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 solvent solubility, high sensitivity, high contrast, and lithography properties such as LWR, CDU, MEF, EL, DOF, etc., in optical lithography using high-energy rays; a chemically amplified resist composition containing the sulfonium salt as a photo-acid generator; and a pattern forming method using the chemically amplified resist composition. The solution means of the present invention is a sulfonium salt represented by the following formula (1). In the formula, Z ‑ is an aromatic sulfonic acid anion having at least one cyclic structure.

Description

Technical Field

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

[0002] In recent years, with the increasing integration and speed of LSI, and the pursuit of miniaturization in pattern regularity, far-ultraviolet lithography and extreme ultraviolet (EUV) lithography have been regarded as promising next-generation microfabrication technologies.

[0003] ArF lithography, using ArF excimer lasers, was partially adopted starting with 130nm node devices and became the dominant lithography technology from the 90nm node onwards. As the next-generation 45nm node lithography technology, lithography using the 157nm F2 laser was initially considered promising, but development was delayed due to various problems. Therefore, ArF immersion lithography, which achieves high resolution by inserting liquids with higher refractive indices than air (such as water, ethylene glycol, or glycerol) between the projection lens and the wafer, was put into practical use. This allows for a projection lens aperture number (NA) of 1.0 or higher. In this immersion lithography, a resist composition that is not easily dissolved in water is required.

[0004] In ArF lithography, to prevent the degradation of delicate and expensive optical materials, it is necessary to seek resist compositions with high sensitivity that can achieve sufficient resolution with low exposure. Regarding methods to achieve this, selecting components with high transparency at a wavelength of 193 nm is the most common approach. For example, regarding the base polymer, some have proposed polyacrylic acid and its derivatives, norbornene-maleic anhydride alternating polymers, polynorbornene, ring-opening metathesis polymers, and hydrides of ring-opening metathesis polymers, etc., which, considering the idea of ​​increasing the transparency of the resin monomers, have yielded some success.

[0005] In recent years, along with positive tone resists developed with alkaline aqueous solutions, negative tone resists developed with organic solvents have also attracted attention. To resolve extremely fine aperture patterns that cannot be achieved with positive tone exposure, researchers have used high-resolution positive resist compositions and developed them with organic solvents to form negative patterns. Furthermore, research is underway to achieve twice the resolution through a combination of alkaline aqueous solution development and organic solvent development. Regarding ArF resist compositions used for negative tone development with organic solvents, known positive ArF resist compositions can be used, and methods for forming patterns using these compositions are described in Patent Documents 1-3.

[0006] To adapt to the rapid miniaturization in recent years, in addition to process technology, the development of photoresist compositions has also made great strides. Various studies have been conducted on photoacid generators, generally using sulfonium salts composed of triphenylsulfonium cations and perfluoroalkyl sulfonate anions. However, the resulting acid, namely perfluoroalkyl sulfonates, especially perfluorooctanoic acid (PFOS), raises concerns about its poor biocompatibility, bioconcentration potential, and toxicity, making its application in photoresist compositions strictly controlled. Currently, photoacid generators that produce perfluorobutanesulfonate are used. However, if these are used in photoresist compositions, the resulting acid diffuses significantly, making it difficult to achieve high resolution. To address this issue, various developments have been made regarding partially fluorinated alkyl sulfonic acids and their salts. For example, Patent Document 1, in the current technology, describes a photoacid generator that produces α,α-difluoroalkyl sulfonic acid upon exposure; specifically, it is a photoacid generator that produces bis(4-tert-butylphenyl)monazine-1,1-difluoro-2-(1-naphthyl)ethanesulfonate and α,α,β,β-tetrafluoroalkyl sulfonic acid. However, although their fluorine substitution rates are all reduced, the lack of decomposable substituents such as ester structures makes the environmental safety considerations regarding easy decomposition insufficient. Furthermore, there are limitations in the molecular design for changing the size of alkyl sulfonic acids, and the high cost of starting materials containing fluorine atoms.

[0007] Furthermore, with the shrinking of circuit linewidths, the contrast degradation caused by acid diffusion in resist compositions becomes more severe. This is because the pattern size is close to the acid diffusion length, leading to a decrease in mask fidelity and a deterioration in pattern rectangularity due to the increased value of the dimensional deviation on the wafer (mask error factor (MEF)) relative to the mask dimensional deviation. Therefore, to fully realize the benefits of shorter wavelengths and higher photoluminescence (NA) of the light source, it is necessary to exceed known limits in terms of increasing the dissolution contrast of the material or suppressing acid diffusion. As one improvement method, lowering the baking temperature reduces acid diffusion, which improves MEF, but inevitably results in lower sensitivity.

[0008] Introducing high-barrier (bulky) substituents and polar groups into photoacid generators is effective in suppressing acid diffusion. Patent Document 4 describes a photoacid generator containing 2-acyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonic acid, which exhibits excellent solvent solubility and stability and allows for flexible molecular design. In particular, the photoacid generator containing 2-(1-adamantoxy)-1,1,3,3,3-pentafluoropropane-1-sulfonic acid with high-barrier (bulky) substituents exhibits low acid diffusion. Furthermore, Patent Documents 5-7 describe photoacid generators formed by introducing condensed ring lactones, sulfonyl lactones, and thiolactones as polar groups. Although it has been confirmed that the acid diffusion suppression effect caused by the introduction of polar groups results in a certain degree of performance improvement, the control of acid diffusion to a high degree is still insufficient. Considering factors such as MEF, pattern shape, and sensitivity, the photolithography performance remains unsatisfactory.

[0009] Introducing polar groups into the anion of the photoacid generator is effective in suppressing acid diffusion, but it is disadvantageous from the perspective of solvent solubility. In Patent Documents 8 and 9, experiments were conducted to improve solvent solubility by introducing alicyclic groups into the cationic portion of the photoacid generator to ensure solvent solubility; specifically, cyclohexane and adamantane rings were introduced. Although the solubility is improved by introducing such alicyclic groups, a certain number of carbon atoms is required to ensure solubility. As a result, the molecular structure of the photoacid generator becomes larger, and photolithographic performance such as linewidth roughness (LWR) and dimensional uniformity (CDU) deteriorates during the formation of fine patterns.

[0010] Furthermore, Patent Document 10 describes a photoacid generator that produces fluoroalkyl sulfonic acid with an aromatic condensation ring derived from anthracene in the anion. While this may confirm some improvement in photolithography performance, alkyl sulfonic acid lacks rigidity and has been restricted in recent years as an organofluorine compound targeted by PFAS. Concerns remain regarding its impact on the environment and human health.

[0011] Iodine atoms exhibit very high absorption at EUV wavelengths of 13.5 nm, confirming their ability to generate secondary electrons during exposure, thus attracting attention in EUV lithography. Patent Document 11 discloses a photoacid generator formed by introducing iodine atoms into anions, and Patent Document 12 discloses a photoacid generator containing polymerizable groups formed by introducing iodine atoms into anions. Patent Document 13 discloses a photoacid generator formed by introducing iodine atoms into both cations and anions. These methods have confirmed some improvement in lithography performance, but the increased solubility of iodine atoms in organic solvents raises the risk of precipitation in solvents.

[0012] Patent document 14 describes a photoacid generator in which multiple fluorine atoms are introduced into a cation. By introducing multiple fluorine atoms, the solvent solubility of the photoacid generator is improved, but it is still insufficient considering EUV absorption, and there is still room for improvement.

[0013] Patent documents 15-19 disclose photoacid generators and quenchers (acid diffusion control agents) containing iodine and fluorine atoms in the cation. Patent document 20 discloses a photoacid generator containing sulfonium cations with introduced iodine atoms and acid-indestabilizing groups. Through these developments, improvements in the performance of photoresist materials have been confirmed, but current considerations regarding acid diffusion control are still unsatisfactory, and there is a search for the development of photoresist materials that are more useful in the formation of fine patterns.

[0014] Existing technical documents

[0015] Patent documents

[0016] [Patent Document 1] Japanese Patent Application Publication No. 2008-281974

[0017] [Patent Document 2] Japanese Patent Application Publication No. 2008-281975

[0018] [Patent Document 3] Japanese Patent No. 4554665

[0019] [Patent Document 4] Japanese Patent Application Publication No. 2007-145797

[0020] [Patent Document 5] Japanese Patent No. 5061484

[0021] [Patent Document 6] Japanese Patent Application Publication No. 2016-147879

[0022] [Patent Document 7] Japanese Patent Application Publication No. 2015-63472

[0023] [Patent Document 8] Japanese Patent No. 5573098

[0024] [Patent Document 9] Japanese Patent No. 6461919

[0025] [Patent Document 10] Japanese Patent No. 7109178

[0026] [Patent Document 11] Japanese Patent No. 6720926

[0027] [Patent Document 12] Japanese Patent No. 6973274

[0028] [Patent Document 13] Japanese Patent No. 7041204

[0029] [Patent Document 14] Japanese Patent No. 7389562

[0030] [Patent Document 15] Japanese Patent Application Publication No. 2021-123579

[0031] [Patent Document 16] Japanese Patent Application Publication No. 2021-123580

[0032] [Patent Document 17] Japanese Patent Application Publication No. 2022-123839

[0033] [Patent Document 18] Japanese Patent Application Publication No. 2023-88869

[0034] [Patent Document 19] Japanese Patent Application Publication No. 2023-88870

[0035] [Patent Document 20] Japanese Patent No. 7367185

[0036] Non-patent literature

[0037] [Non-patent literature 1] Journal of Photopolymer Science and Technology, Vol. 17, No. 4, p. 587-601 (2004) Summary of the Invention

[0038] [The problem that the invention aims to solve]

[0039] In response to the high resolution requirements of resist patterns in recent years, resist compositions using known onium salt-type photoacid generators cannot adequately suppress acid diffusion. As a result, there is a possibility of degradation in lithography performance such as contrast, LWR, CDU, MEF, exposure margin (EL), and depth of focus (DOF).

[0040] The present invention was made in view of the foregoing circumstances, and aims to provide a sulfonium salt for use in chemical amplified resist compositions, particularly in optical lithography using high-energy rays such as KrF excimer lasers, ArF excimer lasers, electron beams (EB), and EUV, which has excellent solvent solubility, high sensitivity, high contrast, and excellent lithographic performance such as LWR, CDU, MEF, EL, and DOF; a chemical amplified resist composition containing the sulfonium salt as a photoacid generator; and a patterning method using the chemical amplified resist composition.

[0041] [Methods for solving the problem]

[0042] To achieve the aforementioned objectives, the inventors of this application conducted repeated and dedicated research, and as a result, discovered that a sulfonate salt composed of an aromatic sulfonic acid anion having at least one cyclic structure and a triarylsulfonate cation having a nitro group and an acid-unstable group having a tertiary / secondary ether structure, a tertiary / secondary ester structure, a tertiary / secondary carbonate structure, or an acetal structure on the same aromatic ring exhibits excellent solvent solubility. When used as a photoacid generator, this chemically amplified resist composition exhibits high sensitivity and high contrast, is extremely effective in suppressing acid diffusion, and demonstrates excellent photolithography performance in LWR, CDU, MEF, EL, and DOF formats. It is also extremely effective in forming fine patterns, thus leading to the completion of this invention.

[0043] That is, the present invention provides the following matte salt, chemically amplified resist composition and pattern formation method.

[0044] 1. A sulfite salt, represented by the following formula (1).

[0045] [Chemistry 1]

[0046]

[0047] 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; but 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; but 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; but 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, 1 ≤ n3 + n7 + n11 ≤ 6;

[0048] R 1 R 2 and R 3 Each can independently be 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, 2 Rs 1 They can also bond with each other and form rings together with the carbon atoms they bond with; when n8 is 2, each R 2 They can be the same or different, 2 Rs 2 They can also bond with each other and form rings together with the carbon atoms they bond with; when n12 is 2, each R 3 They can be the same or different, 2 Rs 3They can also bond with each other and form rings together with the carbon atoms they bond with;

[0049] 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;

[0050] 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;

[0051] 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;

[0052] Z - It is an aromatic sulfonic acid anion having at least one cyclic structure.

[0053] 2. The sulfonium salt of 1 is represented by the following formula (1A).

[0054] [Chemistry 2]

[0055]

[0056] 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.

[0057] 3. A sulfonium salt as in 1, wherein the unstable group of the acid is represented by the formula (AL-1) or (AL-2).

[0058] [Chemistry 3]

[0059]

[0060] In the formula, p1 and p2 are each independently 0 or 1; q1 and q2 are each independently 0, 1, 2, 3 or 4;

[0061] 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 be substituted with -O- or -S-. When the hydrocarbon group contains an aromatic ring, some or all of the hydrogen atoms in the aromatic ring may be substituted with halogen atoms, cyano, nitro, or alkyl groups containing halogen atoms with 1 to 4 carbon atoms, or alkoxy groups containing halogen atoms with 1 to 4 carbon atoms; furthermore, R L1 and R L2 They can also bond with each other to form a ring with the carbon atoms they bond to; a portion of the -CH2- in this ring can also be replaced by -O- or -S-; however, R L3 When R is a hydrogen atom L1 and R L2 The carbon atoms bonded to each other together form an alicyclic ring containing multiple bonds; furthermore, some of the hydrogen atoms in this alicyclic ring can be replaced by halogen atoms.

[0062] 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 with each other, and the carbon atoms and L atoms bonded to them 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-.

[0063] L 4 It can be -O- or -S-;

[0064] R La ~R Ld Each is an independent hydrocarbon group consisting of 1 to 20 carbon atoms, or may contain heteroatoms;

[0065] Indicates with L 1 L 2 and L 3 Atomic bonds.

[0066] 4. Such as the sulfite salt in 1, where Z - Z represents the anion.

[0067] [Chemistry 4]

[0068]

[0069] In the formula, m1 is 0 or 1; m2 is 0, 1, 2, 3, 4 or 5; m3 is 0, 1, 2, 3, 4 or 5; m4 is 0, 1, 2, 3, 4 or 5; however, when m1 is 0, 0 ≤ m2 + m3 + m4 ≤ 5, and when m1 is 1, 0 ≤ m2 + m3 + m4 ≤ 7.

[0070] W is a hydrocarbon group with 6 to 40 carbon atoms containing at least one alicyclic or aromatic ring, and the hydrocarbon group may also contain heteroatoms;

[0071] R F It consists of a fluorine atom, a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group with 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon thio group with 1 to 6 carbon atoms, or a pentafluorothio group; when m2 is 2, 3, or 4, each R F They can be the same or different;

[0072] R 11 It can be a halogen atom other than fluorine, a hydroxyl group, a nitro 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 m3 is 2, 3 or 4, each R 11 Multiple Rs can be the same or different. 11 They can also bond with each other and form rings together with the carbon atoms they bond with;

[0073] L A and L B Each bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond;

[0074] X L1 It is a single bond, or may contain heteroatoms and a hydrocarbon group with 1 to 40 carbon atoms.

[0075] 5. Sulfonium salts such as 4, wherein W is represented by the following formula (W-1) or (W-2).

[0076] [Chemistry 5]

[0077]

[0078] In the formula, m5 is 0 or 1; m6 is 0, 1, 2, 3 or 4; m7 is 1, 2, 3 or 4; m8 is 0 or 1; m9 is 0 or 1; m10 is 0, 1, 2, 3 or 4; m11 is 0, 1, 2, 3 or 4.

[0079] R 12 Each is an independent halogen atom other than a hydrogen atom or an iodine atom, or may contain a hydrocarbon group with 1 to 20 carbon atoms and heteroatoms;

[0080] R13 and R 14 Each is an independent hydrocarbon group consisting of 1 to 20 carbon atoms, a hydrogen atom, a halogen atom, or may also contain heteroatoms;

[0081] R 15 ~R 19 Each is an independent hydrocarbon group consisting of 1 to 40 carbon atoms, which may be hydrogen atoms, halogen atoms, or heteroatoms;

[0082] The dashed line indicates the L A Atomic bonds.

[0083] 6. A sulfonium salt such as 4, wherein the anion is represented by the formula (Z1).

[0084] [Chemistry 6]

[0085]

[0086] In the formula, m1~m4, W, R F R 11 and L A Same as above.

[0087] 7. A photoacid generator comprising a sulfonium salt of any one of 1 to 6.

[0088] 8. A chemically amplified resist composition comprising a photoacid generator, such as 7.

[0089] 9. The chemically amplified resist composition of 8 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).

[0090] [Chemistry 7]

[0091]

[0092] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group;

[0093] X 1 It is a single bond, phenylene, naphthylene or -C(=O)-OX 11 - The phenylene or naphthylene group may also be substituted with a saturated hydrocarbon group containing 1 to 10 carbon atoms, or a saturated hydroxyl group containing 1 to 10 carbon atoms, or a halogen atom containing fluorine atoms; X 11 It is a saturated hydrocarbon group, phenylene or naphthylene with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, ether bond, ester bond or lactone ring;

[0094] X2 For single key or -C(=O)-O-;

[0095] Indicates the atomic bond with the carbon atom in the main chain;

[0096] R 21 It can be a halogen atom, cyano group, hydroxyl group, nitro group, pentafluorosulfur group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; when a1 is 2, 3 or 4, each R 21 They can be the same or different;

[0097] AL 1 and AL 2 Each is an independent acid-labile group;

[0098] a1 can be 0, 1, 2, 3 or 4;

[0099] [Chemistry 8]

[0100]

[0101] 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;

[0102] R A It consists of hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups;

[0103] X 3 For single bond, -C(=O)-O- or -C(=O)-N(H)-; Indicates the atomic bond with the carbon atom in the main chain;

[0104] 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;

[0105] X 5 and X 6 Each can be independently an oxygen atom or a sulfur atom; but X 4 and X 6 It is bonded to an adjacent carbon atom of the aromatic ring;

[0106] R 22 and R 23 Each is an independent hydrocarbon group consisting of 1 to 20 carbon atoms, or may contain heteroatoms; also, R 22 and R23 They can also bond with each other and form rings together with the carbon atoms they bond with;

[0107] 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; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen carbonyl 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 Multiple Rs can be the same or different. 24 They can also bond with each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0108] 10. A chemically amplified resist composition as described in 9, wherein the polymer comprises repeating units represented by formula (b1) or (b2).

[0109] [Chemistry 9]

[0110]

[0111] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group;

[0112] Y 1 For single bonds, phenylene, naphthylene, -C(=O)-OY 11 -or -C(=O)-N(H)-Y 11 - The phenylene or naphthylene group may also be substituted with a saturated hydrocarbon group containing 1 to 10 carbon atoms, or a saturated hydrocarbon oxygen group containing 1 to 10 carbon atoms, or a halogen atom; Y 11 It is a saturated hydrocarbon group, phenylene or naphthylene with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, ether bond, ester bond or lactone ring;

[0113] Y 2 For single key or -C(=O)-O-; Indicates the atomic bond with the carbon atom in the main chain;

[0114] R 31It is a hydrogen atom, or a group having at least one structure with 1 to 20 carbon atoms selected from hydroxyl groups other than phenolic hydroxyl groups, cyano groups, nitro groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, and carboxylic anhydrides (-C(=O)-OC(=O)-).

[0115] R 32 The group can be a halogen atom, carboxyl group, nitro group, cyano group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, 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;

[0116] c1 can be 1, 2, 3 or 4; c2 can be 0, 1, 2, 3 or 4; but 1≤c1+c2≤5.

[0117] 11. The chemically amplified resist composition of 9, wherein the polymer comprises at least one selected from repeating units represented by formula (c1), formula (c2), formula (c3), formula (c4), and formula (c5).

[0118] [Chemistry 10]

[0119]

[0120] In the formula, d1 and d2 are each independently 0, 1, 2 or 3;

[0121] e1 is 0 or 1; e2 is 0, 1, 2, 3 or 4; e3 is 0, 1, 2, 3 or 4; but when e1 is 0, 0 ≤ e2 + e3 ≤ 4, and when e1 is 1, 0 ≤ e2 + e3 ≤ 6;

[0122] R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group;

[0123] Z 1 It is a single bond or may have substituents;

[0124] Z 2 For single bond, -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;

[0125] Z 3 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond;

[0126] Z 4 It can be 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; it may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups.

[0127] Z 5 Each can be a single bond, or a phenylene group with substituents, or a naphthylene group with substituents. -C(=O)-OZ 51 -or -C(=O)-N(R)-Z 51 -;Z 51 It is an aliphatic hydrocarbon group, phenylene, or naphthylene with 1 to 10 carbon atoms, 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 containing heteroatoms;

[0128] Z 6 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond;

[0129] Z 7 Each is an independent single bond. -Z 71 -C(=O)-O-、 -C(=O)-N(R)-Z 71 -or -OZ 71 -;Z 71 It may also contain a alkylene group with 1 to 20 carbon atoms; R is the same as described above;

[0130] Z 8 Each is an independent single bond. -Z 81 -C(=O)-O-、 -C(=O)-N(R)-Z 81 -or -OZ 81 -;Z 81 It may also contain a alkylene group with 1 to 20 carbon atoms; R is the same as described above;

[0131] 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 phenylene substituted with trifluoromethyl, having 1 to 6 carbon atoms; it may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; R is the same as described above;

[0132] Indicates the atomic bond with the carbon atom in the main chain; Indicates with Z 1 atomic bonds; Indicates with Z 6 atomic bonds; Indicates with Z 7 atomic bonds;

[0133] L 11 It can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond;

[0134] Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms;

[0135] 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;

[0136] Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; but Rf 5 and Rf 6They are not all hydrogen atoms at the same time;

[0137] 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;

[0138] R 41 and R 42 Each can be an independent hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms; furthermore, R 41 and R 42 They can also bond with each other and form rings together with the sulfur atoms they bond with;

[0139] R 43 It can be a halogen atom other than fluorine, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; when e3 is 2, 3 or 4, each R 43 Multiple Rs can be the same or different. 43 They can also bond with each other and form rings together with the carbon atoms they bond with;

[0140] M - It is a non-nucleophilic relative ion;

[0141] A + It is a ium cation.

[0142] 12. As in 8, chemically amplified resist compositions also contain organic solvents.

[0143] 13. As in 8, the chemically amplified resist composition also contains a quencher.

[0144] 14. Chemically amplified resist compositions, such as 8, also contain photoacid generators other than those in 7.

[0145] 15. As in 8, chemically amplified resist compositions also contain surfactants.

[0146] 16. A pattern forming method comprising the following steps: forming a resist film on a substrate using a chemically amplified resist composition such as 8; exposing the resist film to high-energy radiation; and developing the exposed resist film using a developer.

[0147] 17. The pattern forming method of 16, wherein the high-energy ray is a KrF excimer laser, an ArF excimer laser, an EB, or an EUV with a wavelength of 3 to 15 nm.

[0148] [The effects of the invention]

[0149] When patterning is performed using chemically amplified resist compositions containing the matte salt of the present invention as photoacid generators, high sensitivity and excellent acid diffusion suppression performance are achieved, and the photolithography performance of LWR, CDU, MEF, EL, DOF, etc. is improved, which can suppress the collapse of resist patterns during the formation of fine patterns. Detailed Implementation

[0150] The present invention will now be described in detail. Furthermore, in the following description, depending on the structure represented by the chemical formula, there may be enantiomers and diastereomers due to the presence of asymmetric carbons; however, in this case, one chemical formula is used to represent these isomers. These isomers may be used individually or in mixtures of two or more.

[0151] [Sulfate]

[0152] The sulfite salt of the present invention is represented by the following formula (1).

[0153] [Chemistry 11]

[0154]

[0155] 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. However, considering solvent solubility, a benzene ring with n1 of 0 is more ideal. n2 is 0, 1, or 2. n3 is 0, 1, or 2. n4 is 0, 1, or 2. Considering raw material supply, 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.

[0156] 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. However, considering solvent solubility, a benzene ring with n5 of 0 is more ideal. n6 is 0, 1, or 2. n7 is 0, 1, or 2. n8 is 0, 1, or 2. Considering raw material supply, 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.

[0157] 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. However, considering solvent solubility, a benzene ring with n9 of 0 is more ideal. n10 is 0, 1, or 2. n11 is 0, 1, or 2. n12 is 0, 1, or 2. Considering raw material supply, 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.

[0158] In equation (1), 1≤n2+n6+n10≤6, but ideally it is 1≤n2+n6+n10≤3, and even more ideally it is 1≤n2+n6+n10≤2. Also, 1≤n3+n7+n11≤6, but ideally it is 1≤n3+n7+n11≤3, and even more ideally it is 1≤n3+n7+n11≤2.

[0159] In equation (1), R 1 R 2 and R 3 Each group can be independently 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 atoms. 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; 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; cyclohexenyl and other cyclounsaturated hydrocarbon groups with 3 to 20 carbon atoms; 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. Of these, aryl is the most ideal. 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. As a result, it may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc.

[0160] When n4 is 2, each R 1 They can be the same or different. Also, when n⁴ is 2, there are 2 R... 1 They can also bond with each other and form rings together with the carbon atoms they bond to. Regarding the aforementioned rings, 5- to 8-membered rings are ideal. When n8 is 2, each R... 2 They can be the same or different. Also, when n8 is 2, there are 2 R... 2They can also bond with each other and form rings together with the carbon atoms they bond to. Regarding the aforementioned rings, 5- to 8-membered rings are ideal. 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 with each other to form rings together with the carbon atoms they bond with. Among the aforementioned rings, 5- to 8-membered rings are more ideal.

[0161] In equation (1), L 1 L 2 and L 3 Each bond can be independently formed by an ether bond, ester bond, or carbonate bond. Among these, ether bonds or ester bonds are more ideal. 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.

[0162] In equation (1), R AL1 R AL2 and R AL3 Each is an unstable acid 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.

[0163] Regarding the aforementioned acid-instable groups, those represented by the formula (AL-1) or (AL-2) are more ideal.

[0164] [Chemistry 12]

[0165]

[0166] In the formula, Indicates with L 1 L 2 and L 3 Atomic bonds.

[0167] In equations (AL-1) and (AL-2), p1 and p2 are each independently 0 or 1. q1 and q2 are each independently 0, 1, 2, 3, or 4. Ideally, q1 should be 1 or 2 when p1 is 1, and q1 should be 0 when p1 is 0. Similarly, ideally, q2 should be 1 or 2 when p2 is 1, and q2 should be 0 when p2 is 0.

[0168] 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. RL1 R L2 and R L3 The -CH2- group of the hydrocarbon group may be substituted by -O- or -S-. When the hydrocarbon group contains an aromatic ring, some or all of the hydrogen atoms of the aromatic ring may be substituted 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.

[0169] R L1 R L2 and R L3 The hydrocarbon group represented has 1 to 12 carbon atoms and can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, norbornelmethyl, adamantyl, adamantylmethyl, and 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 indanyl; aralkyl groups with 7 to 12 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these groups, etc.]

[0170] Also, R L1 and R L2 They can also bond to each other and form rings together with the carbon atoms they bond 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 rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, norcamphene rings, adamantane rings, and tricyclic rings [5.2.1.0]. 2,6 Decane ring, tetracyclic ring [6.2.1.1] 3,6 .0 2,7 Dodecane 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 L2The carbon atoms bonded to each other form alicyclic rings containing multiple bonds. Furthermore, some of the hydrogen atoms in the aforementioned alicyclic rings can be replaced by halogen atoms.

[0171] In equation (AL-2), R L4 and R L5 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R L4 and R L5 The hydrocarbon group representing 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include those related to R. L1 R L2 and R L3 The hydrocarbon groups represented are the same as those with 1 to 10 carbon atoms.

[0172] 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 also 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 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; 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, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, tert-butylnaphthyl 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 L6 They can also bond with each other, and the carbon atoms and L atoms bonded to them 4 Together they form a heterocyclic group with 3 to 20 carbon atoms. A portion of the -CH2- of this heterocyclic group can also be replaced by -O- or -S-.

[0173] In equation (AL-2), L 4 It can be either -O- or -S-.

[0174] In equations (AL-1) and (AL-2), R La ~R Ld Each group consists independently of a hydrogen atom, or may contain heteroatoms, and has 1 to 20 carbon atoms as a hydrocarbon group. These 1 to 20 carbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include those related to R. L6 The hydrocarbon groups represented are the same as those shown, but are not limited to these.

[0175] Specific examples of acid-instable groups represented by formula (AL-1) can be listed as shown below, but are not limited to these. Additionally, in the following formula, Indicates with L 1 L 2 and L 3 Atomic bonds.

[0176] [Chemistry 13]

[0177]

[0178] [Chemistry 14]

[0179]

[0180] [Chemistry 15]

[0181]

[0182] [Chemistry 16]

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[0184] [Chemistry 17]

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[0186] [Chemistry 18]

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[0188] [Chemistry 19]

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[0190] [Chemistry 20]

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[0192] [Chemistry 21]

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[0194] [Chemistry 22]

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[0196] [Chemistry 23]

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[0198] [Chemistry 24]

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[0200] [Chemistry 25]

[0201]

[0202] [Chemistry 26]

[0203]

[0204] [Chemistry 27]

[0205]

[0206] [Chemistry 28]

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[0208] [Chemistry 29]

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[0210] [Chemistry 30]

[0211]

[0212] [Chemistry 31]

[0213]

[0214] [Chemistry 32]

[0215]

[0216] [Chemistry 33]

[0217]

[0218] [Chemistry 34]

[0219]

[0220] Specific examples of the acid-instable groups represented by formula (AL-2) are shown below, but are not limited to these. Additionally, in the following formula, Indicates with L 1 L 2 and L 3 Atomic bonds.

[0221] [Chemistry 35]

[0222]

[0223] [Chemistry 36]

[0224]

[0225] [Chemistry 37]

[0226]

[0227] In formula (1), the nitro group and -L 1 -R AL1 Ideally, the nitro group should be bonded to adjacent carbon atoms. This proximity allows the -R group to bond more readily due to the electron attraction of the nitro group. AL1 The increased acidity of phenols and carboxylic acids generated during deprotection will improve the solubility contrast.

[0228] In formula (1), the nitro group and -L 2 -R AL2 Ideally, the nitro group should be bonded to adjacent carbon atoms. This proximity allows the -R group to bond more readily due to the electron attraction of the nitro group. AL2 The increased acidity of phenols and carboxylic acids generated during deprotection will improve the solubility contrast.

[0229] In formula (1), the nitro group and -L 3 -R AL3 Ideally, the nitro group should be bonded to adjacent carbon atoms. This proximity allows the -R group to bond more readily due to the electron attraction of the nitro group. AL3 The increased acidity of phenols and carboxylic acids generated during deprotection will improve the solubility contrast.

[0230] 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. In this case, specific examples of the aforementioned ring structures can be listed as follows.

[0231] [Chemistry 38]

[0232]

[0233] In the formula, the dashed lines represent atomic bonds.

[0234] For the sulfite salt represented by equation (1), the one represented by equation (1A) is more ideal.

[0235] [Chemistry 39]

[0236]

[0237] 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 later.

[0238] Specific examples of cations of sulfonium salts represented by formula (1) can be listed as shown below, but are not limited to these. In addition, Me is a methyl group in the following formula.

[0239] [Chemistry 40]

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[0633] In equations (1) and (1A), Z - It is an aromatic sulfonic acid anion having at least one cyclic structure. For the aforementioned aromatic sulfonic acid anion, the one represented by the following formula (Z) is more ideal.

[0634] [Chemistry 237]

[0635]

[0636] In formula (Z), m1 is 0 or 1. When m1 is 0, it is a benzene ring; when m1 is 1, it is a naphthalene ring. However, considering solvent solubility, a benzene ring with m1 of 0 is more ideal. m2 is 0, 1, 2, 3, 4, or 5. Considering raw material supply, m2 is more ideal when m2 is 1 or higher. m3 is 0, 1, 2, 3, 4, or 5. m4 is 0, 1, 2, 3, 4, or 5. However, considering acid diffusion control, m4 is more ideal. But, when m1 is 0, 0 ≤ m2 + m3 + m4 ≤ 5; when m1 is 1, 0 ≤ m2 + m3 + m4 ≤ 7.

[0637] In formula (Z), R F It consists 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, a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms, or a pentafluorothio group. Regarding R... F For these substituents, fluorine atoms, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, or difluoromethylthio are preferred, with fluorine atoms, trifluoromethyl, or trifluoromethoxy being even more desirable. These substituents containing or having fluorine atoms enhance the acid strength of the resulting acid due to electron attraction, thus facilitating the deprotection reactions of unstable acid groups such as tertiary esters and tertiary ethers described later. When m2 is 2, 3, or 4, each R... FThey can be the same or different.

[0638] In formula (Z), R 11 The halogen atom can be any halogen other than fluorine, a hydroxyl group, a nitro 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. Examples of halogen atoms other than fluorine include chlorine, bromine, and iodine, but iodine is preferred. The aforementioned hydrocarbon 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; 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; cyclohexenyl and other cyclounsaturated hydrocarbon groups with 3 to 20 carbon atoms; 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. Of these, aryl is the most ideal. 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. As a result, it may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. When m3 is 2, 3, or 4, each R... 11 They can be the same or different. Also, when m3 is 2, 3, or 4, multiple R... 11 They can also bond with each other to form rings together with the carbon atoms they bond with. Among the aforementioned rings, 5- to 8-membered rings are more ideal.

[0639] In formula (Z), W is a hydrocarbon group with 6 to 40 carbon atoms containing at least one alicyclic or aromatic ring, and the hydrocarbon group may also contain heteroatoms.

[0640] In formula (Z), for W, it is more ideal to use a group represented by formula (W-1) or (W-2).

[0641] [Chemistry 238]

[0642]

[0643] In the formula, the dashed line represents the intersection with L. A Atomic bonds.

[0644] In formula (W-1), m5 is 0 or 1. When m5 is 0, it is a benzene ring; when m5 is 1, it is a naphthalene ring. However, considering solvent solubility, a benzene ring with m5 of 0 is more ideal. m6 is 0, 1, 2, 3, or 4. When m5 is 0, m6 being 2, 3, or 4 is more ideal. Considering EUV light absorption, m6 being 3 or 4 is more ideal. m7 is 1, 2, 3, or 4. Considering raw material supply, m7 being 1, 2, or 3 is more ideal. Considering acid diffusion control, m7 being 2 or 3 is more ideal.

[0645] In equation (W-1), R 12 Each group can be a halogen atom other than a hydrogen atom or an iodine atom, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms. Examples of halogen atoms other than iodine atoms include fluorine, chlorine, and bromine atoms, but fluorine atoms are preferred from the perspective of solvent solubility. Furthermore, specific examples of hydrocarbon groups with 1 to 20 carbon atoms that may also contain heteroatoms include those mentioned in the explanation of formula (1) regarding R. 1 and R 2 The hydrocarbon groups represented are those that are identical, but not limited to these. Regarding R... 12 In this regard, groups with branched or cyclic structures are more ideal.

[0646] In equation (W-1), the derivatives are selected from R. 12 At least one of the iodine atoms is bonded to L A Ideally, the carbon atoms adjacent to the bonded carbon atoms should be on the ring. This allows for rotation between the aromatic rings bonded by these groups and those bonded by the sulfonic acid groups within the -L... A -X L1 -L B The bonding axis around - is inhibited by steric barriers, which can reduce acid diffusion.

[0647] In formula (W-2), m8 is 0 or 1. When m8 is 0, it is a benzene ring; when m8 is 1, it is a naphthalene ring. However, considering solvent solubility, a benzene ring with m7 being 0 is more ideal. m9 is 0 or 1. When m9 is 0, it is a benzene ring; when m9 is 1, it is a naphthalene ring. However, considering solvent solubility, a benzene ring with m9 being 0 is more ideal. m10 is 0, 1, 2, 3, or 4. Considering raw material supply, m10 being 0, 1, or 2 is more ideal. m11 is 0, 1, 2, 3, or 4. Considering raw material supply, m11 being 0, 1, or 2 is more ideal.

[0648] In equation (W-2), R 13 and R 14Each group is a hydrocarbon group with 1 to 20 carbon atoms, which may be independently composed of hydrogen atoms, halogen atoms, or heteroatoms. Regarding the aforementioned halogen atoms, examples include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, but fluorine atoms and iodine atoms are more ideal. Furthermore, regarding specific examples of hydrocarbon groups with 1 to 20 carbon atoms that may also contain heteroatoms, examples include those mentioned in the explanation of formula (1) regarding R... 1 and R 2 The hydrocarbon groups represented are those that are identical, but not limited to these. Regarding R... 13 and R 14 In this regard, groups with branched or cyclic structures are more ideal.

[0649] In equation (W-2), R 15 ~R 19 Each group is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of hydrogen atoms, halogen atoms, or heteroatoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, but fluorine and iodine atoms are preferred. Furthermore, specific examples of hydrocarbon groups with 1 to 20 carbon atoms that may also contain heteroatoms include those described in the explanation of formula (1) regarding R. 1 and R 2 The hydrocarbon groups represented are those that are identical, but not limited to these. Regarding R... 15 ~R 19 In this regard, groups with branched or cyclic structures are more ideal.

[0650] In equation (W-2), R 15 ~R 19 Any two of the atoms in the ring can bond to each other and form a ring together with the carbon atoms they bond to. As for the aforementioned rings, 5- to 8-membered rings are more ideal.

[0651] In formula (Z), L A and L B Each bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. Among these, single bonds, ether bonds, or ester bonds are more ideal.

[0652] In formula (Z), X L1 It is a single-bonded or heteroatom-containing hydrocarbon group with 1 to 40 carbon atoms. The aforementioned hydrocarbon group can be linear, branched, or cyclic; specific examples include alkyldiyl, cyclic saturated hydrocarbon groups, and arylyl groups. Specific examples of the aforementioned heteroatom include oxygen, nitrogen, and sulfur atoms.

[0653] Regarding X L1 Specific examples of hydrocarbon groups with 1 to 40 carbon atoms that may contain heteroatoms can be listed as shown below, but are not limited to these. Additionally, in the following formula, To represent L respectively A and L B Atomic bonds.

[0654] [Chemistry 239]

[0655]

[0656] [Chemistry 240]

[0657]

[0658] [Chemistry 241]

[0659]

[0660] [Chemistry 242]

[0661]

[0662] Among these, X L1 In other words, for X L -0~X L -22, X L -29~X L -34 and X L -47~X L -61 is ideal.

[0663] For anions represented by formula (Z), the one represented by formula (Z1) is more ideal.

[0664] [Chemistry 243]

[0665]

[0666] In the formula, m1~m4, W, R F R 11 and L A Same as above.

[0667] Specific examples of anions represented by formula (Z) include paragraphs

[0027] to

[0029] of Japanese Patent No. 6248882, paragraphs

[0029] to

[0034] of Japanese Patent No. 6648726, paragraphs

[0220] to

[0225] of Japanese Patent No. 7032549, paragraphs

[0186] to

[0188] of Japanese Patent No. 7398551, paragraphs

[0028] to

[0029] of Japanese Patent No. 7067271, paragraphs

[0034] to

[0037] of Japanese Patent No. 6090585, and Japanese Unexamined Patent Application Publication No. 2024-104830. The paragraphs

[0037] to

[0060] of the report, the paragraphs

[0040] to

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

[0039] to

[0057] of Japanese Patent Application Publication No. 2023-177038, the paragraphs

[0033] to

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

[0220] to

[0225] of Japanese Patent Application Publication No. 7032549, the paragraphs

[0229] to

[0231] of Japanese Patent Application Publication No. 2024-077330, and the paragraphs

[0056] to

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

[0668] Other specific examples of anions represented by formula (Z) are listed below, but are not limited to these. Additionally, in the following formula, Me is a methyl group.

[0669] [Chemistry 244]

[0670]

[0671] [Chemistry 245]

[0672]

[0673] [Chemistry 246]

[0674]

[0675] [Chemistry 247]

[0676]

[0677] [Chemistry 248]

[0678]

[0679] [Chemistry 249]

[0680]

[0681] [Chemistry 250]

[0682]

[0683] [Chemistry 251]

[0684]

[0685] [Chemistry 252]

[0686]

[0687] [Chemistry 253]

[0688]

[0689] [Chemistry 254]

[0690]

[0691] [Chemistry 255]

[0692]

[0693] [Chemistry 256]

[0694]

[0695] [Chemistry 257]

[0696]

[0697] [Chemistry 258]

[0698]

[0699] [Chemistry 259]

[0700]

[0701] [Chemistry 260]

[0702]

[0703] [Chemistry 261]

[0704]

[0705] [Chemistry 262]

[0706]

[0707] [Chemistry 263]

[0708]

[0709] [Chemistry 264]

[0710]

[0711] [Chemistry 265]

[0712]

[0713] [Chemistry 266]

[0714]

[0715] [Chemistry 267]

[0716]

[0717] [Chemistry 268]

[0718]

[0719] [Chemistry 269]

[0720]

[0721] [Chemistry 270]

[0722]

[0723] [Chemistry 271]

[0724]

[0725] [Chemistry 272]

[0726]

[0727] [Chemistry 273]

[0728]

[0729] [Chemistry 274]

[0730]

[0731] [Chemistry 275]

[0732]

[0733] [Chemistry 276]

[0734]

[0735] [Chemistry 277]

[0736]

[0737] [Chemistry 278]

[0738]

[0739] [Chemistry 279]

[0740]

[0741] [Chemistry 280]

[0742]

[0743] [Chemistry 281]

[0744]

[0745] [Chemistry 282]

[0746]

[0747] [Chemistry 283]

[0748]

[0749] [Chemistry 284]

[0750]

[0751] [Chemistry 285]

[0752]

[0753] [Chemistry 286]

[0754]

[0755] [Chemistry 287]

[0756]

[0757] [Chemistry 288]

[0758]

[0759] [Chemistry 289]

[0760]

[0761] [Chemistry 290]

[0762]

[0763] [Chemistry 291]

[0764]

[0765] [Chemistry 292]

[0766]

[0767] [Chemistry 293]

[0768]

[0769] [Chemistry 294]

[0770]

[0771] [Chemistry 295]

[0772]

[0773] [Chemistry 296]

[0774]

[0775] [Chemistry 297]

[0776]

[0777] [Chemistry 298]

[0778]

[0779] [Chemistry 299]

[0780]

[0781] [Chemical 300]

[0782]

[0783] [Chemical Engineering 301]

[0784]

[0785] [Chemical 302]

[0786]

[0787] [Chemical 303]

[0788]

[0789] [Chemical 304]

[0790]

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[0792]

[0793] [Chemical 306]

[0794]

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[0858]

[0859] [Chemistry 339]

[0860]

[0861] [Transformation 340]

[0862]

[0863] [Chemistry 341]

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[0907] [Chem. 363]

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[0909] [Chem. 364]

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[0911] [Chem. 365]

[0912]

[0913] [Chem. 366]

[0914]

[0915] [Chem. 367]

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[0917] [Chem. 368]

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[0919] [Chem. 369]

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[0921] [Chem. 370]

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[0953] [Chemistry 386]

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[0957] [Chem.388]

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[0970]

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[0983] [Chemical Engineering 401]

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[0989] [Chemical 404]

[0990]

[0991] [Chemical 405]

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[0993] [Chemical 406]

[0994]

[0995] [Chemical 407]

[0996]

[0997] [Chemical 408]

[0998]

[0999] [Chemical 409]

[1000]

[1001] [Chemical 410]

[1002]

[1003] [Chemistry 411]

[1004]

[1005] [Chemistry 412]

[1006]

[1007] [Chemistry 413]

[1008]

[1009] [Chemistry 414]

[1010]

[1011] [Chemical 415]

[1012]

[1013] [Chemistry 416]

[1014]

[1015] [Chemistry 417]

[1016]

[1017] [Chemistry 418]

[1018]

[1019] [Chemistry 419]

[1020]

[1021] [Chemistry 420]

[1022]

[1023] [Chemistry 421]

[1024]

[1025] [Chemistry 422]

[1026]

[1027] [Chemistry 423]

[1028]

[1029] [Chemistry 424]

[1030]

[1031] [Chemical 425]

[1032]

[1033] [Chemistry 426]

[1034]

[1035] [Chemistry 427]

[1036]

[1037] [Chemistry 428]

[1038]

[1039] [Chemistry 429]

[1040]

[1041] In particular, any combination of anions and cations as described above can be cited as examples of the matte salts of the present invention.

[1042] Regarding the synthesis method of the matte salt of the present invention, examples can be found in Japanese Patent Application Publication No. 2010-155824 and Japanese Patent No. 7067271, but the aforementioned manufacturing methods are merely illustrative, and the manufacturing method of the matte salt of the present invention is not limited to these.

[1043] Regarding the structural features of the sulfonate salts of the present invention, examples include: aromatic sulfonic acid anions substituted with a hydrocarbon group comprising at least one ring structure, and triarylsulfonate cations having a nitro group and an acid-unstable group having a tertiary / secondary ether structure, a tertiary / secondary ester structure, a tertiary / secondary carbonate structure, or an acetal structure on the same aromatic ring. It is known that irradiation of the base polymer with EUV light will release secondary electrons. Furthermore, regarding iodine atoms, especially in EUV lithography at a wavelength of 13.5 nm, the absorption of EUV due to iodine atoms is very large, thus generating secondary electrons during exposure. The cyano group bonded to the aromatic ring of the sulfonate cation is known as a strong electron-withdrawing group. Therefore, it is believed to lower the LUMO energy level in the Frontier orbital theory. Therefore, it becomes easier to accept secondary electrons generated from the iodine atom in the anion, promoting the decomposition of the cation and efficiently producing acid. Furthermore, the nitro group possesses a resonance structure with a positive charge on its nitrogen atom and a negative charge on one of its oxygen atoms. Therefore, it is expected that the negative charge on the oxygen atom will interact with the protons of the generated acid, thus functioning as an acid diffusion inhibitor. Due to this charge, it has a high affinity for alkaline developers, and the residue after cation decomposition is efficiently removed by the alkaline developer, reducing the risk of development defects in the exposed area. The acid-unstable groups with tertiary / secondary ether, tertiary / secondary ester, tertiary / secondary carbonate, or acetal structures bonded to the same aromatic ring in the sulfonium cation will undergo deprotection reactions caused by the acid generated during exposure, generating the corresponding phenols or carboxylic acids. The structure changes from lipophilic to hydrophilic, resulting in increased contrast between the exposed and unexposed areas. Moreover, the acidity of the phenols or carboxylic acids increases due to the electron attraction of the nitro group, as it bonds to the carbon atom adjacent to the carbon atom bonded to the phenolic hydroxyl or carboxyl group generated during the deprotection reaction. When the exposed section that has undergone the deprotection reaction is developed with an alkaline developer, the increased acidity of phenols enhances their solubility in the alkaline developer, thus suppressing development residue.

[1044] The aforementioned hydrocarbon group containing at least one ring structure, excluding those with large volume, functions as a large substituent, thus significantly suppressing the diffusion of the generated acid. This effect is particularly pronounced when the aforementioned hydrocarbon group containing at least one aromatic ring is a substituent-containing aromatic ring structure as shown in Formula (W-1) or a substituent-containing condensed ring structure as shown in Formula (W-2). Furthermore, because it is resistant to alkaline developers, film loss in unexposed areas is reduced. On the other hand, the structure of the acid generated by the aromatic sulfonic acid structure is rigid, exhibiting an effect of suppressing acid diffusion. In the aromatic ring forming the aromatic sulfonic acid structure, sulfonate bonds with fluorine atoms or electron-attracting linkage groups are ideal, thereby increasing the acidity of the generated acid and efficiently deprotecting the acid-unstable groups of the base polymer. Although fluorine atoms are less abundant than iodine atoms, they are highly absorbent of EUV light; therefore, increasing the number of fluorine atoms increases the generation of secondary electrons, promoting cation decomposition and contributing to higher sensitivity. While Japanese Patent No. 7109178 discloses alkylsulfonic acid-type photoresist with 2 to 4 fluorine atoms, these alkylsulfonic acids exhibit high acid diffusion and poor solvent solubility, raising concerns about development defects. Through these synergistic effects, the resist composition containing the matte salt of this invention possesses high sensitivity and low acid diffusion, thereby enabling the formation of patterns with excellent photolithography performance and strong resistance to pattern collapse, such as LWR and CDU, making it ideal for forming fine patterns.

[1045] The aforementioned sulfonium salt can be ideally used as a photoacid generator.

[1046] [Chemical amplification resist composition]

[1047] [(A) Photoacid generator]

[1048] The chemically amplified resist composition of the present invention contains a photoacid generator composed of a sulfonium salt represented by formula (1) as an essential component.

[1049] In the chemically amplified resist composition of the present invention, the content of the photoacid generating agent composed of sulfonium salt in component (A) is preferably 0.1 to 40 parts by mass relative to 80 parts by mass of the base polymer described later, and more preferably 0.5 to 30 parts by mass. If the content of component (A) falls within the aforementioned range, the sensitivity and resolution are good, and there is no risk of foreign matter being generated after the resist film is developed or peeled off, which is therefore ideal. The photoacid generating agent (A) can be used alone or in combination of two or more.

[1050] [(B) Basic Polymer]

[1051] The chemically amplified resist composition of the present invention may also contain a base polymer as component (B). Regarding the base polymer (B), it is preferable to have repeating units containing acid-labile groups. The aforementioned repeating units containing acid-labile groups may be used alone or in combination of two or more.

[1052] With regard to the specific examples of repeating units containing acid-labile groups mentioned above, repeating units represented by the following formula (a1) (hereinafter also referred to as repeating unit a1.) and repeating units represented by the following formula (a2) (hereinafter also referred to as repeating unit a2.) can be listed.

[1053] [Chemistry 430]

[1054]

[1055] In equations (a1) and (a2), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[1056] In equation (a1), X 1 It is a single bond, phenylene, naphthylene or -C(=O)-OX 11 - The phenylene or naphthylene group may also be substituted with a saturated hydrocarbon group containing 1 to 10 carbon atoms, or a saturated hydrocarbon oxygen group containing 1 to 10 carbon atoms, or a halogen atom. X 11 It is a saturated alkylene group, phenylene group, or naphthylene group with 1 to 10 carbon atoms. The saturated alkylene group may also contain hydroxyl groups, ether bonds, ester bonds, or lactone rings. This represents the atomic bond with the carbon atoms in the main chain.

[1057] In equation (a2), X 2 For single key or -C(=O)-O-. Represents the 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 oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. a1 is 0, 1, 2, 3, or 4, ideally 0 or 1. When a1 is 2, 3, or 4, each R 21 They can be the same or different.

[1058] In equations (a1) and (a2), AL 1 and AL 2Each is an acid-indestructible group independently. Specific examples of the aforementioned acid-indestructible groups can be cited in Japanese Patent Application Publication Nos. 2013-80033 and 2013-83821.

[1059] For representativeness, specific examples of the aforementioned acid-instable groups can be listed as those represented by formulas (AL-3) to (AL-5).

[1060] [Chemistry 431]

[1061]

[1062] In the formula, It represents an atomic bond.

[1063] In equations (AL-3) and (AL-4), R L11 and R L12 Each hydrocarbon group consists independently of a carbon group numbering 1 to 40, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Of these, hydrocarbon groups with 1 to 20 carbon atoms are considered ideal.

[1064] In equation (AL-3), a2 is an integer from 0 to 10, and 1, 2, 3, 4 or 5 is more ideal.

[1065] In equation (AL-4), R L13 and R L14 Each group is independently composed of a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Furthermore, R... L12 R L13 and R L14 Any two of them can also bond to each other to form a ring with 3 to 20 carbon atoms, together with the carbon atoms they bond to, or carbon atoms and oxygen atoms. Among the aforementioned rings, rings with 4 to 16 carbon atoms are more ideal, especially alicyclic rings.

[1066] In equation (AL-5), R L15 R L16 and R L17 Each group is an independent hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Furthermore, R... L15 R L16 and R L17 Any two of them can also bond to each other to form a ring with 3 to 20 carbon atoms together with the carbon atoms they bond to. Among the aforementioned rings, rings with 4 to 16 carbon atoms are more ideal, especially alicyclic rings.

[1067] Other specific examples of the aforementioned acid-indestructible 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 are examples where the formation of conjugated olefins or acrylate derivatives is the driving force for the reaction after the acid desorption reaction.

[1068] Regarding specific examples of the repeating unit a1, examples as shown below can be listed, but are not limited to these. Additionally, in the following formula, R... A and AL 1 Same as above.

[1069] [Chemistry 432]

[1070]

[1071] [Chemistry 433]

[1072]

[1073] [Chemistry 434]

[1074]

[1075] [Chemistry 435]

[1076]

[1077] Specific examples of the repeating unit a2 can be listed as shown below, but are not limited to these. Additionally, in the following formula, R... A and AL 2 Same as above.

[1078] [Chemistry 436]

[1079]

[1080] [Chemistry 437]

[1081]

[1082] [Chemistry 438]

[1083]

[1084] As for other specific examples of repeating units containing acid-labile groups mentioned above, repeating units represented by the following formula (a3) ​​(hereinafter also referred to as repeating unit a3) can be listed.

[1085] [Chemistry 439]

[1086]

[1087] 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. However, considering solvent solubility, a benzene ring with b1 of 0 is more ideal. b2 is 0, 1, 2, or 3 when b1 is 0, and 0, 1, 2, 3, 4, or 5 when b1 is 1. Considering raw material supply, b2 being 0, 1, 2, or 3 is more ideal, and 0, 1, or 2 is even more ideal.

[1088] In equation (a3), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Regarding R... A In this regard, hydrogen atoms or methyl groups are more ideal, with hydrogen atoms being even more ideal.

[1089] In equation (a3), X 3 For single bond, -C(=O)-O- or -C(=O)-N(H)-. These represent atomic bonds with carbon atoms in the main chain. Among them, single bonds, double bonds, and triple bonds are used to bond atoms to carbon atoms in the main chain. -C(=O)-O- is ideal, and a single bond is even more ideal.

[1090] In equation (a3), X 4 It 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 raw materials, a single bond, a carbonyl group, or a sulfonyl group is more ideal; considering the polar groups formed after the reaction, a single bond or a carbonyl group is more ideal.

[1091] 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 It is bonded to an adjacent carbon atom of the aromatic ring. X 5 and X 6 They can be the same or different, but considering the perspective of reactivity, X 5 and X 6 Ideally, all of them should be composed of oxygen atoms.

[1092] In equation (a3), R 22 and R 23Each hydrocarbon group consists of 1 to 20 carbon atoms, which may be hydrogen atoms or 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; 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; cyclohexenyl and other cyclounsaturated hydrocarbon groups with 3 to 20 carbon atoms; aryl groups with 6 to 20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1093] Also, R 22 and R 23 They can also bond with each other to form rings together with the carbon atoms they bond to. Specific examples of rings formed in this way 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. A portion of the -CH2- group in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1094] 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; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen carbonyl 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 group 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 ideal. The hydrocarbon group, as well as the hydrocarbon oxy, hydroxyl, and thioyl groups, can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include those related to R... 22 and R 23 The hydrocarbon groups represented are the same. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups 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 groups can be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, the hydrocarbon groups may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. When b2 is 2 or more, each R... 24 They can be the same or different.

[1095] Furthermore, when b2 is 2 or more, multiple R 24 They can also bond with each other, forming rings together with the carbon atoms of the aromatic rings they are bonded to. Specific examples of rings formed in this way 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 also contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1096] Regarding specific examples of the repeating unit a3, examples as shown below can be listed, 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 also be interchanged.

[1097] [Chemistry 440]

[1098]

[1099] [Chemistry 441]

[1100]

[1101] [Chemistry 442]

[1102]

[1103] [Chemistry 443]

[1104]

[1105] [Chemistry 444]

[1106]

[1107] [Chemistry 445]

[1108]

[1109] [Chemistry 446]

[1110]

[1111] [Chemistry 447]

[1112]

[1113] [Chemistry 448]

[1114]

[1115] [Chemistry 449]

[1116]

[1117] [Chemistry 450]

[1118]

[1119] [Chemistry 451]

[1120]

[1121] [Chemistry 452]

[1122]

[1123] [Chemistry 453]

[1124]

[1125] [Chemistry 454]

[1126]

[1127] [Chemistry 455]

[1128]

[1129] [Chemistry 456]

[1130]

[1131] [Chemistry 457]

[1132]

[1133] [Chemistry 458]

[1134]

[1135] [Chemistry 459]

[1136]

[1137] [Chemistry 460]

[1138]

[1139] [Chemistry 461]

[1140]

[1141] [Chemistry 462]

[1142]

[1143] [Chemistry 463]

[1144]

[1145] [Chemistry 464]

[1146]

[1147] [Chemistry 465]

[1148]

[1149] [Chemistry 466]

[1150]

[1151] [Chemistry 467]

[1152]

[1153] [Chemistry 468]

[1154]

[1155] [Chemistry 469]

[1156]

[1157] [Chemistry 470]

[1158]

[1159] [Chemistry 471]

[1160]

[1161] [Chemistry 472]

[1162]

[1163] [Chemistry 473]

[1164]

[1165] [Chemistry 474]

[1166]

[1167] [Chemistry 475]

[1168]

[1169] [Chemistry 476]

[1170]

[1171] [Chemistry 477]

[1172]

[1173] [Chemistry 478]

[1174]

[1175] [Chemistry 479]

[1176]

[1177] [Chemistry 480]

[1178]

[1179] [Chemistry 481]

[1180]

[1181] [Chemistry 482]

[1182]

[1183] [Chemistry 483]

[1184]

[1185] [Chemistry 484]

[1186]

[1187] [Chemistry 485]

[1188]

[1189] [Chemistry 486]

[1190]

[1191] [Chemistry 487]

[1192]

[1193] [Chemistry 488]

[1194]

[1195] [Chemistry 489]

[1196]

[1197] The aforementioned 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.).

[1198] [Chemistry 490]

[1199]

[1200] In equations (b1) and (b2), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 For single bonds, phenylene, naphthylene, -C(=O)-OY 11 -or -C(=O)-N(H)-Y 11 - The phenylene or naphthylene group may also be substituted with a saturated hydrocarbon group containing 1 to 10 carbon atoms, or a saturated hydrocarbon oxygen group containing 1 to 10 carbon atoms, or a halogen atom. 11 It is a saturated hydrocarbon group, phenylene, or naphthylene with 1 to 10 carbon atoms; the saturated hydrocarbon group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. 2 For single key or -C(=O)-O-. Represents the atomic bond with a carbon atom in the main chain. R 31It is a hydrogen atom, or a group containing at least one structure with 1 to 20 carbon atoms selected from hydroxyl groups other than phenolic hydroxyl groups, cyano groups, nitro groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, and carboxylic anhydrides (-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; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. c2 can be 2, 3, or 4, and 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. But 1 ≤ c1 + c2 ≤ 5.

[1201] Regarding specific examples of the repeating unit b1, examples as shown below can be listed, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1202] [Chemistry 491]

[1203]

[1204] [Chemistry 492]

[1205]

[1206] [Chemistry 493]

[1207]

[1208] [Chemistry 494]

[1209]

[1210] [Chemistry 495]

[1211]

[1212] [Chemistry 496]

[1213]

[1214] [Chemistry 497]

[1215]

[1216] [Chemistry 498]

[1217]

[1218] [Chemistry 499]

[1219]

[1220] [Chemical 500]

[1221]

[1222] [Chemical 501]

[1223]

[1224] [Chemical 502]

[1225]

[1226] [Chemical 503]

[1227]

[1228] [Chemical 504]

[1229]

[1230] [Chemical 505]

[1231]

[1232] [Chemical 506]

[1233]

[1234] [Chem. 507]

[1235]

[1236] [Chemical 508]

[1237]

[1238] [Chemical 509]

[1239]

[1240] [Chem.510]

[1241]

[1242] Regarding specific examples of the repeating unit b2, examples as shown below can be listed, but are not limited to these. Furthermore, in the following formula, R... A Same as above.

[1243] [Chem.511]

[1244]

[1245] [Chem.512]

[1246]

[1247] [Chem.513]

[1248]

[1249] [Chem.514]

[1250]

[1251] [Chem.515]

[1252]

[1253] Regarding repeating units b1 or b2, in ArF lithography, those with lactone rings as polar groups are more ideal, while in KrF lithography, EB lithography, and EUV lithography, those with phenolic sites are more ideal.

[1254] 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 units represented by formula (c2) (hereinafter also referred to as repeating unit c2.), the repeating units represented by formula (c3) (hereinafter also referred to as repeating unit c3.), the repeating units represented by formula (c4) (hereinafter also referred to as repeating unit c4.), and the repeating units represented by formula (c5) (hereinafter also referred to as repeating unit c5.).

[1255] [Chem.516]

[1256]

[1257] In equations (c1) to (c5), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It is a single bond or may have substituents. Z 2 For single bond, -C(=O)-OZ 21 -、 -C(=O)-N(H)-Z 21 -or -OZ 21 -. Z 21 It is an aliphatic hydrocarbon group, phenylene group, or a divalent group obtained by combining them, having 1 to 6 carbon atoms. It may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups. 3 It can be a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond.4 It can be 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; it 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. -C(=O)-OZ 51 -or -C(=O)-N(R)-Z 51 -. Z 51 R is an aliphatic hydrocarbon group, phenylene, or naphthylene, having 1 to 10 carbon atoms. This aliphatic hydrocarbon group may also contain a halogen atom, hydroxyl group, ether bond, ester bond, or lactone ring. R is a hydrogen atom, or may also contain a heteroatom and is a hydrocarbon group having 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. 7 Each is an independent single bond. -Z 71 -C(=O)-O-、 -C(=O)-N(R)-Z 71 -or -OZ 71 -. Z 71 It may also contain a 1-20 carbon-containing hydrocarbon group, which may also contain heteroatoms. R is the same as described above. Z 8 Each is an independent single bond. -Z 81 -C(=O)-O-、 -C(=O)-N(R)-Z 81 -or -OZ 81 -. Z 81 It may also contain a 1-20 carbon-containing hydrocarbon group, which may also contain 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)-Z91 -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. This represents the atomic bond with the carbon atoms in the main chain. Indicates with Z 1 Atomic bonds. Indicates with Z 6 Atomic bonds. Indicates with Z 7 Atomic bonds.

[1258] Z 21 Z 51 and Z 91 The aliphatic alkylene group represented can be 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.

[1259] Z 71 and Z 81 The expression may also contain heteroatoms and is a hydrocarbon group, which may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples are shown below, but are not limited to these.

[1260] [Chem.517]

[1261]

[1262] In the formula, the dashed lines represent atomic bonds.

[1263] In equation (c1), R 41 and R 42Each of these can be an independent hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; 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; cyclohexenyl and other cyclounsaturated hydrocarbon groups with 3 to 20 carbon atoms; 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, but aryl is preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, 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.

[1264] Also, R 41 and R 42 They can also bond to each other and form rings together with the sulfur atoms they bond to. In this case, specific examples of the aforementioned rings can be listed as follows.

[1265] [Chem.518]

[1266]

[1267] In the formula, the dashed line represents the intersection with Z. 4 Atomic bonds.

[1268] Specific examples of the cation in repeating unit c1 can be listed as shown below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1269] [Chem.519]

[1270]

[1271] [Chem.520]

[1272]

[1273] [Chem.521]

[1274]

[1275] [Chem.522]

[1276]

[1277] [Chem.523]

[1278]

[1279] [Chem.524]

[1280]

[1281] [Chem.525]

[1282]

[1283] [Chem.526]

[1284]

[1285] [Chem.527]

[1286]

[1287] [Chem.528]

[1288]

[1289] In equation (c1), M - The ions are non-nucleophilic relative ions. Among the aforementioned non-nucleophilic relative ions, halide ions, sulfonic acid anions, imide acid anions, and methylated acid anions are more ideal. Specific examples of halide ions include chloride ions and bromide ions. Specific examples of sulfonic acid anions (sulfonate ions) include fluoroalkyl sulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion, and nonafluorobutanesulfonate ion; aryl sulfonate ions such as toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, and 1,2,3,4,5-pentafluorobenzenesulfonate ion; and alkyl sulfonate ions such as methanesulfonate ion and butanesulfonate ion. Specific examples of the aforementioned imide acid anions (imide ions) include bis(trifluoromethylsulfonyl)imide ions, bis(perfluoroethylsulfonyl)imide ions, and bis(perfluorobutylsulfonyl)imide ions. Specific examples of the aforementioned methylated acid anions (methylated ions) include tris(trifluoromethylsulfonyl)methylated ions and tris(perfluoroethylsulfonyl)methylated ions.

[1290] Regarding other examples of the aforementioned non-nucleophilic relative ions, those that are the same as those exemplified in the specific examples of anions represented by formula (Z) can be listed.

[1291] For other examples of the aforementioned non-nucleophilic relative ions, anions represented by any of the following formulas (c1-1) to (c1-4) can be listed.

[1292] [Chem. 529]

[1293]

[1294] In equation (c1-1), R fa It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain fluorine atoms or heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed as R in formula (c1-1-1) described later. fa1 The hydrocarbon groups represented are the same as those shown. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. Similarly, some of the -CH2- group in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, the hydrocarbon groups 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, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1295] For anions represented by formula (c1-1), the one represented by formula (c1-1-1) is more ideal.

[1296] [Chem.530]

[1297]

[1298] In equation (c1-1-1), Q 1 and Q 2 Each group can be independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, but for improved solvent solubility, at least one of them being trifluoromethyl is preferred. m can be 0, 1, 2, 3, or 4, with 1 being particularly ideal. R fa1 It can also contain hydrocarbon groups with 1 to 40 carbon atoms and heteroatoms. Regarding the aforementioned heteroatoms, oxygen, nitrogen, sulfur, and halogen atoms are more ideal, with oxygen atoms being even more ideal. Regarding the aforementioned hydrocarbon groups, considering the need to obtain high resolution in the formation of fine patterns, those with 6 to 30 carbon atoms are particularly ideal.

[1299] In equation (c1-1-1), R fa1The hydrocarbon group represented by carbon atoms from 1 to 40 can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with carbon atoms from 1 to 40, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecanyl, and eicosyl; and alkyl groups with carbon atoms from 3 to 40, such as cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornel, norbornelmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl. Cyclic saturated hydrocarbon groups with 0 carbon atoms; unsaturated aliphatic hydrocarbon groups with 2 to 40 carbon atoms, such as 2-propenyl and 3-cyclohexenyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, and 9-fluorenyl; aralkyl groups with 7 to 40 carbon atoms, such as benzyl and diphenylmethyl; polycyclic hydrocarbon groups containing aromatic rings with 7 to 40 carbon atoms, such as 9,10-ethylbridged-9,10-dihydroanthrayl and 6,13-ethylbridged-6,13-dihydropentaphenyl; hydrocarbon groups with 17 to 40 carbon atoms having a steroid skeleton; and groups obtained by combining them.

[1300] 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. As a result, it may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Specific examples of hydrocarbon groups containing heteroatoms include tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidemethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, 3-oxocyclohexyl, etc.

[1301] In equation (c1-1-1), L a1 The bonds can be single bonds, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, or carbamate bonds, but from a synthetic point of view, ether bonds or ester bonds are more ideal, with ester bonds being even more ideal.

[1302] Specific examples of the anion represented by formula (c1-1) can be listed as shown below, but are not limited to these. Additionally, in the following formula, Q... 1 As mentioned above, Ac is an acetyl group.

[1303] [Chemistry 531]

[1304]

[1305] [Chemistry 532]

[1306]

[1307] [Chem.533]

[1308]

[1309] [Chemistry 534]

[1310]

[1311] [Chem.535]

[1312]

[1313] [Chemistry 536]

[1314]

[1315] [Chemistry 537]

[1316]

[1317] [Chem.538]

[1318]

[1319] [Chem.539]

[1320]

[1321] [Chem.540]

[1322]

[1323] [Chemistry 541]

[1324]

[1325] [Chemistry 542]

[1326]

[1327] Other specific examples of anions represented by formula (c1-1) include those described in paragraphs

[0042] to

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

[0015] to

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

[0145] and

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

[0022] to

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

[0224] of Japanese Patent Publication No. 7109178.

[1328] 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. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include those shown in formula (c1-1-1) for R... fa1 The hydrocarbon groups represented are the same. Regarding R... fb1 and R fb2 Ideally, it should be a straight-chain fluorinated alkyl group with fluorine atoms or 1 to 4 carbon atoms. Also, R fb1 and R fb2 Groups that can also bond with each other (-CF2-SO2-N) - -SO2-CF2-) together form a ring, at which point R fb1 and R fb2 In terms of the groups that can be obtained by mutual bonding, fluorinated ethylidene or fluorinated propyleneide are more ideal.

[1329] 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. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include those shown in formula (c1-1-1) for R... fa1 The hydrocarbon groups represented are the same. Regarding R... fc1 R fc2 and R fc3 Ideally, it should be a straight-chain fluorinated alkyl group with fluorine atoms or 1 to 4 carbon atoms. Also, R fc1 and R fc2 Groups that can also bond with each other (-CF2-SO2-C) - -SO2-CF2-) together form a ring, at which point R fc1 and R fc2 In terms of the groups that can be obtained by mutual bonding, fluorinated ethylidene or fluorinated propyleneide are more ideal.

[1330] In equation (c1-4), R fd It can be a hydrocarbon group with 1 to 40 carbon atoms, and 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 as R in formula (c1-1-1). fa1The hydrocarbon groups represented are the same as those shown. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. Similarly, some of the -CH2- group in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, the hydrocarbon groups 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, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1331] Specific examples of anions represented by formula (c1-4) can be listed as shown below, but are not limited to these.

[1332] [Chemistry 543]

[1333]

[1334] [Chemistry 544]

[1335]

[1336] Other specific examples of anions represented by formula (c1-4) include those described in paragraphs

[0050] to

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

[1337] In addition to the aforementioned examples of non-nucleophilic relative ions, anions having aromatic rings substituted with iodine or bromine atoms can also be cited. Specific examples of such anions can be represented by the following formula (c1-5).

[1338] [Chem.545]

[1339]

[1340] In equation (c1-5), x is 1, 2, or 3. y is 1, 2, 3, 4, or 5. z is 0, 1, 2, or 3. However, 1 ≤ y + z ≤ 5. y being 1, 2, or 3 is more ideal, with 2 or 3 being even more ideal. z being 0, 1, or 2 is more ideal.

[1341] In equation (c1-5), X BI It is an iodine atom or a bromine atom. When x and / or y are 2 or more, each X BI They can be the same or different.

[1342] In equation (c1-5), L 11 It can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond, carbamate bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms. Part of the -CH2- of this hydrocarbon group can also be replaced by an ether bond or ester bond. The aforementioned saturated hydrocarbon group can be linear, branched, or cyclic.

[1343] In equation (c1-5), L 12 When x is 1, it is a single bond or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms; when x is 2 or 3, it is a (x+1) valence hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms.

[1344] L 12 The carbon-numbered alkylene groups (C1-20) can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl diyl groups with 1-20 carbons, such as 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, and dodecane-1,12-diyl; cyclopentanediyl, cyclohexanediyl, norcamphenediyl, adamantanediyl, and tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3-20 carbon atoms, such as decanediyl; unsaturated aliphatic hydrocarbon groups with 2-20 carbon atoms, such as vinylene and propene-1,3-diyl; aryl groups with 6-20 carbon atoms, such as phenylene, naphthylene, and anthracenediyl; polycyclic hydrocarbon groups containing aromatic rings with 7-20 carbon atoms, such as 9,10-ethylbridged-9,10-dihydroanthracenediyl and 6,13-ethylbridged-6,13-dihydropentaphenyl; and groups obtained by combining them, etc.] 12 The (x+1) valence hydrocarbon group representing 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include groups obtained by removing one or two hydrogen atoms from the aforementioned examples of hydrocarbon groups representing 1 to 20 carbon atoms.

[1345] Furthermore, some or all of the hydrogen atoms in the aforementioned alkylene group and (x+1) valence hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned alkylene group and (x+1) valence hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1346] In equation (c1-5), L 13 It can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond.

[1347] In equation (c1-5), R feIt can be a hydroxyl group, carboxyl group, fluorine atom, chlorine atom, bromine atom, amino group, hydrocarbon group with 1 to 20 carbon atoms, hydrocarbon oxygen group with 1 to 20 carbon atoms, hydrocarbon sulfonyl group with 1 to 20 carbon atoms, hydrocarbon carbonyl group with 2 to 20 carbon atoms, hydrocarbon carbonyl group with 2 to 20 carbon atoms, or hydrocarbon sulfonyl group with 1 to 20 carbon atoms, -N(R feA (R) feB ), -N(R feC )-C(=O)-R feD or -N(R) feC )-C(=O)-OR feD The hydrocarbon group, hydrocarbon oxy group, hydrocarbon thio group, hydrocarbon carbonyl group, hydrocarbon oxy carbonyl group, hydrocarbon carbonyloxy group, and hydrocarbon sulfonyloxy group may also contain at least one selected from fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, amino group, ester bond, and ether bond. feA and R feB Each is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. R feC It is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms. R feD It can be an aliphatic hydrocarbon group with 1 to 16 carbon atoms, an aryl group with 6 to 12 carbon atoms, or an aralkyl group with 7 to 15 carbon atoms. It may also contain halogen atoms, hydroxyl groups, saturated alkyloxy groups with 1 to 6 carbon atoms, saturated alkylcarbonyl groups with 2 to 6 carbon atoms, or saturated alkylcarbonyloxy groups with 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned hydrocarbon group, alkyloxy group, alkylcarbonyl group, alkyloxycarbonyl group, alkylcarbonyloxy group, and alkylsulfonyloxy group can be linear, branched, or cyclic. When x and / or z are 2 or more, each R... fe They can be the same or different.

[1348] Among these, R fe In this regard, it is hydroxyl, -N(R) feC )-C(=O)-R feD -N(R) feC )-C(=O)-OR feD Fluorine atoms, chlorine atoms, bromine atoms, methyl groups, and methoxy groups are relatively ideal.

[1349] In equation (c1-5), Rf 11 ~Rf 14 Each of them is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of them is a fluorine atom or a trifluoromethyl group. Also, Rf 11 With Rf 12 They can also combine to form carbonyl groups. In particular, Rf 13 and Rf 14 Ideally, all atoms should be fluorine atoms.

[1350] Specific examples of the anion represented by formula (c1-5) include those shown below, but are not limited thereto. In addition, in the following formula, X BI is the same as described above.

[1351] [Chemical 546]

[1352]

[1353] [Chemical 547]

[1354]

[1355] [Chemical 548]

[1356]

[1357] [Chemical 549]

[1358]

[1359] [Chemical 550]

[1360]

[1361] [Chemical 551]

[1362]

[1363] [Chemical 552]

[1364]

[1365] [Chemical 553]

[1366]

[1367] [Chemical 554]

[1368]

[1369] [Chemical 555]

[1370]

[1371] [Chemical 556]

[1372]

[1373] [Chemical 557]

[1374]

[1375] [Chemical 558]

[1376]

[1377] [Chemical Formula 559]

[1378]

[1379] [Chemical Formula 560]

[1380]

[1381] [Chemical Formula 561]

[1382]

[1383] [Chemical Formula 562]

[1384]

[1385] [Chemical Formula 563]

[1386]

[1387] [Chemical Formula 564]

[1388]

[1389] [Chemical Formula 565]

[1390]

[1391] [Chemical Formula 566]

[1392]

[1393] [Chemical Formula 567]

[1394]

[1395] [Chemical Formula 568]

[1396]

[1397] [Chemical Formula 569]

[1398]

[1399] Regarding 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 / 122423, paragraphs

[0205] to

[0220] of Japanese Patent Application Publication No. 2023-123183, and paragraphs

[0170] to

[0178] of Japanese Patent Application Publication No. 2024-62406.

[0028] , Paragraphs from Japanese Patent Application Publication No. 2024-62407

[0022] ~

[0025] , Paragraphs from Japanese Patent Application Publication No. 2024-62408

[0026] ~

[0028] , Paragraphs from Japanese Patent Application Publication No. 2024-68156

[0028] ~

[0030] , Paragraphs from Japanese Patent Application Publication No. 2024-68157

[0026] ~

[0028] , Paragraphs from Japanese Patent Application Publication No. 2024-68158

[0028] ~

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

[0028] ~

[0030] , Paragraphs from Japanese Patent Application Publication No. 2024-72280

[0031] ~

[0033] Paragraphs from Japanese Patent Application Publication No. 2024-72281

[0023] ~

[0025] , Japanese Patent Application Publication No. 2024-77618

[0026] ~

[0029] , Japanese Patent Application Publication No. 2024-77619

[0020] ~

[0021] , Japanese Patent Application Publication No. 2024-80672

[0140] ~

[0143] , Japanese Patent Application Publication No. 2024-83303

[0023] ~

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

[0028] ~

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

[0030] ~

[0033] , Japan Paragraphs

[0028] to

[0030] of Japanese Patent Application Publication No. 2024-99502, paragraphs

[0030] to

[0032] of Japanese Patent Application Publication No. 2024-101557, paragraphs

[0025] to

[0027] of Japanese Patent Application Publication No. 2024-102842, paragraphs

[0033] to

[0035] of Japanese Patent Application Publication No. 2024-102843, paragraphs

[0021] to

[0022] of Japanese Patent Application Publication No. 2024-127832, paragraphs

[0169] to

[0172] of Japanese Patent Application Publication No. 2024-144354, and paragraphs

[0178] to

[0181] of Japanese Patent Application Publication No. 2024-144356.The authors described in paragraphs

[0040] to

[0143] of Japanese Patent Application Publication No. 2024-160436, paragraphs

[0030] to

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

[0157] to

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

[0227] to

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

[0253] to

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

[0309] to

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

[1400] Regarding the aforementioned non-nucleophilic relative ions, the anions of disulfonic acid described in Japanese Patent Application Publication No. 2015-206932, the anions of sulfonamides and sulfonamides described in International Publication No. 2020 / 158366 which are sulfonic acid on one side and different from it on the other side, and the anions of sulfonic acid on one side and carboxylic acid on the other side described in Japanese Patent Application Publication No. 2015-24989 can also be used.

[1401] In equations (c2) and (c3), d1 and d2 are each independently 0, 1, 2 or 3, but 1 is more ideal.

[1402] 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.

[1403] In equations (c2), (c3) and (c4), L 11 The bonds can be single bonds, ether bonds, ester bonds, carbonyl groups, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. Among these, from a synthetic point of view, ether bonds, ester bonds, and carbonyl groups are more ideal, with ester bonds and carbonyl groups being even more ideal.

[1404] 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 In order to increase the acid strength of the produced acid, fluorine atoms are preferred. Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, Rf is used to improve solvent solubility. 3 and Rf 4 Ideally, at least one of them should be trifluoromethyl.

[1405] In equation (c3), Rf 5 and Rf 6Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. However, Rf 5 and Rf 6 Not all of them are simultaneously hydrogen atoms. Among these, Rf... (The sentence is incomplete and requires more context to translate accurately.) 5 and Rf 6 Ideally, at least one of them should be trifluoromethyl.

[1406] 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, a fluorinated alkyl thio group having 1 to 6 carbon atoms, or a pentafluorothio group. Regarding Rf 7 For example, fluorine atoms, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, or difluoromethylthio are more ideal, with fluorine atoms, trifluoromethyl, or trifluoromethoxy being even more ideal. When e2 is 2, 3, or 4, each Rf 7 They can be the same or different.

[1407] In equation (c4), R 43 It is a hydrocarbon group with 1 to 20 carbon atoms other than fluorine atoms, or it may contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. For specific examples, those mentioned in the description of formula (1) regarding R can be listed. 1 and R 2 The hydrocarbon groups represented are those that are identical, but not limited to these. Also, when e3 is 2, 3, or 4, each R... 43 They can be the same or different.

[1408] Furthermore, when e3 is 2, 3, or 4, multiple R... 43 They can also bond with each other to form rings together with the carbon atoms they bond to. Specific examples of rings formed in this way include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1409] Specific examples of the anion in repeating unit c2 can be listed as shown below, but are not limited to these. Additionally, in the following formula, R... A As mentioned above, Me is a methyl group.

[1410] [Chemistry 570]

[1411]

[1412] [Chemistry 571]

[1413]

[1414] [Chemistry 572]

[1415]

[1416] [Chem.573]

[1417]

[1418] [Chemistry 574]

[1419]

[1420] [Chemistry 575]

[1421]

[1422] [Chemistry 576]

[1423]

[1424] [Chemistry 577]

[1425]

[1426] [Chem.578]

[1427]

[1428] [Chemistry 579]

[1429]

[1430] [Chem.580]

[1431]

[1432] [Chem.581]

[1433]

[1434] [Chem.582]

[1435]

[1436] As for other specific examples of the repeating unit c2, those described in Paragraphs

[0043] to

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

[0067] to

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

[0057] to

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

[0020] to

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

[0067] to

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

[0075] to

[0084] of Japanese Patent No. 7520258, Paragraphs

[0032] to

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

[0385] to

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

[0062] to

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

[1437] As for specific examples of the anion of the repeating unit c3, those shown below can be cited, but the present invention is not limited thereto. In addition, in the following formula, R A is the same as described above.

[1438] [Chemical Formula 583]

[1439]

[1440] [Chemical Formula 584]

[1441]

[1442] [Chemical Formula 585]

[1443]

[1444] [Chemical Formula 586]

[1445]

[1446] [Chemical Formula 587]

[1447]

[1448] [Chemical Formula 588]

[1449]

[1450] [Chemical Formula 589]

[1451]

[1452] [Chemical Formula 590]

[1453]

[1454] [Chem.591]

[1455]

[1456] [Chem. 592]

[1457]

[1458] [Chem.593]

[1459]

[1460] Specific examples of the anion in repeating unit c4 can be listed as shown below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1461] [Chem. 594]

[1462]

[1463] [Chem.595]

[1464]

[1465] [Chem.596]

[1466]

[1467] [Chem.597]

[1468]

[1469] [Chem.598]

[1470]

[1471] [Chem.599]

[1472]

[1473]

[600]

[1474]

[1475] [Chemical 601]

[1476]

[1477] [Chemical 602]

[1478]

[1479] [Chemical 603]

[1480]

[1481] [Chemical 604]

[1482]

[1483] [Chemical 605]

[1484]

[1485] [Chemical 606]

[1486]

[1487] [Chem.607]

[1488]

[1489] [Chemical 608]

[1490]

[1491] [Chemical 609]

[1492]

[1493] [Chemical 610]

[1494]

[1495] Other specific examples of the anion of the repeating unit c4 include those described in paragraphs

[0023] to

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

[0419] to

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

[1496] Specific examples of the anion in repeating unit c5 can be listed as shown below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1497] [Chem.611]

[1498]

[1499] In equations (c2) to (c5), A +The cation is a sulfonium cation. Among the aforementioned sulfonium cations, examples include sulfonium cations, monium cations, and ammonium cations, with sulfonium cations and monium cations being more ideal. Among the specific examples of the aforementioned sulfonium cations, examples include those exemplified as cations of 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, but are not limited to these.

[1500] Furthermore, regarding the aforementioned sulfonium cations, sulfonium cations represented by the formula (sulfo-1) are also more desirable.

[1501] [Chem.612]

[1502]

[1503] 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. However, considering solvent solubility, a benzene ring with f1 = 0 is more ideal. f2 is 0 or 1. When f2 is 0, it is a benzene ring; when f2 is 1, it is a naphthalene ring. However, considering solvent solubility, a benzene ring with f2 = 0 is more ideal. f3 is 0 or 1. When f3 is 0, it is a benzene ring; when f3 is 1, it is a naphthalene ring. However, considering solvent solubility, a benzene ring with f3 = 0 is more ideal.

[1504] In formula (sulfo-1), f4 can be 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption, especially for EUV. However, there is a concern that the solvent solubility will be reduced, leading to precipitation in the resist composition. Therefore, f4 of 0, 1, 2, or 3 is more ideal, with 0, 1, or 2 being even more ideal.

[1505] In formula (sulfo-1), f5 can be 0, 1, 2, 3, or 4. Considering raw material supply, f5 being 0, 1, 2, or 3 is ideal, with 0, 1, or 2 being even more ideal. f6 can be 0, 1, 2, 3, 4, 5, or 6. Considering raw material supply, f6 being 0, 1, 2, or 3 is ideal, with 0, 1, or 2 being even more ideal. f7 can be 0, 1, 2, 3, 4, 5, or 6. Considering raw material supply, f7 being 0, 1, 2, or 3 is ideal, with 0, 1, or 2 being even more ideal.

[1506] In formula (sulfo-1), f8 is 0, 1, or 2. Considering raw material supply, f8 being 0 or 1 is more ideal. f9 is 0, 1, or 2. Considering raw material supply, f9 being 0 or 1 is more ideal. f10 is 0, 1, or 2. Considering raw material supply, f10 being 0 or 1 is more ideal.

[1507] 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. However, considering the solvent solubility, a benzene ring with f11 of 0 is more ideal.

[1508] In formula (sulfo-1), f12 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption, especially for EUV. However, there is a concern that the solvent solubility will be reduced, leading to precipitation in the resist composition. Therefore, f12 of 0, 1, 2, or 3 is more ideal, with 0, 1, or 2 being even more ideal.

[1509] In formula (sulfo-1), f13 is 0, 1, or 2. From the perspective of raw material supply, f13 being 0 or 1 is more ideal. f14 is 0, 1, or 2. From a synthetic perspective, f14 being 0 or 1 is more ideal.

[1510] 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.

[1511] In formula (sulfo-1), R F1 ~R F3 Each R is independently a fluorine atom, a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group with 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group with 1 to 6 carbon atoms. Among these, trifluoromethyl, trifluoromethoxy, and trifluorothiomethoxy are more ideal. When f5 is 2, 3, or 4, each R F1 They can be the same or different. When f6 is 2, 3, 4, 5 or 6, each R F2 They can be the same or different. When f7 is 2, 3, 4, 5 or 6, each R F3 They can be the same or different.

[1512] In formula (sulfo-1), R ct1 ~R ct4 The halogen atom other than iodine and fluorine atoms, nitro, cyano, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. The hydrocarbon group, hydrocarbon oxy group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be cited as shown in the description of formula (1) regarding R. 1 and R2 The hydrocarbon groups represented are the same as those shown. Furthermore, some or all of the hydrogen atoms in the hydrocarbon groups, alkyl groups, and alkyl sulfides mentioned above may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon groups 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, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1513] Also, when f8 is 2, there are 2 Rs. ct1 They can be the same or different, 2 Rs ct1 They can also bond with each other and form rings together with the carbon atoms they bond with. When f9 is 2, there are 2 R atoms. ct2 They can be the same or different, 2 Rs ct2 They can also bond with each other and form rings together with the carbon atoms they bond with. When f10 is 2, there are 2 R atoms. ct3 They can be the same or different, 2 Rs ct3 They can also bond with each other and form rings together with the carbon atoms they bond with. When f13 is 2, there are 2 R atoms. ct4 They can be the same or different, 2 Rs ct4 They can also bond with each other to form rings together with the carbon atoms they bond to. Specific examples of rings formed in this way include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1514] Furthermore, the sulfonium cation represented by formula (sulfo-1) is directly bonded to S. + The aromatic rings can also bond with each other and with S + Together they form a ring. In this case, specific examples of the aforementioned ring structure can be given by the following expressions, etc.

[1515] [Chemistry 613]

[1516]

[1517] In the formula, the dashed lines represent atomic bonds.

[1518] In formula (sulfo-1), L C and L D Each bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. Among these, L... C In this regard, single bonds, ether bonds, ester bonds, or sulfonate bonds are more ideal, with ester bonds or sulfonate bonds being even more ideal. Regarding L... D In this regard, single bonds, ether bonds, or ester bonds are more ideal, with single bonds being the most desirable.

[1519] In formula (sulfo-1), X L2 A single-bonded or heteroatom-containing hydrocarbon group with 1 to 40 carbon atoms. The aforementioned hydrocarbon group can be linear, branched, or cyclic; specific examples include alkyldiyl, cyclic saturated hydrocarbon groups, and arylyl groups. Specific examples of the aforementioned heteroatom include oxygen, nitrogen, and sulfur atoms. Regarding X... L2 The specific examples that may also represent a hydrocarbon group containing 1 to 40 carbon atoms and containing heteroatoms can be cited as shown in the description of formula (Z) regarding X. L1 The example X, which may also contain a heteroatom of a hydrocarbon group having 1 to 40 carbon atoms, is exemplified by... L -0~X L -61. Among these, X L2 In other words, for X L -0~X L -22, X L -29~X L -34 and X L -47~X L -61 is ideal.

[1520] For sulfonium cations represented by formula (sulfo-1), those represented by formula (sulfo-1-1) are more ideal.

[1521] [Chemical 614]

[1522]

[1523] In the formula, f4~f10, f12~f14, R F1 ~R F3 R ct1 ~R ct4 L C L D and X L2 Same as above.

[1524] For sulfonium cations represented by formula (sulfo-1-1), those represented by formula (sulfo-1-2) are more ideal.

[1525] [Chemical 615]

[1526]

[1527] In the formula, f4~f10, R F1 ~R F3 and R ct1 ~R ct3 Same as above.

[1528] Specific examples of sulfonium cations represented by formula (sulfo-1) are shown below, but are not limited to these. Additionally, in the following formula, Me is a methyl group.

[1529] [Chem.616]

[1530]

[1531] [Chemistry 617]

[1532]

[1533] [Chem.618]

[1534]

[1535] [Chem.619]

[1536]

[1537] [Chem.620]

[1538]

[1539] [Chemistry 621]

[1540]

[1541] [Chemistry 622]

[1542]

[1543] [Chemistry 623]

[1544]

[1545] [Chemistry 624]

[1546]

[1547] [Chemical 625]

[1548]

[1549] [Chemistry 626]

[1550]

[1551] [Chemistry 627]

[1552]

[1553] [Chemistry 628]

[1554]

[1555] [Chemistry 629]

[1556]

[1557] [Chemistry 630]

[1558]

[1559] [Chemistry 631]

[1560]

[1561] [Chemistry 632]

[1562]

[1563] [Chemistry 633]

[1564]

[1565] [Chemistry 634]

[1566]

[1567] [Chemistry 635]

[1568]

[1569] [Transformation 636]

[1570]

[1571] [Chemistry 637]

[1572]

[1573] [Chemistry 638]

[1574]

[1575] [Chemistry 639]

[1576]

[1577] [Transformation 640]

[1578]

[1579] [Chemistry 641]

[1580]

[1581] [Chemistry 642]

[1582]

[1583] [Chemistry 643]

[1584]

[1585] Regarding specific examples of the aforementioned citric acid, those described in paragraph

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

[1586] For specific examples of the aforementioned ammonium cations, those represented by the following formula (am-1) can be listed.

[1587] [Chemistry 644]

[1588]

[1589] In equation (am-1), R ct5 ~R ct8 Each can be an independent hydrocarbon group with 1 to 40 carbon atoms, and 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 as those in the description of formula (1) regarding R. 1 and R 2 The hydrocarbon groups represented are the same as those shown.

[1590] Specific examples of ammonium cations represented by formula (am-1) can be listed as shown below, but are not limited to these.

[1591] [Chemistry 645]

[1592]

[1593] Regarding the specific structure of the repeating units c1 to c5, any combination of anions and cations as described above can be listed.

[1594] Among the repeating units c1 to c5, considering the control of acid diffusion, repeating units c2 to c5 are more ideal; considering the acid strength of the produced acid, repeating units c2, c4, and c5 are more ideal; and considering the solvent solubility, repeating unit c2 is even more ideal.

[1595] 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. As for repeating units d, there is no particular limitation as long as they have a structure in which one or two or more hydroxyl groups are protected and the protecting groups decompose and generate hydroxyl groups due to the action of acid, but it is more ideal to be represented by the following formula (d1).

[1596] [Transformation 646]

[1597]

[1598] 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 heteroatoms and is a hydrocarbon group with a carbon number of 1 to 30 and a (g+1) valence. R 52 It is an acid-labile group. g can be 1, 2, 3, or 4.

[1599] In equation (d1), R 52 The acid-insecure group can be any group that will deprotect and generate a hydroxyl group due to the action of an acid. R 52 The structure is not particularly limited, but acetal, ketal, hydrocarbon carbonyl, and hydrocarbon methoxy groups represented by formula (d2) are more ideal, especially hydrocarbon methoxy groups represented by formula (d2).

[1600] [Chemistry 647]

[1601]

[1602] In the formula, Represents an atomic bond. R 53 It consists of hydrocarbon groups with 1 to 15 carbon atoms.

[1603] Regarding R 52 For specific examples of the acid-unstable group represented, the hydrocarbon methoxy group represented by formula (d2), and the repeating unit d, examples can be listed as those that are the same as those illustrated in the description of the repeating unit d described in Japanese Patent Application Publication No. 2020-111564.

[1604] The aforementioned base polymer may also contain repeating units e derived from indene, benzofuran, benzothiophene, acenaphthene, crromone, coumarin, norbornadiene, or derivatives thereof. Specific examples of monomers providing repeating units e may be listed below, but are not limited to these.

[1605] [Chemistry 648]

[1606]

[1607] The aforementioned polymer may also contain a repeating unit f derived from indane, vinylpyridine or vinylcarbazole.

[1608] In the aforementioned polymer, the content ratios of the repeating units a1, a2, a3, b1, b2, c1 to c5, d, e and f are preferably 0 < a1 ≤ 0.8, 0 ≤ a2 ≤ 0.8, 0 ≤ a3 ≤ 0.6, 0 ≤ b1 ≤ 0.6, 0 ≤ b2 ≤ 0.6, 0 ≤ c1 ≤ 0.4, 0 ≤ c2 ≤ 0.4, 0 ≤ c3 ≤ 0.4, 0 ≤ c4 ≤ 0.4, 0 ≤ c5 ≤ 0.4, 0 ≤ d ≤ 0.5, 0 ≤ e ≤ 0.3 and 0 ≤ f ≤ 0.3, more preferably 0 < a1 ≤ 0.7, 0 ≤ a2 ≤ 0.7, 0 ≤ a3 ≤ 0.5, 0 ≤ b1 ≤ 0.5, 0 ≤ b2 ≤ 0.5, 0 ≤ c1 ≤ 0.3, 0 ≤ c2 ≤ 0.3, 0 ≤ c3 ≤ 0.3, 0 ≤ c4 ≤ 0.3, 0 ≤ c5 ≤ 0.3, 0 ≤ d ≤ 0.3, 0 ≤ e ≤ 0.3 and 0 ≤ f ≤ 0.3. However, a1 + a2 + a3 + b1 + b2 + c1 + c2 + c3 + c4 + c5 + d + e + f ≤ 1.0.

[1609] The weight average molecular weight (Mw) of the aforementioned polymer is preferably from 1,000 to 500,000, more preferably from 3,000 to 100,000. When Mw falls within this range, sufficient etching resistance can be obtained, and there is no risk of reduction in resolution caused by failure to secure the difference in dissolution rate before and after exposure. In addition, in the present invention, Mw is a polystyrene-equivalent measured value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as a solvent.

[1610] Regarding the molecular weight distribution (Mw / Mn) of the aforementioned polymer, since the influence of Mw / Mn tends to increase as patterns are regularly miniaturized, a narrow dispersion with Mw / Mn of 1.0 to 2.0 is preferable in order to obtain a resist composition that can be desirably used for fine pattern dimensions. When the value is within the aforementioned range, there are few low-molecular-weight and high-molecular-weight polymers, and there is no risk of finding foreign matter on the pattern or deterioration of the pattern shape after exposure.

[1611] Examples of the method for synthesizing the aforementioned polymer include a method in which a monomer providing the aforementioned repeating unit is added with a radical polymerization initiator in an organic solvent and heated to carry out polymerization.

[1612] Specific examples of organic solvents used in polymerization include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Specific examples of polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The ideal amount of these initiators, relative to the total monomers used in polymerization, is 0.01–25 mol%. The ideal reaction temperature is 50–150 °C, with 60–100 °C being more ideal. A reaction time of 2 to 24 hours is ideal, but from the perspective of production efficiency, 2 to 12 hours is even more ideal.

[1613] The aforementioned polymerization initiator can be added to the monomer solution before being supplied to the reactor, or the initiator solution can be prepared separately from the monomer solution and then supplied to the reactor independently. During the waiting time, there is a possibility that polymerization may occur due to free radicals generated by the initiator, resulting in the formation of ultrapolymers. Therefore, from a quality management perspective, it is ideal to prepare the monomer solution and initiator solution independently and add them dropwise. Acid-labile groups can be used directly in 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 this case, the amount of these chain transfer agents added relative to the total amount of monomers used for polymerization is ideally 0.01 to 20 mol%.

[1614] 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, and then deprotected by weak acids and water after polymerization. Alternatively, they can be replaced with acetyl, formyl, trimethylacetyl, etc., and then subjected to alkaline hydrolysis after polymerization.

[1615] When copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, hydroxystyrene or hydroxyvinylnaphthalene can be copolymerized with other monomers in an organic solvent by adding a free radical polymerization initiator and heating. Alternatively, acetoxystyrene or acetoxyvinylnaphthalene can be used, and the acetoxy groups can be deprotected by alkaline hydrolysis after polymerization to produce polyhydroxystyrene or hydroxyvinylnaphthalene.

[1616] For example, ammonia or triethylamine can be used as the base in alkaline hydrolysis. The ideal reaction temperature is -20 to 100°C, and more ideally 0 to 60°C. The ideal reaction time is 0.2 to 100 hours, and more ideally 0.5 to 20 hours.

[1617] In addition, the amount of each monomer in the aforementioned monomer solution can be appropriately set, for example, in a manner that would constitute a preferred content ratio for the aforementioned repeating unit.

[1618] The polymer obtained by the aforementioned manufacturing method can be used as the final product by the reaction solution obtained through the polymerization reaction, or the polymer solution can be added to a poor solvent and the powder obtained through refining steps such as reprecipitation to obtain powder can be used as the final product. However, considering the viewpoints of work efficiency and quality stability, it is more ideal to use the polymer solution obtained by dissolving the powder obtained through the refining step in a solvent as the final product.

[1619] Specific examples of solvents used at this time include ketones such as cyclohexanone and methyl-2-n-pentyl ketone, as described in paragraphs

[0144] to

[0145] of Japanese Patent Application Publication No. 2008-111103; 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.

[1620] In the aforementioned polymer solution, a polymer concentration of 0.01 to 30% by mass is ideal, and 0.1 to 20% by mass is even more ideal.

[1621] The aforementioned reaction solutions and polymer solutions are ideally suited for filtration using filter media. Filter media filtration effectively removes foreign matter and gels that could cause defects, thus ensuring consistent quality.

[1622] Regarding the materials used in the aforementioned filter media filtration, examples include fluorocarbon, cellulose, nylon, polyester, and hydrocarbon-based materials. However, in the filtration step involving the resist composition, filter media formed from fluorocarbon (such as Teflon, a registered trademark), polyethylene, polypropylene, or nylon are more ideal. The pore size of the filter media can be appropriately selected according to the target cleanliness level, ideally below 100 nm, and even more ideally below 20 nm. Furthermore, these filter media can be used individually or in combination. Regarding the filtration method, the solution can be passed through only once, but multiple filtrations through solution circulation are more ideal. The filtration steps can be performed in any order and number of times during the polymer manufacturing process; filtering the reaction solution, polymer solution, or both after the polymerization reaction is more ideal.

[1623] (B) A single base polymer may be used alone, or two or more polymers with different composition ratios, Mw and / or Mw / Mn ratios may be used in combination. Furthermore, (B) the base polymer may contain hydrides of ring-opening metathesis polymers in addition to the aforementioned polymers; in this regard, those described in Japanese Patent Application Publication No. 2003-66612 may be used.

[1624] [(C) Organic solvent]

[1625] The chemically amplified resist composition of the present invention may also contain an organic solvent as component (C). As for the organic solvent (C), there is no particular limitation as long as it can dissolve 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 mixed solvents thereof.

[1626] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, ethyl lactate, DAA, and their mixed solvents are particularly ideal as they have excellent solubility for the base polymer of component (B).

[1627] In the chemically amplified resist composition of the present invention, the content of (C) organic solvent is ideally 200-5000 parts by mass relative to 80 parts by mass of (B) base polymer, and more ideally 400-3500 parts by mass. (C) organic solvent can be used alone or in combination of two or more.

[1628] [(D) Quenching agent]

[1629] The chemically amplified resist composition of the present invention may also contain a quencher as component (D). Furthermore, the quencher referred to in the present invention is a material used to capture the strong acid generated by the photoacid generator in the chemically amplified resist composition, thereby preventing its diffusion to unexposed areas and forming the desired pattern. Additionally, the term "strong acid" refers to an acid with sufficient acidity to induce deprotection reactions in unstable acid groups.

[1630] For specific examples of (D) quenchers, onium salts represented by formulas (2) or (3) can be listed.

[1631] [Chemistry 649]

[1632]

[1633] In equation (2), R q1 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain hydrogen atoms or heteroatoms, but excludes the case where the hydrogen atom at the α-position of the sulfonic acid group is replaced by a fluorine atom or a fluoroalkyl group. In formula (3), Rq2 is a hydrocarbon group with 1 to 40 carbon atoms, which may contain hydrogen atoms or heteroatoms.

[1634] Regarding R q1 Specifically, the hydrocarbon groups representing 1 to 40 carbon atoms can be listed as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., which are alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl and adamantyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, the hydrocarbon groups may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc.]

[1635] Regarding R q2 Specifically, the hydrocarbon group represented, except for R q1 In addition to the substituents exemplified in the specific examples, other examples include fluorinated saturated hydrocarbon groups such as trifluoromethyl and trifluoroethyl, and fluorinated aryl groups such as pentafluorophenyl and 4-trifluoromethylphenyl.

[1636] Specific examples of the anions of the onium salts represented by equation (2) can be listed as shown below, but are not limited to these.

[1637] [Chemical 650]

[1638]

[1639] [Chemistry 651]

[1640]

[1641] [Chemistry 652]

[1642]

[1643] [Chemistry 653]

[1644]

[1645] [Chem. 654]

[1646]

[1647] Regarding other specific examples of the anion of the onium salt represented by formula (2), examples include those described in paragraphs

[0027] to

[0029] of Japanese Patent No. 6248882, paragraphs

[0029] to

[0034] of Japanese Patent No. 6648726, paragraphs

[0220] to

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

[0028] to

[0029] of Japanese Patent No. 7067271. The authors are those 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.

[1648] Specific examples of the anions of the onium salts represented by equation (3) can be listed as shown below, but are not limited to these.

[1649] [Chemistry 655]

[1650]

[1651] [Chemistry 656]

[1652]

[1653] [Chemistry 657]

[1654]

[1655] [Chemistry 658]

[1656]

[1657] [Chemistry 659]

[1658]

[1659] Other specific examples of onium salt anions represented by formula (3) include paragraphs

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

[0231] to

[0233] and

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

[0240] to

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

[0203] to

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

[0282] to

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

[0013] to

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

[0022] ~

[0024] of the Japanese JP 2022-141598, paragraphs

[0026] ~

[0031] of the Japanese JP 2023-018671, paragraphs

[0017] ~

[0018] of the Japanese JP 2023-062898, paragraphs

[0157] of the Japanese JP 2023-108593, paragraphs

[0147] of the Japanese JP 2024-040793, paragraphs

[0181] ~

[0194] of the Japanese JP 2024-067732, paragraphs

[0171] of the Japanese JP 2024-074267, paragraphs

[0029] ~

[0030] of the Japanese JP 2 Paragraphs from Japanese Patent Application Publication No. 024-074268

[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.

[1660] In equations (2) and (3), Mq + The cation is a sulfonium cation. Examples of sulfonium cations include sulfonium cations, monium cations, and ammonium cations. Examples of sulfonium cations include those exemplified as cations of 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), but are not limited to these. Examples of monium cations include those described in paragraph

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

[1661] For specific examples of onium salts represented by formula (2) or (3), any combination of anions and cations as described above can be listed. Furthermore, these onium salts can be readily prepared by ion exchange reactions using known organic chemical methods. Regarding ion exchange reactions, Japanese Patent Application Publication No. 2007-145797 can be referenced, for example.

[1662] The onium salts represented by formula (2) or (3) 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, a weak acid is defined as an acid that exhibits an acidity that cannot deprotect the acid-instable groups of units containing acid-instable groups used in the base polymer. The onium salts represented by formula (2) or (3) function as quenchers when used in combination with onium salt-type photoacid generators that have a conjugate base of a strong acid, such as α-fluorinated sulfonic acid, as a relative anion. That is, when an onium salt that produces a strong acid, such as α-fluorinated sulfonic acid, is mixed with an onium salt that produces a weak acid, such as unfluorinated sulfonic acid or carboxylic acid, if the strong acid generated from the photoacid generator due to high-energy radiation reacts with the onium salt having unreacted weak acid anions, the weak acid will be released due to salt exchange, generating an onium salt having strong acid anions. In this process, strong acids are exchanged for weaker acids with lower catalytic activity, so the acid appears to be deactivated and its diffusion can be controlled.

[1663] Furthermore, regarding the quencher (D), the onium salt having a sulfonium cation and a benzene oxide anion site in the same molecule as described in Japanese Patent No. 6848776, the onium salt having a sulfonium cation and a carboxylate anion site in the same molecule as described in Japanese Patent No. 6583136 and Japanese Patent Application Publication No. 2020-200311, and the onium salt having a monazine cation and a carboxylate anion site in the same molecule as described in Japanese Patent No. 6274755 can also be used.

[1664] Here, when the photoacid generator that produces a strong acid is an onium salt, as mentioned above, the strong acid produced by high-energy ray irradiation will be exchanged for a weak acid. However, on the other hand, it is believed that the weak acid produced by high-energy ray irradiation is not likely to react with the unreacted onium salt that produces a strong acid and undergo salt exchange. This is because onium cations readily form ion pairs with the anions of stronger acids.

[1665] When the chemically amplified resist composition of the present invention contains an onium salt represented by formula (2) or (3) as the (D) quencher, its content is preferably 0.1 to 20 parts by mass relative to 80 parts by mass of the (B) base polymer, and more preferably 0.1 to 10 parts by mass. If the content of the aforementioned onium salt-type quencher falls within the aforementioned range, the resolution is good and there is no risk of a significant decrease in sensitivity, which is therefore ideal. The onium salt represented by formula (2) or (3) can be used alone or in combination of two or more.

[1666] The chemically amplified resist composition of the present invention may also contain a nitrogen-containing compound as a (D) quencher. Specific examples of the aforementioned nitrogen-containing compounds include primary, secondary, or tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103, particularly amine compounds having hydroxyl, ether, ester, lactone ring, cyano, or sulfonate ester bonds. Also, compounds formed by protecting a primary or secondary amine with a carbamate group, as described in Japanese Patent Publication No. 3790649, are also examples. Furthermore, compounds having a structure in which any of the following coexists with an acid-instable group, such as a lactone ring, sulfonyl lactone ring, lactam ring, or sultam ring, as described in Japanese Patent Publication No. 7615989, are also examples.

[1667] Furthermore, regarding nitrogen-containing compounds, sulfonate sulfonates with nitrogen-containing substituents can also be used. This type of compound functions as a quencher in the unexposed area, while in the exposed area, it loses its quencher properties due to neutralization with the acid it generates, thus functioning as a so-called photodegrading base. By using a photodegrading base, the contrast between the exposed and unexposed areas can be enhanced. For example, Japanese Patent Application Laid-Open Nos. 2009-109595 and 2012-46501 can be referenced regarding photodegrading bases.

[1668] When the chemically amplified resist composition of the present invention contains a nitrogen-containing compound as a (D) quencher, its content is preferably 0.001 to 12 parts by mass relative to 80 parts by mass of the (B) base polymer, 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.

[1669] [(E) Other photoacid generating agents]

[1670] The chemically amplified resist composition of the present invention may also contain a photoacid generator (hereinafter also referred to as other photoacid generators) other than component (A) as component (E). As for the aforementioned other photoacid generators, there is no particular limitation as long as they are compounds that can generate strong acids when irradiated by high-energy rays. Ideal other photoacid generators can be represented by the following formulas (4) or (5).

[1671] [Chemistry 660]

[1672]

[1673] In equation (4), R 101 ~R 105 Each group consists 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. For specific examples of the aforementioned hydrocarbon groups, examples such as those mentioned in the explanation of formula (1) regarding R... 1 and R 2 The hydrocarbon groups represented are the same as those shown.

[1674] Regarding specific examples of sulfonium salt cations represented by formula (4), examples such as those exemplified by 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 examples of sulfonium cations represented by formula (sulfo-1) are provided, but these examples are not limited to these. Regarding specific examples of ferrous salt cations represented by formula (5), examples such as those described in paragraph

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

[1675] In equations (4) and (5), Xa -It is an anion of a strong acid. Specific examples of the aforementioned anions of strong acids can be represented by any of the formulas (c1-1) to (c1-5). Furthermore, aromatic sulfonic acid anions containing fluorine atoms described in paragraphs

[0029] to

[0034] of Japanese Patent No. 6648726, paragraphs

[0264] to

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

[0040] to

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

[1676] Furthermore, for other photoacid generators of component (E), the one represented by formula (6) is more ideal.

[1677] [Chemistry 661]

[1678]

[1679] In equation (6), R 201 and R 202 Each can be an independent hydrocarbon group with 1 to 30 carbon atoms, and may also contain heteroatoms. R 203 It can also contain a hydrocarbon group with 1 to 30 carbon atoms and a heteroatom. Also, R 201 R 202 and R 203 Any two of them can also bond to each other and form a ring together with the sulfur atoms they are bonded to.

[1680] R 201 and R 202 The hydrocarbon group represented has 1 to 30 carbon atoms and can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, oxanorbornel, and tricyclic [5.2.1.0]. 2,6] Decyl, adamantyl, and other cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms; phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, tert-butylnaphthyl, anthracene, and other aryl groups with 6 to 30 carbon atoms; groups obtained by combining them, etc. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[1681] R 203 The derivatized hydrocarbon group, representing 1 to 30 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, 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 -diyl and heptadecan-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, and halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned alkylene group can be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, it may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. Regarding the aforementioned heteroatoms, oxygen atoms are preferred.

[1682] In equation (6), L21 It is a hydrocarbon group with 1 to 20 carbon atoms, which may 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 include those related to R. 203 The analyte groups represented are the same.

[1683] In equation (6), X a X b X c and X d Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group. But X a X b X c and X d At least one of them is a fluorine atom or a trifluoromethyl group.

[1684] Regarding the photoacid generator represented by formula (6), the one represented by formula (6') is more ideal.

[1685] [Chem.662]

[1686]

[1687] In equation (6'), L 21 Same as above. X e It can be a hydrogen atom or a trifluoromethyl group, with trifluoromethyl being the more ideal. R 301 R 302 and R 303 Each hydrocarbon group consists independently of a hydrogen atom, or may contain heteroatoms, and has 1 to 20 carbon atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include those shown in formula (c1-1-1) for R... fa1 The hydrocarbon groups represented are identical. p and q are each independently 0, 1, 2, 3, 4 or 5, and r is 0, 1, 2, 3 or 4.

[1688] Regarding specific examples of photoacid generators represented by formula (6), examples that are the same as those exemplified in Japanese Patent Application Publication No. 2017-26980 for photoacid generators represented by formula (2) can be cited.

[1689] Among the aforementioned photoacid generators, those containing anions represented by formula (c1-1-1) or (c1-2) exhibit low acid diffusion and excellent solvent solubility, making them particularly desirable. Furthermore, those represented by formula (6') exhibit extremely low acid diffusion, making them particularly desirable.

[1690] When the chemically amplified resist composition of the present invention includes (E) other photoacid generating agents, the content of these agents is ideally 0.1 to 40 parts by mass relative to 80 parts by mass of the (B) base polymer, and more ideally 0.5 to 20 parts by mass. If the amount of photoacid generating agent added in component (E) falls within the aforementioned range, the resolution is good, and there is no risk of foreign matter formation after development or stripping of the resist film, which is therefore ideal. (E) Other photoacid generating agents can be used alone or in combination of two or more.

[1691] [(F) Surfactant]

[1692] The chemically amplified resist composition of the present invention may also contain a surfactant as component (F). Regarding the surfactant (F), it is preferable to be 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. For such surfactants, refer to those described in Japanese Patent Application Publication Nos. 2010-215608 and 2011-16746.

[1693] Regarding surfactants that are insoluble or poorly soluble in water and alkaline developing solutions, among the surfactants described in the aforementioned announcement, 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 the oxobutane ring-opening polymer represented by the following formula (surf-1) are particularly desirable.

[1694] [Chem.663]

[1695]

[1696] Here, R, Rf, A, B, C, m, and n are irrelevant to the foregoing description and only apply to formula (surf-1). R is an aliphatic group with 2 to 5 carbon atoms in a 2 to 4-valent configuration. Examples of divalent aliphatic groups include ethylene, 1,4-butylene, 1,2-propylene, 2,2-dimethyl-1,3-propylene, and 1,5-pentane, while examples of trivalent or tetravalent groups include the following.

[1697] [Chem.664]

[1698]

[1699] In the formula, the dashed lines represent atomic bonds, each of which is a partial structure derived from glycerol, trimethylolethane, trimethylolpropane, and neopentyl tertrol.

[1700] Among these, 1,4-butylene and 2,2-dimethyl-1,3-propylene are more ideal.

[1701] Rf is trifluoromethyl or pentafluoroethyl, preferably trifluoromethyl. m is an integer from 0 to 3, n is an integer from 1 to 4, and the sum of n and m is the valence of R, which 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 limited; 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 in US Patent No. 5,650,483, etc.

[1702] Surfactants that are insoluble or sparingly soluble in water but soluble in alkaline developing solutions are useful when no resist film is used during ArF lithography. They reduce water penetration and leaching by aligning with the surface of the resist film. Therefore, they are useful for inhibiting the leaching of water-soluble components from the resist film and reducing damage to the exposure equipment. Furthermore, they are soluble in alkaline aqueous solutions after exposure or post-exposure baking (PEB) and do not easily form foreign matter that could cause defects. These surfactants, being insoluble or sparingly soluble in water but soluble in alkaline developing solutions, are polymeric surfactants, also known as hydrophobic resins. Those with high water repellency and improved hydrophobicity are particularly desirable.

[1703] Specific examples of such polymeric surfactants include polymeric surfactants comprising at least one of the repeating units represented by formula (7A) (hereinafter also referred to as repeating unit 7A.), repeating units represented by formula (7B) (hereinafter also referred to as repeating unit 7B.), repeating units represented by formula (7C) (hereinafter also referred to as repeating unit 7C.), repeating units represented by formula (7D) (hereinafter also referred to as repeating unit 7D.), and repeating units represented by formula (7E) (hereinafter also referred to as repeating unit 7E.).

[1704] [Chem.665]

[1705]

[1706] 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 is 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. Rs3 Each is 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, ether bonds or carbonyl groups may also be present between the carbon-carbon bonds. R s4 It is a (u+1) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 20 carbon atoms. u is an integer from 1 to 3. s5 Each is independently a hydrogen atom, or -C(=O)-OR sa The group indicated by R. sa It is a fluorinated hydrocarbon group with 1 to 20 carbon atoms. R s6 It consists of a hydrocarbon group or a fluorinated hydrocarbon group with 1 to 15 carbon atoms, and there may also be ether bonds or carbonyl groups between the carbon-carbon bonds.

[1707] R s1 The hydrocarbon group represented has 1 to 10 carbon atoms, and it is ideally a saturated hydrocarbon group. It can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornel. Among these, those with 1 to 6 carbon atoms are preferred.

[1708] R s2 Ideally, the represented hydrocarbon group should be a saturated hydrocarbon group, which can be linear, branched, or cyclic. Specific examples include methylene, ethylene, propylene, butylene, and pentylene.

[1709] R s3 or R s6 The hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include aliphatic unsaturated hydrocarbon groups such as saturated hydrocarbon groups, alkenyl groups, and alkynyl groups, but saturated hydrocarbon groups are preferred. Regarding the aforementioned specific examples of saturated hydrocarbon groups, besides R... s1 In addition to the hydrocarbon groups exemplified, other examples include undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. Regarding R... s3 or R s6 In the case of fluorinated hydrocarbon groups, examples include groups in which some or all of the hydrogen atoms of the carbon atoms bonded to the aforementioned hydrocarbon group are replaced by fluorine atoms. As mentioned above, these carbon-carbon bonds may also be separated by ether bonds or carbonyl groups.

[1710] Regarding R s3Specific examples of the acid-labile group represented may include groups represented by the aforementioned formulas (AL-3) to (AL-5), trialkylsilyl groups each having an alkyl group of 1 to 6 carbon atoms, alkyl groups of 4 to 20 carbon atoms containing an oxygen-substituted group, and the like.

[1711] R s4 The (u+1)-valent hydrocarbon group or fluorinated hydrocarbon group represented may be linear, branched, or cyclic, and specific examples thereof include groups obtained by removing u hydrogen atoms from the aforementioned hydrocarbon group, fluorinated hydrocarbon group, or the like.

[1712] R sa The fluorinated hydrocarbon group represented is preferably a saturated one, and may be linear, branched, or cyclic. Specific examples thereof include those in which part or all of the hydrogen atoms of the aforementioned hydrocarbon group are substituted with fluorine atoms, and specific examples thereof include trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoro-1-propyl, 3,3,3-trifluoro-2-propyl, 2,2,3,3-tetrafluoropropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 2,2,3,3,4,4,4-heptafluorobutyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, and the like.

[1713] Specific examples of the repeating units 7A to 7E include those shown below, but are not limited thereto. In addition, in the following formulas, R B is the same as described above.

[1714] [Chemical Formula 666]

[1715]

[1716] [Chemical Formula 667]

[1717]

[1718] [Chemical Formula 668]

[1719]

[1720] [Chemical Formula 669]

[1721]

[1722] [Chemical Formula 670]

[1723]

[1724] [Chemical Formula 671]

[1725]

[1726] The aforementioned polymeric surfactants may also contain repeating units other than 7A-7E. Specific examples of other repeating units include repeating units derived from methacrylic acid, α-trifluoromethacrylic acid derivatives, etc. In polymeric surfactants, it is ideal for the content of repeating units 7A-7E to be 20 mol% or more, more ideally 60 mol% or more, and even more ideally 100 mol% among all repeating units.

[1727] For the aforementioned polymeric surfactants, a Mw of 1,000 to 500,000 is more ideal, and a Mw of 3,000 to 100,000 is even more ideal. A Mw / Mn ratio of 1.0 to 2.0 is more ideal, and a Mw / Mn ratio of 1.0 to 1.6 is even more ideal.

[1728] Regarding the method for synthesizing the aforementioned polymeric surfactants, examples include methods that involve providing monomers containing unsaturated bonds selected from at least one of repeating units 7A to 7E, and other repeating units as needed, adding a free radical initiator to an organic solvent, and heating to polymerize them. Specific examples of organic solvents used in polymerization include toluene, benzene, THF, diethyl ether, and dioxane. Specific examples of polymerization initiators include AIBN, 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. A reaction temperature of 50–100°C is ideal. A reaction time of 4–24 hours is ideal. Acid-labile groups can be used directly as introduced into the monomer, or they can be protected or partially protected after polymerization.

[1729] In the synthesis of 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 is ideally 0.01 to 10 mol% relative to the total molar number of monomers used for polymerization.

[1730] When the chemically amplified resist composition of the present invention contains (F) a surfactant, its content is ideally 0.1 to 50 parts by mass relative to 80 parts by mass of the (B) base polymer, and more ideally 0.5 to 10 parts by mass. If the content of (F) surfactant is 0.1 parts by mass or more, the receding contact angle between the resist film surface and water will be sufficiently improved; if it is 50 parts by mass or less, the dissolution rate of the developer relative to the resist film surface will be low, thus ensuring the height of the formed fine pattern. One type of (F) surfactant may be used alone, or two or more may be used in combination.

[1731] [(G) Other ingredients]

[1732] The chemically amplified resist composition of the present invention may, with regard to other components (G), contain compounds that decompose due to acid and produce acid (acid-increasing compounds), organic acid derivatives, fluorinated alcohols, and compounds with a solubility of Mw3000 or less that change due to acid (dissolution inhibitors). For the aforementioned acid-increasing compounds, refer to the compounds described in Japanese Patent Application Publication No. 2009-269953 or Japanese Patent Application Publication No. 2010-215608. When containing the aforementioned acid-increasing compounds, it is ideally 0 to 5 parts by mass relative to 80 parts by mass of the base polymer (B), and more ideally 0 to 3 parts by mass. If the content is too high, acid diffusion control becomes difficult, and there is a risk of degradation in resolvability and pattern shape. For the aforementioned organic acid derivatives, fluorinated alcohols, and dissolution inhibitors, refer to the compounds described in Japanese Patent Application Publication No. 2009-269953 or Japanese Patent Application Publication No. 2010-215608.

[1733] [Pattern Formation Method]

[1734] 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 radiation; and developing the aforementioned exposed resist film using a developing solution.

[1735] Regarding the aforementioned substrate, substrates such as those used for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.) or substrates used for mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.) can be used.

[1736] A resist film is formed by coating the aforementioned chemically amplified resist composition onto a substrate using methods such as spin coating, with a film thickness of 0.05 to 2 μm, and then pre-baking it on a hot plate at a temperature of 60 to 150°C for 1 to 10 minutes, or more preferably 80 to 140°C for 1 to 5 minutes.

[1737] Regarding the high-energy rays used in the exposure of resist films, examples include KrF excimer lasers, ArF excimer lasers, EB, and EUV with wavelengths of 3-15 nm. When using KrF excimer lasers, ArF excimer lasers, or EUV for exposure, a mask for forming the desired pattern can be used, with an ideal exposure dose of 1-200 mJ / cm². 2 Ideally, it should be 10~100mJ / cm 2 Irradiation is performed in this manner. When using EB, a mask to form the desired pattern can be used, or the exposure dose can ideally be 1~300 μC / cm.2 Ideally, it should be 10~200μC / cm 2 Irradiation is performed in this manner.

[1738] In addition to the usual 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 placed between the resist film and the projection lens. In this case, a protective film that is insoluble in water can also be used.

[1739] The aforementioned water-insoluble protective film is used to prevent leaching from the resist film and improve the hydrophobicity of the film surface. It can be broadly classified into two types. One type is the organic solvent-stripping type, which must be stripped with an organic solvent that does not dissolve the resist film before alkaline aqueous development. The other type is the alkaline aqueous solution-soluble type, which is soluble in alkaline developing solution and removes the protective film simultaneously with the removal of the soluble portion of the resist film. The latter is particularly ideally based on a polymer containing 1,1,1,3,3,3-hexafluoro-2-propanol residues that are water-insoluble but soluble in alkaline developing solution, and dissolved in an alcohol solvent with 4 or more carbon atoms, an ether solvent with 8 to 12 carbon atoms, or a mixture thereof. Alternatively, it can be a material obtained by dissolving the aforementioned water-insoluble but alkaline developing solution-soluble surfactant in an alcohol solvent with 4 or more carbon atoms, an ether solvent with 8 to 12 carbon atoms, or a mixture thereof.

[1740] After exposure, PEB can also be performed. PEB can be performed, for example, by heating on a hot plate at a temperature of 60-150°C for 1-5 minutes, or more ideally at 80-140°C for 1-3 minutes.

[1741] Development is performed, for example, using an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH) at a concentration of 0.1-5% by mass, or more preferably 2-3% by mass, and by conventional methods such as dip, immersion, or spraying for 0.1-3 minutes, or more preferably 0.5-2 minutes, thereby dissolving the exposed portion and forming the desired pattern on the substrate.

[1742] 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 after exposure to remove residual water from the film.

[1743] Then, pattern formation can also be achieved using a dual-patterning method. Examples of dual-patterning methods include: a trenching method where a substrate with a 1:3 trench pattern is processed by first exposure and etching, and then offset, and a second exposure is used to form a 1:3 trench pattern to create a 1:1 pattern; and a line method where a first substrate with a 1:3 isolation pattern is processed by first exposure and etching, and then offset, and a second exposure is used to form a second substrate with a 1:3 isolation pattern under the first substrate to create a 1:1 pattern with a pitch of half.

[1744] In the pattern forming method of the present invention, a negative tone development method in which an organic solvent is used instead of the aforementioned alkaline aqueous solution as the developer to dissolve the unexposed portion can also be used.

[1745] In the aforementioned organic solvent development, the developer may include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butyl acetate, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl valerate, methyl crotonate, etc. 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 formate, phenyl ethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, etc. These organic solvents can be used alone or in combination.

[1746] Example

[1747] The following describes the invention in detail with examples of synthesis, embodiments, and comparative examples, but the invention is not limited to the following embodiments. The apparatus used is as follows.

[1748] MALDI TOF-MS: S3000 manufactured by Nippon Electronics Co., Ltd.

[1749] [1] Synthesis of sulfonium salts

[1750] [Example 1-1] Synthesis of Sulfonium Salt PAG-1

[1751] [Chemistry 672]

[1752]

[1753] (1) Synthesis of intermediate In-1

[1754] Under nitrogen atmosphere, compounds SM-1 (25.0 g), SM-2 (43.5 g), DMAP (1.2 g), and dichloromethane (150 g) were added to a reaction vessel and cooled in an ice bath. While maintaining the temperature inside the reaction vessel below 20°C, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (24.9 g) was added in powder form. After addition, the temperature was raised to room temperature and allowed to mature for 12 hours. After maturation, water was added to stop the reaction, and a standard aqueous work-up was performed. The solvent was distilled off, and diisopropyl ether was added to wash away the residue, thereby obtaining intermediate In-1 57.7 g (92% yield) as an oil.

[1755] (2) Synthesis of PAG-1

[1756] Under nitrogen atmosphere, intermediate In-1 (12.6 g), compound SM-3 (10.6 g), dichloromethane (50 g), and water (30 g) were added. After stirring for 15 minutes, the organic layer was separated, sampled, and washed with water, followed by vacuum concentration. Methyl isobutyl ketone (50 g) was added to the concentrate for azeotropic dehydration, and diisopropyl ether was added to wash away the residue, thereby obtaining 18.0 g of the target compound PAG-1 (93% yield) in the form of an oil.

[1757] MALDI TOF-MS: POSITIVE M + 492 (equivalent to C) 25 H 22 F4NO3S + )

[1758] NEGATIVE M - 477 (equivalent to C) 23 H 13 F4O5S - )

[1759] [Examples 1-2~1-9] Synthesis of Sulfonium Salts PAG-2~PAG-9

[1760] Using the corresponding raw materials and known organic synthesis reactions, the sulfonium salts PAG-2 to PAG-9 represented by the following formulas were synthesized.

[1761] [Chemistry 673]

[1762]

[1763] [Chemistry 674]

[1764]

[1765] [Chemistry 675]

[1766]

[1767] [2] Synthesis of basic polymers

[1768] [Synthetic Example] Synthesis of basic polymers (P-1~P-5)

[1769] The monomers were combined and copolymerized in MEK as solvent. The reaction solution was added to hexane, and the precipitated solid was washed with hexane, separated, and dried to obtain the base polymers (P-1~P-5) with the compositions shown below. The composition of the obtained base polymers was determined by... 1 H-NMR confirmed Mw and Mw / Mn by GPC (solvent: THF, standard: polystyrene).

[1770] [Transformation 676]

[1771]

[1772] [3] Preparation of chemically amplified resist composition

[1773] [Examples 2-1 to 2-30, Comparative Examples 1-1 to 1-20]

[1774] The photoacid generators (PAG-1 to PAG-9), comparative photoacid generators (PAG-A to PAG-E), other photoacid generators (PAG-X), base polymers (P-1 to P-5), and quenchers (Q-1 to Q-4) composed of the sulfonium salts of the present invention, as shown in Tables 1 and 2 below, were dissolved in a solvent containing 0.01% by mass of surfactant A (Omnova Corporation) to prepare a solution. The solution was then filtered through a 0.2 μm Teflon (registered trademark) type filter media to prepare chemically amplified resist compositions (R-1 to R-30 and CR-1 to CR-20).

[1775] [Table 1]

[1776]

[1777] [Table 2]

[1778]

[1779] In Tables 1 and 2, the solvent, other photoacid generator PAG-X, comparative photoacid generators PAG-A to PAG-E, quenchers Q-1 to Q-4, and surfactant A are as follows.

[1780] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[1781] EL (ethyl lactate)

[1782] DAA (diacetone alcohol)

[1783] Other photoacid generators: PAG-X

[1784] [Transformation 677]

[1785]

[1786] • Comparison of photoacid generating agents: PAG-A~PAG-E

[1787] [Transformation 678]

[1788]

[1789] Quenching agents: Q-1~Q-4

[1790] [Chemistry 679]

[1791]

[1792] Surfactant A: 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane-tetrahydrofuran-2,2-dimethyl-1,3-propanediol copolymer (manufactured by Omnova).

[1793] [Transformation 680]

[1794]

[1795] a : (b + b') : (c + c') = 1 : 4~7 : 0.01~1 (molar ratio)

[1796] Mw = 1500

[1797] [4] Evaluation of EUV lithography (1)

[1798] [Examples 3-1 to 3-30, Comparative Examples 2-1 to 2-20]

[1799] The chemically amplified resist compositions (R-1 to R-30, CR-1 to CR-20) shown in Tables 1-3 were spin-coated onto a Si substrate containing a silicon spin-coating hard mask SHB-A940 (43% by mass silicon content) manufactured by Shin-Etsu Chemical 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 create a resist film with a thickness of 50 nm. The resist film was then subjected to exposure and focal length variation (exposure pitch: 1 mJ / cm) using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, dipole illumination). 2(Focus pitch: 0.020 μm) While exposing an LS pattern with a size of 18 nm and a pitch of 36 nm on the wafer, after exposure, PEB is performed for 60 seconds at the temperatures shown in Tables 3 and 4. Then, it is immersed and developed for 30 seconds with a 2.38% by mass TMAH aqueous solution, rinsed with a rinsing material containing surfactant, and vortexed to obtain a positive pattern.

[1800] The obtained LS patterns were observed using a Hitachi Advanced CD-SEM (CG6300), 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 patterns were evaluated. The results are shown in Tables 3 and 4.

[1801] [Sensitivity Evaluation]

[1802] Determine the optimal exposure Eop (mJ / cm) for obtaining an LS pattern with a linewidth of 18nm and a pitch of 36nm. 2 This value is used as the sensitivity. The smaller the value, the higher the sensitivity.

[1803] [EL Review]

[1804] Based on the exposure amount formed within ±10% (16.2~19.8nm) of the aforementioned LS pattern with an 18nm spacing width, the EL (unit: %) is calculated using the following formula. The larger this value, the better the performance.

[1805] EL(%)=(|E1-E2| / Eop)×100

[1806] E1: Provides optimal exposure for LS patterns with a linewidth of 16.2nm and a pitch of 36nm.

[1807] E2: Provides optimal exposure for LS patterns with a linewidth of 19.8nm and a pitch of 36nm.

[1808] Eop: Provides optimal exposure for LS patterns with a linewidth of 18nm and a pitch of 36nm.

[1809] [LWR Evaluation]

[1810] For the LS pattern obtained by Eop irradiation, the dimensions at 10 points along the long side of the line are measured, and the value of 3 times the standard deviation (σ) (3σ) is taken as the LWR. The smaller the value, the smaller the roughness, and a pattern with uniform linewidth can be obtained.

[1811] [DOF Rating]

[1812] In terms of depth of focus evaluation, the focal length range formed within ±10% (16.2~19.8nm) of the aforementioned LS pattern at a size of 18nm is determined. The larger the value, the wider the depth of focus.

[1813] [Collapse Limit Assessment of Line Patterns]

[1814] The line dimensions of each exposure at the optimal focal length for 10 of the aforementioned LS patterns were measured along the long side. The finest line dimension that could be obtained without collapse was taken as the collapse limit dimension. The smaller the value, the better the collapse limit.

[1815] [Evaluation of Development Defects]

[1816] For an LS pattern with a linewidth of 18nm and a pitch of 36nm formed using the aforementioned optimal exposure, a defect inspection device KLA2360 (trade name) manufactured by KLA-Tencor was used. The pixel size of the defect inspection device was set to 0.16μm, and the threshold was set to 20. Defects (number / cm) extracted from the differences caused by the overlap between the comparison image and the pixel unit were detected. 2 ), calculate the number of defects per unit area (defects / cm²) 2 Next, a defect evaluation is performed to classify and extract developing defects from all defects, and the number of developing defects per unit area (defects / cm²) is calculated. 2 Values ​​less than 0.5 are rated A, values ​​greater than 0.5 but less than 1.0 are rated B, values ​​greater than 1.0 but less than 5.0 are rated C, and values ​​greater than 5.0 are rated D. Smaller values ​​indicate better performance.

[1817] [Table 3]

[1818]

[1819] [Table 4]

[1820]

[1821] Based on the results shown in Tables 3 and 4, it can be understood that the chemically amplified resist composition containing the photoacid generator composed of the sulfonium salt 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's resistance to collapse is also strong during fine pattern formation. It was further confirmed that it also suppresses development defects. Therefore, the chemically amplified resist composition of the present invention is ideal as a material for EUV lithography.

[1822] [5] Evaluation of EUV lithography (2)

[1823] [Examples 4-1 to 4-30, Comparative Examples 3-1 to 3-20]

[1824] The chemically amplified resist compositions (R-1 to R-30, CR-1 to CR-20) shown in Tables 1-3 were spin-coated onto a Si substrate with a silicon-containing spin-coated hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., with a film thickness of 20 nm. The resist film was pre-baked at 105°C for 60 seconds using a heated plate to create a 50 nm thick resist film. The resist film was then exposed using an ASML NXE3400 EUV scanning exposure machine (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, a mask with a wafer-sized hole pattern of 46 nm pitch and +20% tolerance). PEB was performed for 60 seconds using a heated plate at the temperatures described 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.

[1825] Using a Hitachi Advanced CD-SEM (CG6300), the exposure was measured when the aperture size was 23 nm, and this was used as the sensitivity. Furthermore, the size of 50 apertures at this time was measured, and three times the standard deviation (σ) calculated from these results (3σ) was taken as the CDU. The results are shown in Tables 5 and 6.

[1826] [Table 5]

[1827]

[1828] [Table 6]

[1829]

[1830] Based on the results shown in Tables 5 and 6, it was confirmed that the chemically amplified resist composition containing the photoacid generator composed of the sulfonium salt 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; but 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; but 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; but 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, 1 ≤ n3 + n7 + n11 ≤ 6; R 1 R 2 and R 3 Each can independently be 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, 2 Rs 1 They can also bond with each other and form rings together with the carbon atoms they bond with; when n8 is 2, each R 2 They can be the same or different, 2 Rs 2 They can also bond with each other and form rings together with the carbon atoms they bond with; when n12 is 2, each R 3 They can be the same or different, 2 Rs 3 They can also bond with each other and form rings together with the carbon atoms they bond with; L 1 L 2 and L 3 Each is independently an ether bond, ester bond, or carbonate bond; when n3 is 2, each L 1 They can be the same or different; when n7 is 2, each L 2 They can be the same or different; when n11 is 2, each L 3 They can be the same or different; R AL1 R AL2 and R AL3 Each is an independent acid-labile group; when n3 is 2, each R AL1 They can be the same or different; when n7 is 2, each R AL2 They can be the same or different; when n11 is 2, each R AL3 They can be the same or different; Furthermore, the bond is to S + Two of the three aromatic rings can also bond to each other and form a ring together with the sulfur atoms they are bonded to; Z - It is an aromatic sulfonic acid anion having at least one cyclic structure.

2. The matte salt according to claim 1, 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 formula (AL-1) or (AL-2); In the formula, p1 and p2 are each independently 0 or 1; q1 and q2 are each 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 hydrocarbon group may be substituted with -O- or -S-. When the hydrocarbon group contains an aromatic ring, some or all of the hydrogen atoms in the aromatic ring may be substituted with halogen atoms, cyano, nitro, or alkyl groups containing halogen atoms with 1 to 4 carbon atoms, or alkoxy groups containing halogen atoms with 1 to 4 carbon atoms; furthermore, R L1 and R L2 They can also bond with each other to form a ring with the carbon atoms they bond to; a portion of the -CH2- in this ring can also be replaced by -O- or -S-; however, R L3 When R is a hydrogen atom L1 and R L2 The carbon atoms bonded to each other together form an alicyclic ring containing multiple bonds; furthermore, some of the hydrogen atoms in this alicyclic ring can 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 with each other, and the carbon atoms and L atoms bonded to them 4 Together they form a heterocyclic group with 3 to 20 carbon atoms, and part of the -CH2- of the heterocyclic group can also be replaced by -O- or -S-. L 4 It can be -O- or -S-; R La ~R Ld Each is an independent hydrocarbon group consisting of 1 to 20 carbon atoms, or may contain heteroatoms; Indicates with 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, m1 is 0 or 1; m2 is 0, 1, 2, 3, 4 or 5; m3 is 0, 1, 2, 3, 4 or 5; m4 is 0, 1, 2, 3, 4 or 5; however, when m1 is 0, 0 ≤ m2 + m3 + m4 ≤ 5, and when m1 is 1, 0 ≤ m2 + m3 + m4 ≤ 7. W is a hydrocarbon group with 6 to 40 carbon atoms containing at least one alicyclic or aromatic ring, and the hydrocarbon group may also contain heteroatoms; R F It consists of a fluorine atom, a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group with 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon thio group with 1 to 6 carbon atoms, or a pentafluorothio group; when m2 is 2, 3, or 4, each R F They can be the same or different; R 11 It can be a halogen atom other than fluorine, a hydroxyl group, a nitro 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 m3 is 2, 3 or 4, each R 11 Multiple Rs can be the same or different. 11 They can also bond with each other and form rings together with the carbon atoms they bond with; L A and L B Each bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond; X L1 It is a single bond, or may contain heteroatoms and a hydrocarbon group with 1 to 40 carbon atoms.

5. The matte salt according to claim 4, wherein, W is represented by the formula (W-1) or (W-2); In the formula, m5 is 0 or 1; m6 is 0, 1, 2, 3 or 4; m7 is 1, 2, 3 or 4; m8 is 0 or 1; m9 is 0 or 1; m10 is 0, 1, 2, 3 or 4; m11 is 0, 1, 2, 3 or 4. R 12 Each is an independent halogen atom other than a hydrogen atom or an iodine atom, or may contain a hydrocarbon group with 1 to 20 carbon atoms and heteroatoms; R 13 and R 14 Each is an independent hydrocarbon group consisting of 1 to 20 carbon atoms, a hydrogen atom, a halogen atom, or may also contain heteroatoms; R 15 ~R 19 Each is an independent hydrocarbon group consisting of 1 to 40 carbon atoms, which may be hydrogen atoms, halogen atoms, or heteroatoms; The dashed line indicates the L A Atomic bonds.

6. The matte salt according to claim 4, wherein, The anion is represented by the formula (Z1); In the formula, m1~m4, W, R F R 11 and L A Same as above.

7. A photoacid generator comprising a sulfonium salt according to any one of claims 1 to 6.

8. A chemically amplified resist composition comprising the photoacid generator according to claim 7.

9. The chemically amplified resist composition according to claim 8, 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 a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; X 1 It is a single bond, phenylene, naphthylene or -C(=O)-OX 11 - The phenylene or naphthylene group may also be substituted with a saturated hydrocarbon group containing 1 to 10 carbon atoms, or a saturated hydroxyl group containing 1 to 10 carbon atoms, or a halogen atom containing fluorine atoms; X 11 It is a saturated hydrocarbon group, phenylene or naphthylene with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, ether bond, ester bond or lactone ring; X 2 For single key or -C(=O)-O-; Indicates the atomic bond with the carbon atom in the main chain; R 21 It can be a halogen atom, cyano group, hydroxyl group, nitro group, pentafluorosulfur group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; when a1 is 2, 3 or 4, each R 21 They can be the same or different; AL 1 and AL 2 Each is an unstable acid group; a1 can be 0, 1, 2, 3 or 4; In the formula, b1 is 0 or 1; b2 is 0, 1, 2 or 3 when b1 is 0, and 0, 1, 2, 3, 4 or 5 when b1 is 1; R A It consists of hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups; X 3 For single bond, -C(=O)-O- or -C(=O)-N(H)-; Indicates the atomic bond with the 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; but X 4 and X 6 It is bonded to an adjacent carbon atom of the aromatic ring; R 22 and R 23 Each is an independent hydrocarbon group consisting of 1 to 20 carbon atoms, or may contain heteroatoms; also, R 22 and R 23 They can also bond with each other and form rings together with the carbon atoms they bond with; 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; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen carbonyl 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 Multiple Rs can be the same or different. 24 They can also bond with each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

10. The chemically amplified resist composition according to claim 9, wherein, The polymer contains repeating units represented by formula (b1) or (b2); In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Y 1 For single bonds, phenylene, naphthylene, -C(=O)-OY 11 -or -C(=O)-N(H)-Y 11 - The phenylene or naphthylene group may also be substituted with a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group containing fluorine atoms with 1 to 10 carbon atoms, a saturated hydrocarbon oxygen group containing fluorine atoms with 1 to 10 carbon atoms, or a halogen atom; Y 11 It is a saturated hydrocarbon group, phenylene or naphthylene with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, ether bond, ester bond or lactone ring; Y 2 For single key or -C(=O)-O-; Indicates the atomic bond with the carbon atom in the main chain; R 31 It is a hydrogen atom, or a group having at least one structure with 1 to 20 carbon atoms selected from hydroxyl groups other than phenolic hydroxyl groups, cyano groups, nitro groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, and carboxylic anhydrides (-C(=O)-OC(=O)-). R 32 The group can be a halogen atom, carboxyl group, nitro group, cyano group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, 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; but 1≤c1+c2≤5.

11. The chemically amplified resist composition according to claim 9, wherein, The polymer comprises at least one of the repeating units represented by formula (c1), formula (c2), formula (c3), formula (c4), and formula (c5). In the formula, d1 and d2 are each independently 0, 1, 2 or 3; e1 is 0 or 1; e2 is 0, 1, 2, 3 or 4; e3 is 0, 1, 2, 3 or 4; but when e1 is 0, 0 ≤ e2 + e3 ≤ 4, and when e1 is 1, 0 ≤ e2 + e3 ≤ 6; R A Each can be independently 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 bond, -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 can be 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; it 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. -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 containing heteroatoms; 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 an independent single bond. -Z 71 -C(=O)-O-、 -C(=O)-N(R)-Z 71 -or -OZ 71 -;Z 71 It may also contain a alkylene group with 1 to 20 carbon atoms; R is the same as described above; Z 8 Each is an independent single bond. -Z 81 -C(=O)-O-、 -C(=O)-N(R)-Z 81 -or -OZ 81 -;Z 81 It may also contain a alkylene group with 1 to 20 carbon atoms; 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 phenylene substituted with trifluoromethyl, having 1 to 6 carbon atoms; it may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; R is the same as described above; Indicates the atomic bond with the carbon atom in the main chain; Indicates with Z 1 atomic bonds; Indicates with Z 6 atomic bonds; Indicates with 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 is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; but Rf 5 and Rf 6 They are not all hydrogen atoms at the same time; 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 an independent hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms; furthermore, R 41 and R 42 They can also bond with each other and form rings together with the sulfur atoms they bond with; R 43 It can be a halogen atom other than fluorine, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; when e3 is 2, 3 or 4, each R 43 Multiple Rs can be the same or different. 43 They can also bond with each other and form rings together with the carbon atoms they bond with; M - It is a non-nucleophilic relative ion; A + It is a ium cation.

12. The chemically amplified resist composition according to claim 8 further comprises an organic solvent.

13. The chemically amplified resist composition according to claim 8, further comprising a quenching agent.

14. The chemically amplified resist composition according to claim 8, further comprising a photoacid generator other than the photoacid generator according to claim 7.

15. The chemically amplified resist composition according to claim 8, further comprising a surfactant.

16. 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 8; The resist film was exposed to high-energy radiation; and The exposed resist film was developed using a developer.

17. The pattern forming method according to claim 16, 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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