and DOF. Furthermore, it was confirmed that the collapse limit value is small, and the pattern collapse resistance remains strong even during the formation of fine patterns. In addition, it was confirmed that development defects are easily suppressed. Therefore, it is shown that the chemically amplified resist composition of the present invention is suitable as a material for EUV lithography.

[1649] [5] Evaluation of EUV lithography (2)

[1650] [Examples 4-1 to 4-30, Comparative Examples 3-1 to 3-20]

[1651] Each chemically amplified resist composition (R-1~R-30, CR-1~CR-20) was 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., to a thickness of 20 nm. The substrate 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 then exposed using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, wafer-scale hole pattern with a pitch of 46 nm and +20% tolerance). A PEB process was then performed for 60 seconds using a hot plate at the temperatures listed in Tables 5 and 6, 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.

[1652] Using a Hitachi Advanced Technologies (AG) CG6300 length measuring SEM, the exposure was measured when the hole size was formed at 23 nm, 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 5 and 6.

[1653] [Table 5]

[1654]

[1655] [Table 6]

[1656]

[1657] The results shown in Tables 5 and 6 confirm that the chemically amplified resist composition of the present invention has good sensitivity and excellent CDU.

Claims

1. A matte salt, represented by the following formula (1); 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, cyano 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 can also be an aromatic carboxylic acid anion with substituents.

2. The matte salt according to claim 1, wherein it is represented by the following formula (1A); 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 matte salt 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 Hydrocarbon groups consisting of 1 to 20 carbon atoms, each independently composed of hydrogen atoms, or possibly containing heteroatoms; * indicates L 1 L 2 and L 3 Atomic bonds.

4. The matte salt according to claim 1, wherein, Z - Z represents the anion. In the formula, n21 is 0 or 1; n22 is 0, 1, 2, 3 or 4; n23 is 0, 1 or 2; n24 is 0, 1, 2, 3 or 4; however, when n21 is 0, 2≤n22+n23+n24≤5, and when n21 is 1, 2≤n22+n23+n24≤7; L A It can be a single bond, -O-, -S-, ester bond, or carbonate bond; R 11 In L A When the bond is a single hydrogen atom, it may also contain a hydrocarbon group with 1 to 20 carbon atoms and heteroatoms, in L A When the bond is -O-, -S-, ester bond or carbonate bond, it is a hydrogen atom, or it may contain a hydrocarbon group with 1 to 40 carbon atoms (but exclude acid-instable groups). R 12 It can be a halogen atom other than iodine, a nitro group, a cyano group, a pentafluorothio group, a 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 n24 is 2, 3, or 4, multiple R 12 They can also bond to each other and form a ring structure together with the carbon atoms on the aromatic rings they are bonded to, and part of the -CH2- of the ring can be replaced by -O- or -S-.

5. The matte salt according to claim 4, wherein, Z - Let (Z1) represent the following expression; In the formula, n22~n24, L A R 11 and R 12 Same as above.

6. The matte salt according to claim 4, wherein, L A It is either -O- or an ester bond.

7. The matte salt according to claim 4, wherein, L A For -O-, -S-, ester or carbonate bonds, R 11 It is an acid-labile group.

8. The matte salt according to claim 4, wherein, R 11 The acid-unstable group is represented by the following formula (AL-3) or (AL-4); In the formula, p1 and p2 are independently 0 or 1; q1 and q2 are independently 0, 1, 2, 3 or 4; R L11 and R L12 Each is an independent hydrocarbon group having 1 to 12 carbon atoms; R L13 It consists of a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R L11 R L12 and R L13 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 L11 and R L12 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 L13 When R is a hydrogen atom L11 and R L12 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 L14 and R L15 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; R L16 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 L15 and R L16 They can also bond to each other and to the carbon atoms and L atoms they are bonded to. B 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 B It can be -O- or -S-; R La ~R Ld Hydrocarbon groups consisting of 1 to 20 carbon atoms, each independently composed of hydrogen atoms, or may also contain heteroatoms; * indicates L A Atomic bonds.

9. A quenching agent comprising a sulfite salt according to any one of claims 1 to 8.

10. A chemically amplified resist composition comprising the quencher according to claim 9.

11. The chemically amplified resist composition according to claim 10, further comprising a base polymer containing at least one of the repeating units represented by formula (a1), formula (a2), and 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 Single bond, 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, or a saturated hydrocarbon 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 bonds, *-C(=O)-O- or *-C(=O)-N(H)-X 11 -; * indicates an atomic bond with a carbon atom 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 bonds, *-C(=O)-O- or *-C(=O)-N(H)-; * indicates an atomic bond with a carbon atom 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 of the following groups is a hydrocarbon group consisting of 1 to 20 carbon atoms, which may also contain heteroatoms; and 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 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxycarbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group or -N(R) group with 1 to 20 carbon atoms. 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 of the aromatic rings they are bonded to.

12. The chemically amplified resist composition according to claim 11, wherein, The polymer contains repeating units represented by formula (b1) or (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 Single bond, 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, or a saturated hydrocarbon 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 It represents a single bond or *-C(=O)-O-; * indicates an atomic bond with a carbon atom 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, 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.

13. The chemically amplified resist composition according to claim 11, wherein, The polymer contains at least one of the repeating units represented by formula (c1), repeating units represented by formula (c2), repeating units represented by formula (c3), repeating units represented by formula (c4), and repeating units represented by formula (c5). In the formula, d1 and d2 are 0, 1, 2 or 3 independently, respectively; e1 is 0 or 1; e2 is 0, 1, 2, 3 or 4; e3 is 0, 1, 2, 3 or 4; however, when e1 is 0, 0 ≤ e2 + e3 ≤ 4, and when e1 is 1, 0 ≤ e2 + e3 ≤ 6. R A Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z 1 It is a single bond or may have substituents; Z 2 For single bonds, **-C(=O)-OZ 21 -、**-C(=O)-N(H)-Z 21 -or**-OZ 21 -;Z 21 It is an aliphatic alkylene group, phenylene group, or a divalent group obtained by combining them with 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds or hydroxyl groups; Z 3 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond; Z 4 It is a single bond, or an aliphatic alkylene group with 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups; Z 5 Each can be a single bond, or a phenylene group with substituents, or a naphthylene group with substituents, or *-C(=O)-OZ. 51 -or *-C(=O)-N(R)-Z 51 -;Z 51 It is an aliphatic hydrocarbon group, phenylene, or naphthylene with 1 to 10 carbon atoms, and the aliphatic hydrocarbon group may also contain a halogen atom, hydroxyl group, ether bond, ester bond, or lactone ring; R is a hydrogen atom, or may also contain a hydrocarbon group with 1 to 10 carbon atoms. Z 6 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond; Z 7 Each is independently a single bond, ***-Z 71 -C(=O)-O-、***-C(=O)-N(R)-Z 71 -or ***-OZ 71 -;Z 71 It may also contain a hydrocarbon group with 1 to 20 carbon atoms and heteroatoms; R is the same as described above; Z 8 Each is independently a single bond, ****-Z 81 -C(=O)-O-、****-C(=O)-N(R)-Z 81 -or ****-OZ 81 -;Z 81 It may also contain a hydrocarbon group with 1 to 20 carbon atoms and heteroatoms; R is the same as described above; Z 9 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, *-C(=O)-OZ 91 -、*-C(=O)-N(R)-Z 91 -or *-OZ 91 -;Z 91 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; R is the same as described above; * indicates an atomic bond with a carbon atom in the main chain; ** indicates an atomic bond with a Z atom. 1 atomic bonds; *** indicates and Z 6 atomic bonds; **** represents the bond between Z and Z. 7 atomic bonds; L 11 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; Rf 5 and Rf 6 Each can be independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; however, all Rf 5 and Rf 6 It cannot simultaneously be a hydrogen atom; Rf 7 It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl thio group having 1 to 6 carbon atoms, or a pentafluorothio group; when e2 is 2, 3, or 4, each Rf 7 They can be the same or different; R 41 and R 42 Each can be independently a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms; and R 41 and R 42 They can also bond to each other and form rings together with the sulfur atoms they are bonded to; R 43 It can be a halogen atom other than fluorine, or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms; when e3 is 2, 3 or 4, each R 43 They can be the same or different, and there are multiple Rs. 43 They can also bond to each other and form rings together with the carbon atoms they are bonded to; M - It is a non-nucleophilic relative ion; A + It is a ium cation.

14. The chemically amplified resist composition according to claim 10 further comprises an organic solvent.

15. The chemically amplified resist composition according to claim 10 further comprises a photoacid generator that produces a strong acid.

16. The chemically amplified resist composition according to claim 10, further comprising a quencher other than the quencher according to claim 9.

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

18. 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.

19. The pattern forming method according to claim 18, 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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