Chemically amplified negative resist composition and resist pattern forming method

Abstract

The invention relates to a chemically amplified negative resist composition and a resist pattern forming method. The present invention addresses the problem of providing: a chemically amplified negative resist composition which is capable of improving resolution during pattern formation and which is capable of obtaining a resist pattern having excellent LER and pattern loyalty; and a method for forming a resist pattern. The chemically amplified negative resist composition contains (A) a photoacid generator comprising an onium salt represented by the following formula (A), and (B) a base polymer comprising a polymer containing a repeating unit represented by the following formula (B1).

Description

Technical Field

[0001] This invention relates to a chemically amplified negative resist composition and a method for forming resist patterns. Background Technology

[0002] In recent years, with the increasing integration and speed of LSI (Light Separation Technology), the miniaturization of pattern regularity has also progressed rapidly. In the processing of patterns smaller than 0.2 μm, chemically amplified resist compositions primarily using acids as catalysts are employed. Furthermore, regarding exposure sources, high-energy rays such as ultraviolet light, far-ultraviolet light, and electron beams (EB) are used. EB lithography, in particular, has become indispensable for processing blank photomasks in the fabrication of photomasks used in semiconductor manufacturing, especially as a technique for ultra-fine processing.

[0003] Polymers containing a large number of aromatic backbones with acidic side chains, such as polyhydroxystyrene, are useful as resist compositions for KrF lithography using KrF excimer lasers. However, due to their large absorption of light near 200 nm, they are not used as resist compositions for ArF lithography using ArF excimer lasers. Nevertheless, they have become important materials for EB lithography resist compositions or extreme ultraviolet (EUV) lithography resist compositions, which are powerful techniques for forming patterns with smaller processing limits than those achieved by ArF excimer lasers, due to their high etch resistance.

[0004] In the fabrication of blank photomasks, surface materials such as chromium compound films (e.g., chromium oxide films deposited on the photomask substrate) can easily affect the pattern shape of chemically amplified resist films. Maintaining high resolution and etched shape, regardless of substrate type, while preserving the rectangular pattern outline of the resist film, has become a crucial performance characteristic. Furthermore, in recent years, to achieve miniaturization, MBMW (Multi-Beam Mask Writing) processes have been used in the fabrication of blank photomasks. In this case, low-sensitivity resist compositions (high-dose regions) that are advantageous for roughness are used, and the optimization of the resist composition in these high-dose regions has also attracted attention.

[0005] The resist compositions used in optical lithography include positive resists that dissolve the exposed area to form a pattern and negative resists that leave the exposed area intact to form a pattern. The choice between these is based on the desired shape of the resist pattern and is user-friendly. Chemically amplified negative resist compositions typically contain: a polymer dissolved in an aqueous alkaline developer; an acid-generating agent that decomposes upon exposure to light and produces acid; and a crosslinking agent that uses the acid as a catalyst to form crosslinks between polymers, making the polymer insoluble in the aforementioned developer (in some cases, the polymer and crosslinking agent are integrated). Additionally, a quencher is usually added to control the diffusion of acid generated during exposure.

[0006] Examples of alkali-soluble units constituting the polymers that dissolve in aqueous alkaline developers include units derived from phenols. Previously, many negative resist compositions of this type have been developed, particularly for exposure using KrF excimer lasers. However, they cannot be used with ArF excimer lasers at exposure wavelengths of 150–220 nm because the phenolic units lack light transmittance. However, in recent years, negative resist compositions for exposure methods using shorter wavelengths such as EB and EUV to obtain finer patterns have regained attention, as reported in patent documents 1, 2, and 3, for example.

[0007] Furthermore, as one of the acid generating agents, there is a sulfonate salt that produces sulfonic acid containing an aromatic group with iodine atoms as described in Patent Document 4. It is focused on enhancing the sensitivity in EUV lithography, and its function is mainly as a quencher for fluorinated alkyl sulfonic acid. However, the acid generating agent, especially the acid generating agent used in the negative resist composition based on polyhydroxystyrene in the EB drawing process during blank mask processing, has not been discussed.

[0008] Furthermore, in optical lithography, various improvements are made by altering the selection and combination of materials used in the resist composition, as well as processing conditions, in order to control sensitivity and pattern contours. One of the focuses of these improvements is addressing the problem of acid diffusion, which significantly affects the resolution of chemically amplified resist compositions.

[0009] Quenching agents, used to control acid diffusion, are essential components for improving the performance of resist compositions, especially resolution. Various quenching agents have been explored to date, and amines and weak acid onium salts are generally used. Patent Document 5 describes an example of a weak acid onium salt where the addition of triphenylsulfonate can create a good resist pattern with no T-top formation, minimal linewidth difference between isolated and dense patterns, and low standing waves. Patent Document 6 describes how the addition of ammonium sulfonate or ammonium carboxylate salts improves sensitivity, resolution, and exposure latitude. Furthermore, Patent Document 7 describes a resist composition for KrF and EB lithography containing a combination of photoacid generators that produce fluorine-containing carboxylic acids, exhibiting excellent resolution and improved process tolerances such as exposure latitude and depth of focus. Additionally, Patent Document 8 describes a resist composition for F2 lithography using an F2 laser containing a photoacid generator that produces fluorine-containing carboxylic acids, exhibiting excellent line edge roughness (LER) and improved trailing issues. These are used in KrF lithography, EB lithography, or F2 lithography.

[0010] Patent document 9 describes a positive photosensitive composition for ArF lithography containing carboxylic acid onium salts. These compositions function as quenchers by exchanging a strong acid (sulfonic acid) generated from a photoacid generator during exposure with a weak acid onium salt to form both a weak acid and a strong acid onium salt. The strong acid (sulfonic acid) with higher acidity is replaced by a weak acid (carboxylic acid), thereby inhibiting the acid decomposition reaction of unstable acid groups and reducing (controlling) the acid diffusion distance.

[0011] However, recent years have seen a demand for resist compositions that not only improve surface roughness but also achieve excellent line spacing (LS), isolated lines (IL), isolated spacing (IS), and dot pattern shape. Patent Document 10 describes a photoresist that produces a large volume of acid while suppressing acid diffusion, resulting in patterns with good resolution and surface roughness. However, a rounded corner defect has been observed in the dot pattern. Patent Document 11 proposes a photoresist that produces a non-fluorinated aromatic sulfonic acid with multiple large-volume norbornene groups; Patent Document 12 proposes a photoresist with a triarylbenzenesulfonic acid anionic structure; and Patent Document 13 proposes a photoresist that produces a non-fluorinated aromatic sulfonic acid incorporating an iodine-containing aromatic ring. While the intention is to increase the molecular weight of the produced acid by utilizing multiple alkyl substituents, aromatic rings, and iodine atoms to reduce acid diffusion, the suppression of acid diffusion is still unsatisfactory for the purpose of forming fine patterns, leaving room for further improvement.

[0012] Existing technical documents

[0013] Patent documents

[0014] [Patent Document 1] Japanese Patent Application Publication No. 2006-201532

[0015] [Patent Document 2] Japanese Patent Application Publication No. 2006-215180

[0016] [Patent Document 3] Japanese Patent Application Publication No. 2008-249762

[0017] [Patent Document 4] Japanese Patent No. 6645464

[0018] [Patent Document 5] Japanese Patent No. 3955384

[0019] [Patent Document 6] Japanese Patent Application Publication No. 11-327143

[0020] [Patent Document 7] Japanese Patent No. 4231622

[0021] [Patent Document 8] Japanese Patent No. 4116340

[0022] [Patent Document 9] Japanese Patent No. 4226803

[0023] [Patent Document 10] Japanese Patent No. 6248882

[0024] [Patent Document 11] Japanese Patent No. 7067271

[0025] [Patent Document 12] Japanese Patent No. 7032549

[0026] [Patent Document 13] Japanese Patent Application Publication No. 2023-177038 Summary of the Invention

[0027] [The problem that the invention aims to solve]

[0028] The present invention is made in view of the foregoing circumstances, and aims to provide a chemically amplified negative resist composition that can improve the resolution during pattern formation and obtain resist patterns with good LER and pattern fidelity, as well as a method for resist pattern formation.

[0029] [Methods for solving the problem]

[0030] After repeated and in-depth explorations to achieve the aforementioned objectives, the inventors obtained the following insights, and thus completed the present invention: When an aromatic sulfonic acid photoacid generator is introduced into the resist composition, and the aromatic ring with sulfonyl bonds and another aromatic ring structure containing a bulky substituent are bonded via sulfonamide bonds, thereby suppressing the rotational freedom of the aromatic sulfonic acid type onium salt as a photoacid generator, the acid generated by it will have appropriate acidity, and at the same time, it will suppress the excessive diffusion of acid, thereby obtaining a pattern with good resolution and low LER, and due to the appropriate anti-solution properties, a pattern with good rectangularity can be obtained.

[0031] That is, the present invention provides the following chemically amplified negative resist composition and resist patterning method.

[0032] 1. A chemically amplified negative resist composition, comprising:

[0033] (A) A photoacid generator, composed of an onium salt represented by formula (A), and

[0034] (B) Basic polymer, comprising a polymer containing repeating units represented by the following formula (B1).

[0035] [Chemistry 1]

[0036]

[0037] In the formula, n1 is 0 or 1. n2 is 1, 2, 3, 4 or 5 when n1 is 0, and 1, 2, 3, 4, 5, 6 or 7 when n1 is 1. n3 is 0 or 1. n4 is 0, 1, 2, 3 or 4. n5 is 0, 1, 2, 3 or 4. However, when n3 is 0, 0 ≤ n4 + n5 ≤ 4, and when n3 is 1, 0 ≤ n4 + n5 ≤ 6.

[0038] R 1 Each of the following is an iodine atom, or may contain heteroatoms, a branched or cyclic hydrocarbon group having 3 to 20 carbon atoms, and at least one R. 1 It is bonded to the carbon atom adjacent to the carbon atom bonded to S. When n2 is 2 or more, each R 1 They can be the same or different, and there are multiple Rs. 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0039] R 2 It is a hydrocarbon group with 1 to 20 carbon atoms, consisting of a halogen atom other than fluorine, or possibly containing heteroatoms other than fluorine. When n4 is 2, 3, or 4, each R 2 They can be the same or different, and there are multiple Rs. 2 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0040] R F It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated alkyl thio group having 1 to 6 carbon atoms. When n5 is 2, 3, or 4, each R F They can be the same or different.

[0041] Z + It is a ium cation.

[0042] [Chemistry 2]

[0043]

[0044] In the formula, a1 is 0 or 1. a2 is 0, 1 or 2. a3 is an integer that satisfies 0 ≤ a3 ≤ 5 + 2(a2) - a4. a4 is 1, 2 or 3.

[0045] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0046] R 11 It can be a halogen atom, nitro group, carboxyl group, a saturated hydrocarbon group with 1 to 6 carbon atoms that can also be substituted by a halogen atom, a saturated hydrocarbon carbonyl oxygen group with 1 to 6 carbon atoms that can also be substituted by a halogen atom, or a saturated hydrocarbon carbonyl oxygen group with 2 to 8 carbon atoms that can also be substituted by a halogen atom. When a3 is 2 or more, each R 11 They can be the same or different.

[0047] A 1 It is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms, and part of the -CH2- of the saturated hydrocarbon group can also be replaced by -O-.

[0048] 2. A chemically amplified negative resist composition as in 1, wherein the aforementioned onium salt is represented by the following formula (A1).

[0049] [Chemistry 3]

[0050]

[0051] In the formula, n2, n3, n4, n5, R 1 R 2 R F and Z + Same as above.

[0052] 3. A chemically amplified negative resist composition as described in 2, wherein the aforementioned onium salt is represented by the following formula (A2).

[0053] [Chemistry 4]

[0054]

[0055] In the formula, n3, n4, n5, R 1 R 2 R F and Z + Same as above.

[0056] 4. A chemically amplified negative resist composition as described in any of 1. to 3, wherein Z + It is a sulfonium cation represented by formula (Z-1) or a monazine cation represented by formula (Z-2).

[0057] [Chemistry 5]

[0058]

[0059] In the formula, R ct1 ~R ct5 Each group consists independently of a halogen atom or may contain heteroatoms and is a hydrocarbon group with 1 to 30 carbon atoms. Also, R ct1 and R ct2 They can also bond to each other and form rings together with the sulfur atoms they are bonded to.

[0060] 5. A chemically amplified negative resist composition as described in any of 1. to 3, wherein Z + The sulfonium cation is represented by the following formula (Z-3).

[0061] [Chemistry 6]

[0062]

[0063] In the formula, m1 is 0 or 1. m2 is 0 or 1. m3 is 0 or 1. m4 is 0, 1, 2, 3, or 4. m5 is 0, 1, 2, 3, or 4. m6 is 0, 1, 2, 3, 4, 5, or 6. m7 is 0, 1, 2, 3, 4, 5, or 6. m8 is 0, 1, or 2. m9 is 0, 1, or 2. m10 is 0, 1, or 2. m11 is 0 or 1. m12 is 0, 1, 2, 3, or 4. m13 is 0, 1, or 2. m14 is 0, 1, or 2. However, when m1 is 0, 0 ≤ m6 + m9 ≤ 4; when m1 is 1, 0 ≤ m6 + m9 ≤ 6. When m2 is 0, 0 ≤ m7 + m10 ≤ 4; when m2 is 1, 0 ≤ m7 + m10 ≤ 6. When m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4; when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6. When m11 is 0, 0 ≤ m12 + m13 ≤ 4; when m11 is 1, 0 ≤ m12 + m13 ≤ 6. Also, m4 + m12 ≥ 1.

[0064] R F1 ~R F3 Each R is independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms with an oxygen atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. When m5 is 2, 3 or 4, each R F1 They can be the same or different. When m6 is 2, 3, 4, 5 or 6, each R... F2 They can be the same or different. When m7 is 2, 3, 4, 5 or 6, each R... F3 They can be the same or different.

[0065] R ct6 ~R ct9It can be a halogen atom other than iodine and fluorine atoms, a nitro group, a cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. When m8 is 2, there are 2 R groups. ct6 They can be the same or different, and there are 2 Rs. ct6 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m9 is 2, there are 2 R atoms. ct7 They can be the same or different, and there are 2 Rs. ct7 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m10 is 2, the two R atoms... ct8 They can be the same or different, and there are 2 Rs. ct8 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m13 is 2, there are 2 R atoms. ct9 They can be the same or different, and there are 2 Rs. ct9 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0066] Furthermore, S directly bonded to the sulfonium cation + The aromatic rings can also bond with each other and with S + Together they form a ring.

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

[0068] X L It is a single bond, or may contain a heteroatom and a hydrocarbon group with 1 to 40 carbon atoms.

[0069] 6. A chemically amplified negative resist composition as described in any one of 1 to 5, wherein the aforementioned polymer further contains at least one repeating unit selected from the repeating units represented by formula (B2) and formula (B3).

[0070] [Chemistry 7]

[0071]

[0072] In the formula, b1 is 0 or 1. b2 is 0, 1 or 2. b3 is an integer satisfying 0 ≤ b3 ≤ 5 + 2(b2) - b4. b4 is 1, 2 or 3. b5 is 0, 1 or 2. b6 is 1 or 2.

[0073] R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0074] R 21It is a hydrocarbon group with 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms. When b3 is 2 or more, each R 21 They can be the same or different.

[0075] R 22 and R 23 Each of the following groups is independently composed of a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may also be substituted by a hydroxyl group or a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, and the aryl group may also have substituents. However, R 22 and R 23 It cannot simultaneously be a hydrogen atom. Also, R 22 and R 23 They can also bond to each other and form a ring together with the carbon atoms they are bonded to, and part of the -CH2- in this ring can be replaced by -O- or -S-. When b4 is 2 or 3, each R 22 They can be the same or different. Also, when b4 is 2 or 3, each R... 23 They can be the same or different.

[0076] R 31 It is a hydrocarbon group with 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms. When b5 is 2, each R 31 They can be the same or different.

[0077] R 32 and R 33 Each of the following groups is independently composed of a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may also be substituted by a hydroxyl group or a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, and the aryl group may also have substituents. However, R 32 and R 33 It cannot simultaneously be a hydrogen atom. Also, R 32 and R 33 They can also bond to each other and form a ring together with the carbon atoms they are bonded to, and part of the -CH2- in this ring can be replaced by -O- or -S-. When b6 is 2, each R 32 They can be the same or different. Also, when b6 is 2, each R... 33 They can be the same or different.

[0078] A 2 It is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms, and part of the -CH2- of the saturated hydrocarbon group can also be replaced by -O-.

[0079] W 1 and W 2 Each of the following groups is independently composed of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon carbonyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the aryl group may also have substituents. When b4 is 2 or 3, each W 1They can be the same or different. Also, when b6 is 2, each W... 2 They can be the same or different.

[0080] 7. A chemically amplified negative resist composition as described in any one of 1 to 6, wherein the aforementioned polymer further contains at least one repeating unit selected from the repeating unit represented by formula (B4), the repeating unit represented by formula (B5), and the repeating unit represented by formula (B6).

[0081] [Chemistry 8]

[0082]

[0083] In the formula, c and d are independently 0, 1, 2, 3 or 4. e1 is 0 or 1. e2 is 0, 1 or 2. e3 is 0, 1, 2, 3, 4 or 5.

[0084] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0085] R 41 and R 42 Each R can be independently a hydroxyl group, a halogen atom, a saturated hydrocarbon group with 1 to 8 carbon atoms that can also be substituted by a halogen atom, a saturated hydrocarbon carbonyl group with 1 to 8 carbon atoms that can also be substituted by a halogen atom, or a saturated hydrocarbon carbonyl group with 2 to 8 carbon atoms that can also be substituted by a halogen atom. When c is 2, 3, or 4, each R 41 They can be the same or different. When d is 2, 3, or 4, each R... 42 They can be the same or different.

[0086] R 43 It can be a saturated hydrocarbon group with 1 to 20 carbon atoms, a saturated hydrocarbon oxy group with 1 to 20 carbon atoms, a saturated hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms, a saturated hydrocarbon oxy hydrocarbon group with 2 to 20 carbon atoms, a saturated hydrocarbon thio hydrocarbon group with 2 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, a saturated hydrocarbon sulfinyl group with 1 to 20 carbon atoms, or a saturated hydrocarbon sulfonyl group with 1 to 20 carbon atoms. When e3 is 2, 3, 4, or 5, each R 43 They can be the same or different.

[0087] A 3 It is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms, and part of the -CH2- of the saturated hydrocarbon group can also be replaced by -O-.

[0088] 8. The chemically amplified negative resist composition of 6, wherein the polymer contains at least one repeating unit selected from the repeating unit represented by formula (B7), the repeating unit represented by formula (B8), the repeating unit represented by formula (B9), the repeating unit represented by formula (B10), and the repeating unit represented by formula (B11).

[0089] [Chemistry 9]

[0090]

[0091] In the formula, f1 and f2 are independently 0, 1, 2 or 3. g1 is 0 or 1. g2 is 0, 1, 2, 3 or 4. g3 is 0, 1, 2, 3 or 4. However, when g1 is 0, 0 ≤ g2 + g3 ≤ 4, and when g1 is 1, 0 ≤ g2 + g3 ≤ 6.

[0092] R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0093] Z 1 It is a single bond or may have substituents.

[0094] Z 2 For single bonds, **-C(=O)-OZ 21 -、**-C(=O)-NH-Z 21 -or**-OZ 21 -. Z 21 It is an aliphatic alkylene group, phenylene group, or a divalent group obtained by combining them, having 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups.

[0095] Z 3 It can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0096] Z 4 It is a single bond, or an aliphatic alkylene group with 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups.

[0097] Z 5 Each can be a single bond, or may have substituents such as phenylene, naphthylene, or *-C(=O)-OZ. 51 -. Z 51 It is an aliphatic alkylene group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the aliphatic alkylene group may also contain halogen atoms, hydroxyl groups, ether bonds, ester bonds, or lactone rings.

[0098] Z 6 It can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0099] Z 7 Each is independently a single bond, ***-Z 71 -C(=O)-O-、***-C(=O)-NH-Z 71 -or ***-OZ71 -. Z 71 It may also contain heteroatoms and alkylene groups with 1 to 20 carbon atoms.

[0100] Z 8 Each is independently a single bond, ****-Z 81 -C(=O)-O-、****-C(=O)-NH-Z 81 -or ****-OZ 81 -. Z 81 It may also contain heteroatoms and alkylene groups with 1 to 20 carbon atoms.

[0101] Z 9 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, *-C(=O)-OZ 91 -、*-C(=O)-N(H)-Z 91 -or *-OZ 91 -. Z 91 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or phenylene substituted with trifluoromethyl, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group.

[0102] * indicates an atomic bond with a carbon atom in the main chain. ** indicates an atomic bond with Z. 1 The atomic bonds. *** indicates the relationship between Z and 6 Atomic bonds. **** represents the bond between Z and Z. 7 Atomic bonds.

[0103] L 1 It can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, sulfonamide bond, carbonate bond or carbamate bond.

[0104] Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms.

[0105] 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.

[0106] Rf 5 and Rf 6 Each can be independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. However, all Rf 5 and Rf 6 It cannot be both hydrogen atoms at the same time.

[0107] Rf 7It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated alkyl thio group having 1 to 6 carbon atoms. When g2 is 2, 3, or 4, each Rf 7 They can be the same or different.

[0108] R 51 and R 52 Each can be independently a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms. Also, R 51 and R 52 They can also bond to each other and form rings together with the sulfur atoms they are bonded to.

[0109] R 53 It is a halogen atom other than fluorine, or may contain a hydrocarbon group with 1 to 20 carbon atoms and heteroatoms. When g3 is 2, 3, or 4, each R 53 They can be the same or different, and there are multiple Rs. 53 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0110] M - It is a non-nucleophilic relative ion.

[0111] A + It is a ium cation.

[0112] 9. A chemically amplified negative resist composition as described in 8, wherein the aforementioned polymer contains repeating units represented by formula (B1-1), repeating units represented by formula (B2-1), (B2-2) or (B3-1), and repeating units represented by formula (B8-1).

[0113] [Chemistry 10]

[0114]

[0115] In the formula, a4, b4, b6, and R A R 22 R 23 R 32 R 33 and A + Same as above.

[0116] R HF It can be a hydrogen atom or a trifluoromethyl group.

[0117] Z 10 For single key or *****-Z 101 -C(=O)-O-。 Z 101 It can also contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. ***** represents the atomic bond of the oxygen atom in the formula.

[0118] 10. A chemically amplified negative resist composition as in 8 or 9, wherein the base polymer (B) comprises a polymer that further contains repeating units represented by formula (B1) and repeating units represented by formula (B2) or (B3), and does not contain repeating units represented by formulas (B7) to (B11).

[0119] 11. A chemically amplified negative resist composition as described in any one of 1. to 10, wherein the content of repeating units having an aromatic ring skeleton in all repeating units of the aforementioned base polymer is 60 mol% or more.

[0120] 12. Any chemically amplified negative resist composition as described in 1 to 11, further contains (C) a crosslinking agent.

[0121] 13. A chemically amplified negative resist composition as described in any of 1. to 11, which does not contain a crosslinking agent.

[0122] 14. The chemically amplified negative resist composition of any one of 1. to 13. further comprises (D) a fluorine-containing polymer, the (D) fluorine-containing polymer comprising at least one repeating unit selected from the repeating unit represented by (D1), the repeating unit represented by (D2), the repeating unit represented by (D3) and the repeating unit represented by (D4), and may also further comprise at least one repeating unit selected from the repeating unit represented by (D5) and the repeating unit represented by (D6).

[0123] [Chemistry 11]

[0124]

[0125] In the formula, j1 is 1, 2, or 3. j2 is an integer satisfying 0 ≤ j2 ≤ 5 + 2(j3) - j1. j3 is 0 or 1. k is 1, 2, or 3.

[0126] R B Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0127] R C Each can be a hydrogen atom or a methyl group, independently.

[0128] R 101 R 102 R 104 and R 105 Each is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.

[0129] R 103 R 106 R 107 and R 108Each of the following is independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a fluorinated hydrocarbon group having 1 to 15 carbon atoms, or an acid-unstable group, and R 103 R 106 R 107 and R 108 When the group is a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group can also be inserted between the carbon-carbon bonds.

[0130] R 109 A straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms, which may be hydrogen atoms or may have heteroatom-containing groups inserted between carbon-carbon bonds.

[0131] R 110 It can also be a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms, in which heteroatoms are inserted between carbon-carbon bonds.

[0132] R 111 It is a saturated hydrocarbon group with 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and part of the -CH2- of the aforementioned saturated hydrocarbon group may also be replaced by an ester bond or an ether bond.

[0133] X 1 It is a (k+1) valence hydrocarbon group with 1 to 20 carbon atoms or a (k+1) valence fluorinated hydrocarbon group with 1 to 20 carbon atoms.

[0134] X 2 It is a single bond, *-C(=O)-O- or *-C(=O)-NH-. * represents an atomic bond with a carbon atom in the main chain.

[0135] X 3 For single bonds, -O-, *-C(=O)-OX 31 -X 32 -or *-C(=O)-NH-X 31 -X 32 -. X 31 It is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms. X 32 It is a single bond, ester bond, ether bond, or sulfonamide bond. * indicates an atomic bond with a carbon atom in the main chain.

[0136] 15. Any chemically amplified negative resist composition as described in any of 1. to 14, further contains (E) a quencher.

[0137] 16. A chemically amplified negative resist composition as in 15, wherein the content ratio of (A) photoacid generator to (E) quencher is less than 6 by mass.

[0138] 17. The chemically amplified negative resist composition of any one of 1. to 16. also contains (F) organic solvent.

[0139] 18. Any chemically amplified negative resist composition, such as any one of 1. to 17., also contains a photoacid generator other than (G)(A) component.

[0140] 19. A method for forming a resist pattern, comprising the following steps:

[0141] A resist film is formed on a substrate using a chemically amplified negative resist composition as described in any of 1. to 18.

[0142] The pattern was irradiated with high-energy rays onto the aforementioned resist film, and

[0143] The resist film that has been irradiated with the aforementioned pattern is developed using an alkaline developer.

[0144] 20. The method for forming a resist pattern as described in 19, wherein the aforementioned high-energy rays are extreme ultraviolet rays or electron beams with wavelengths of 3 to 15 nm.

[0145] 21. A method for forming a resist pattern as described in 19 or 20, wherein the outermost surface of the aforementioned substrate is composed of a material containing at least one selected from chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten, and tin.

[0146] 22. A method for forming a resist pattern as described in any one of 19 to 21, wherein the aforementioned substrate is a transmissive or reflective blank mask.

[0147] 23. A transmissive or reflective blank mask coated with a chemically amplified negative resist composition as described in any one of 1. to 18.

[0148] [The effects of the invention]

[0149] The present invention will now be described in detail. Furthermore, in the following description, depending on the structure represented by the chemical formula, asymmetric carbon may be present, and sometimes mirror-image isomers and non-mirror-image isomers may exist. In such cases, a single general formula is used to represent these isomers. These isomers may be used individually or in mixtures of two or more. Detailed Implementation

[0150] The present invention will now be described in detail. Furthermore, in the following description, the structure represented by chemical formulas may contain asymmetric carbons, and may contain mirror-image isomers and non-mirror-image isomers; in such cases, each isomer is represented by a single formula. These isomers may be used individually or in mixtures of two or more.

[0151] [Chemical amplification negative resist composition]

[0152] The chemically amplified negative resist composition of the present invention is characterized by containing: (A) a photoacid generator consisting of an onium salt that generates a predetermined benzenesulfonic acid derivative, and (B) a base polymer comprising a predetermined polymer.

[0153] [(A) Photoacid generator]

[0154] The photoacid generator of component (A) is an onium salt constituting the following formula (A).

[0155] [Chemistry 12]

[0156]

[0157] In formula (A), n1 is 0 or 1. When n1 is 0, it is a benzene ring; when n1 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with n1 = 0. n2 is 1, 2, 3, 4, or 5 when n1 is 0, and 1, 2, 3, 4, 5, 6, or 7 when n1 is 1. Considering the availability of raw materials, n2 is preferably 1, 2, 3, or 4, with 2 or 3 being more preferred. n3 is 0 or 1. When n3 is 0, it is a benzene ring; when n3 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with n3 = 0. n4 is 0, 1, 2, 3, or 4. n5 is 0, 1, 2, 3, or 4. However, when n3 is 0, 0 ≤ n4 + n5 ≤ 4; when n3 is 1, 0 ≤ n4 + n5 ≤ 6.

[0158] In formula (A), R 1 Each of the following is an iodine atom, or may contain heteroatoms, a branched or cyclic hydrocarbon group having 3 to 20 carbon atoms, and at least one R. 1 It is bonded to the carbon atom adjacent to the carbon atom bonded to S. Specific examples of the aforementioned hydrocarbon groups include: branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, tert-pentyl, and 2-ethylhexyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, oxanorbornel, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, such as decyl and adamantyl; aryl groups such as phenyl, naphthyl, and anthracene; and groups obtained by combining them, but not limited to these. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. The result may include hydroxyl, cyano, halogen, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, preferably fluorine or iodine atoms. R] 1It is preferable to have branched alkyl groups with 3 to 20 carbon atoms, such as isopropyl, sec-butyl, tert-butyl, tert-pentyl, and 2-ethylhexyl; aliphatic cyclic hydrocarbon groups with 3 to 20 carbon atoms, such as cyclopentyl, cyclohexyl, norbornel, oxanorbornel, and adamantyl; or aryl groups with 6 to 20 carbon atoms, such as phenyl and naphthyl, which may also have substituents. The substituents that the aforementioned aryl groups may also have are preferably fluorine, chlorine, bromine, or iodine atoms; hydrocarbon groups with 1 to 10 carbon atoms that may contain heteroatoms; hydrocarbon oxy groups with 1 to 10 carbon atoms that may contain heteroatoms; or hydrocarbon oxycarbonyl groups with 2 to 10 carbon atoms that may contain heteroatoms. When n2 is 2 or more, each R... 1 They can be the same or different.

[0159] Furthermore, when n² is 2 or more, multiple R... 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings.

[0160] R in equation (A) 1 Structures formed by bonding with aromatic rings can be represented by examples below, but are not limited to these. Additionally, in the following formula, the dashed lines represent atomic bonds with S.

[0161] [Chemistry 13]

[0162]

[0163] [Chemistry 14]

[0164]

[0165] [Chemistry 15]

[0166]

[0167] [Chemistry 16]

[0168]

[0169] [Chemistry 17]

[0170]

[0171] [Chemistry 18]

[0172]

[0173] [Chemistry 19]

[0174]

[0175] [Chemistry 20]

[0176]

[0177] [Chemistry 21]

[0178]

[0179] In equation (A), at least one R 1 It is bonded to the carbon atom adjacent to the carbon atom bonded to S. Thus, due to the other aromatic ring bonded to by the sulfonate group and R... 1 The spatial proximity creates a steric barrier and inhibits the rotation of sulfonamide bonds, thus significantly suppressing acid diffusion.

[0180] In formula (A), R 2 A hydrocarbon group with 1 to 20 carbon atoms, consisting of halogen atoms other than fluorine atoms, or possibly containing heteroatoms other than fluorine atoms. Examples of halogen atoms other than fluorine atoms include chlorine atoms, bromine atoms, and iodine atoms. The hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 20 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 20 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; aryl groups with 6 to 20 carbon atoms, such as phenyl, naphthyl, and anthracene. 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, and a portion of the -CH2- group can also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, the hydrocarbon group may contain hydroxyl, cyano, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. When n4 is 2, 3, or 4, each R...] 2 They can be the same or different. Also, when n4 is 2, 3, or 4, multiple R... 2 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings.

[0181] In formula (A), R F It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated alkyl thio group having 1 to 6 carbon atoms. R FThe substituents should ideally be fluorine atoms, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, or difluoromethylthio, with fluorine atoms, trifluoromethyl, or trifluoromethoxy being more preferred. These substituents containing or having fluorine atoms improve the acid strength of the resulting acid due to their electron-withdrawing effect, thus facilitating the deprotection reaction of unstable acid groups such as tertiary esters and tertiary ethers. When n5 is 2, 3, or 4, each R... F They can be the same or different.

[0182] The onium salt represented by formula (A) should preferably be represented by the following formula (A1).

[0183] [Chemistry 22]

[0184]

[0185] In the formula, n2, n3, n4, n5, R 1 R 2 R F and Z + Same as above.

[0186] The onium salt represented by formula (A1) should preferably be represented by formula (A2).

[0187] [Chemistry 23]

[0188]

[0189] In the formula, n3, n4, n5, R 1 R 2 R F and Z + Same as above.

[0190] Particularly desirable examples of onium salt anions represented by formula (A) can be listed below, but are not limited thereto.

[0191] [Chemistry 24]

[0192]

[0193] [Chemistry 25]

[0194]

[0195] [Chemistry 26]

[0196]

[0197] [Chemistry 27]

[0198]

[0199] [Chemistry 28]

[0200]

[0201] [Chemistry 29]

[0202]

[0203] [Chemistry 30]

[0204]

[0205] [Chemistry 31]

[0206]

[0207] [Chemistry 32]

[0208]

[0209] [Chemistry 33]

[0210]

[0211] [Chemistry 34]

[0212]

[0213] [Chemistry 35]

[0214]

[0215] [Chemistry 36]

[0216]

[0217] [Chemistry 37]

[0218]

[0219] [Chemistry 38]

[0220]

[0221] [Chemistry 39]

[0222]

[0223] [Chemistry 40]

[0224]

[0225] [Chemistry 41]

[0226]

[0227] [Chemistry 42]

[0228]

[0229] [Chemistry 43]

[0230]

[0231] [Chemistry 44]

[0232]

[0233] [Chemistry 45]

[0234]

[0235] [Chemistry 46]

[0236]

[0237] [Chemistry 47]

[0238]

[0239] [Chemistry 48]

[0240]

[0241] [Chemistry 49]

[0242]

[0243] [Transformation 50]

[0244]

[0245] [Chemistry 51]

[0246]

[0247] [Chemistry 52]

[0248]

[0249] [Chemistry 53]

[0250]

[0251] [Chemistry 54]

[0252]

[0253] [Chemistry 55]

[0254]

[0255] [Chemistry 56]

[0256]

[0257] [Chemistry 57]

[0258]

[0259] [Chem.58]

[0260]

[0261] [Chemistry 59]

[0262]

[0263] [Transformation 60]

[0264]

[0265] [Chemistry 61]

[0266]

[0267] [Chemistry 62]

[0268]

[0269] [Chemistry 63]

[0270]

[0271] [Chemistry 64]

[0272]

[0273] [Chemistry 65]

[0274]

[0275] [Chemistry 66]

[0276]

[0277] [Chemistry 67]

[0278]

[0279] [Chemistry 68]

[0280]

[0281] [Chemistry 69]

[0282]

[0283] [Chemistry 70]

[0284]

[0285] [Chemistry 71]

[0286]

[0287] [Chemistry 72]

[0288]

[0289] [Chemistry 73]

[0290]

[0291] [Chemistry 74]

[0292]

[0293] [Chemistry 75]

[0294]

[0295] [Chemistry 76]

[0296]

[0297] [Chemistry 77]

[0298]

[0299] [Chemistry 78]

[0300]

[0301] [Chemistry 79]

[0302]

[0303] [Chemistry 80]

[0304]

[0305] [Chemistry 81]

[0306]

[0307] [Chemistry 82]

[0308]

[0309] In formula (A), Z + The aforementioned onium cation is preferably a sulfonium cation represented by formula (Z-1) or a sulfonium cation represented by formula (Z-2).

[0310] [Chemistry 83]

[0311]

[0312] In equations (Z-1) and (Z-2), R ct1 ~R ct5 Each is a hydrocarbon group with 1 to 30 carbon atoms, which may be independently composed of halogen atoms or may contain heteroatoms.

[0313] R ct1 ~R ct5 Specific examples of halogen atoms that can be represented include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0314] R ct1 ~R ct5 The hydrocarbon group represented 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, and tert-butyl; cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 30 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 30 carbon atoms such as cyclohexenyl; aryl groups with 6 to 30 carbon atoms such as phenyl, naphthyl, and thiophene; aralkyl groups with 7 to 30 carbon atoms such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these groups, which should preferably be aryl. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and a portion of the -CH2- group of the hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0315] Also, R ct1 and R ct2 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. Specific examples of the aforementioned ring structures can be shown in the following formulas, etc.

[0316] [Chemistry 84]

[0317]

[0318] In the formula, the dashed line represents R. ct3 Atomic bonds.

[0319] Specific examples of sulfonium cations represented by formula (Z-1) include those described in paragraphs

[0102] to

[0125] of Japanese Patent Application Publication No. 2024-003744, those described in paragraphs

[0070] to

[0085] of Japanese Patent Application Publication No. 2023-169812, etc., but are not limited thereto.

[0320] Specific examples of citric acid represented by formula (Z-2) can be cited, such as those described in paragraph

[0181] of Japanese Patent Application Publication No. 2024-000259, but are not limited thereto.

[0321] Z + The onium cation represented should also be the sulfonium cation represented by the following formula (Z-3).

[0322] [Chemistry 85]

[0323]

[0324] In formula (Z-3), m1 is 0 or 1. When m1 is 0, it is a benzene ring; when m1 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with m1 = 0. m2 is 0 or 1. When m2 is 0, it is a benzene ring; when m2 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with m1 = 0. m3 is 0 or 1. When m3 is 0, it is a benzene ring; when m3 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with m3 = 0.

[0325] In formula (Z-3), m4 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption of EUV, but the less solvent solubility there will be concerns about precipitation in the resist composition. Therefore, m4 should preferably be 0, 1, 2, or 3, with 0, 1, or 2 being better.

[0326] In formula (Z-3), m5 can be 0, 1, 2, 3, or 4. Considering the availability of raw materials, m5 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred. m6 can be 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, m6 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred. m7 can be 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, m7 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred.

[0327] In formula (Z-3), m8 is 0, 1, or 2. Considering the availability of raw materials, m8 should preferably be 0 or 1. m9 is 0, 1, or 2. Considering the availability of raw materials, m9 should preferably be 0 or 1. m10 is 0, 1, or 2. Considering the availability of raw materials, m10 should preferably be 0 or 1.

[0328] In formula (Z-3), m11 is 0 or 1. When m11 is 0, it is a benzene ring; when m11 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with m11 of 0.

[0329] In formula (Z-3), m12 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption of EUV, but the less solvent solubility there will be concerns about precipitation in the resist composition. Therefore, m12 should preferably be 0, 1, 2, or 3, with 0, 1, or 2 being more preferred.

[0330] In equation (Z-3), m13 is 0, 1, or 2. From the perspective of raw material availability, m13 should preferably be 0 or 1. m14 is 0, 1, or 2. From a synthetic perspective, m14 should preferably be 0 or 1.

[0331] However, when m1 is 0, 0 ≤ m6 + m9 ≤ 4; when m1 is 1, 0 ≤ m6 + m9 ≤ 6. When m2 is 0, 0 ≤ m7 + m10 ≤ 4; when m2 is 1, 0 ≤ m7 + m10 ≤ 6. When m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4; when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6. When m11 is 0, 0 ≤ m12 + m13 ≤ 4; when m11 is 1, 0 ≤ m12 + m13 ≤ 6. Also, m4 + m12 ≥ 1.

[0332] In equation (Z-3), R F1 ~R F3 Each R is independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, trifluoromethyl, trifluoromethoxy, and trifluorothiomethoxy are preferred. When m5 is 2, 3, or 4, each R... F1 They can be the same or different. When m6 is 2, 3, 4, 5 or 6, each R... F2 They can be the same or different. When m7 is 2, 3, 4, 5 or 6, each R... F3 They can be the same or different.

[0333] In equation (Z-3), R ct6 ~R ct9 The group can be a halogen atom other than iodine or fluorine, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms (which may also contain heteroatoms), a hydrocarbon oxygen group with 1 to 20 carbon atoms (which may also contain heteroatoms), or a hydrocarbon thio group with 1 to 20 carbon atoms (which may also contain heteroatoms). The hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given and illustrated in the description of formula (A) as R. 2The same example applies to the hydrocarbon group. Furthermore, some or all of the hydrogen atoms in the hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon sulfide group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. Also, a portion of the -CH2- group in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0334] Also, when m8 is 2, there are 2 Rs. ct6 They can be the same or different, and there are 2 Rs. ct6 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m9 is 2, there are 2 R atoms. ct7 They can be the same or different, and there are 2 Rs. ct7 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m10 is 2, the two R atoms... ct8 They can be the same or different, and there are 2 Rs. ct8 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m13 is 2, there are 2 R atoms. ct9 They can be the same or different, and there are 2 Rs. ct9 They can also bond with each other and form rings together with the carbon atoms they are bonded to. Specific examples of the rings formed in this case include: cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, adamantane rings, etc. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0335] Furthermore, formula (Z-3) represents the S directly bonded to the sulfonium cation. + The aromatic rings can also bond with each other and with S + Together they form a ring. Specific examples of the aforementioned ring structure can be exemplified by the following formulas, etc.

[0336] [Chemistry 86]

[0337]

[0338] In equation (Z-3), L A and L BThese can be independently identified as single bonds, ether bonds, ester bonds, amide bonds, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. Among them, L... A The bonds should ideally be single bonds, ether bonds, ester bonds, or sulfonate bonds, with ester bonds or sulfonate bonds being preferred. B It is preferable to have a single bond, ether bond, or ester bond, with a single bond being better.

[0339] In equation (Z-3), X L It is a single bond, or may contain heteroatoms, of carbon atoms ranging from 1 to 40. The aforementioned hydrocarbon group can be linear, branched, or cyclic; specific examples include alkyldiyl groups and cyclic saturated hydrocarbon groups. Specific examples of the aforementioned heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0340] X L Specific examples of hydrocarbon groups containing 1 to 40 carbon atoms, which may also contain heteroatoms, are shown below, but are not limited to these. Additionally, in the following formula, * denotes and respectively... A and L B Atomic bonds.

[0341] [Chemistry 87]

[0342]

[0343] [Chemistry 88]

[0344]

[0345] [Chemistry 89]

[0346]

[0347] [Chemistry 90]

[0348]

[0349] Among them, X is the most suitable. L -0~X L -22 and X L -47~X L -58.

[0350] The sulfonium cation represented by formula (Z-3) should preferably be represented by the following formula (Z-3-1).

[0351] [Chemistry 91]

[0352]

[0353] In the formula, m4~m10, m12~m14, R F1 ~R F3 R ct6 ~R ct9 LA L B and X L Same as above. The cation represented by formula (Z-3-1) should preferably be represented by formula (Z-3-2).

[0354] [Chemistry 92]

[0355]

[0356] In the formula, m4~m10, R F1 ~R F3 and R ct6 ~R ct8 Same as above.

[0357] Specific examples of sulfonium cations represented by formula (Z-3) are shown below, but are not limited thereto. Additionally, in the following formula, Me is a methyl group.

[0358] [Chemistry 93]

[0359]

[0360] [Chemistry 94]

[0361]

[0362] [Chemistry 95]

[0363]

[0364] [Chemistry 96]

[0365]

[0366] [Chemistry 97]

[0367]

[0368] [Chem. 98]

[0369]

[0370] [Chemistry 99]

[0371]

[0372] [Chemistry 100]

[0373]

[0374] [Chemistry 101]

[0375]

[0376] [Chemistry 102]

[0377]

[0378] [Chemistry 103]

[0379]

[0380] [Chemistry 104]

[0381]

[0382] [Chemistry 105]

[0383]

[0384] [Chemistry 106]

[0385]

[0386] [Chemistry 107]

[0387]

[0388] [Chemistry 108]

[0389]

[0390] [Chemistry 109]

[0391]

[0392] [Chemical 110]

[0393]

[0394] [Chemistry 111]

[0395]

[0396] [Chemistry 112]

[0397]

[0398] [Chemistry 113]

[0399]

[0400] [Chemistry 114]

[0401]

[0402] [Chemistry 115]

[0403]

[0404] [Chemistry 116]

[0405]

[0406] [Chemistry 117]

[0407]

[0408] [Chemistry 118]

[0409]

[0410] [Chemistry 119]

[0411]

[0412] [Chemistry 120]

[0413]

[0414] Specific examples of the aforementioned onium salts can be listed by any combination of the aforementioned anions and cations.

[0415] The aforementioned onium salts can be synthesized using known methods. As an example, a method for manufacturing an onium salt represented by the following formula (PAG-1-ex) will be described.

[0416] [Chemistry 121]

[0417]

[0418] In the formula, n1~n5, R 1 R 2 R F and Z + Same as above.

[0419] The reaction described above utilizes the sulfonation reaction of raw material SM-1 with amino aromatic sulfonate SM-2 to obtain the aromatic sulfonate onium salt PAG-1-ex. The reaction can be carried out using common methods. Solvents that can be used in the reaction include: ethers such as tetrahydrofuran (THF), diethyl ether, diisopropyl ether, di-n-butyl ether, and 1,4-dioxane; hydrocarbons such as n-hexane, n-heptane, benzene, toluene, and xylene; aprotic polar solvents such as acetonitrile, dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF); and chlorinated organic solvents such as dichloromethane, chloroform, and carbon tetrachloride. These solvents can be selected appropriately according to the reaction conditions; one or more solvents can be used alone or in combination. Raw material SM-1, amino aromatic sulfonate SM-2, and a base are added sequentially or simultaneously to these solvents, and the reaction is carried out by cooling or heating as needed. Examples of bases that can be used in the reaction include: ammonia; amines such as triethylamine, pyridine, dimethylpyridine, trimethylpyridine, and N,N-dimethylaniline; hydroxides such as sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide; and carbonates such as potassium carbonate and sodium bicarbonate. These bases can be used alone or in combination of two or more. Confirmation of the reaction using silica gel thin-layer chromatography (TLC) is ideal from a yield perspective. The ononium salt PAG-1-ex can be obtained by performing a conventional aqueous work-up on the resulting reaction solution. If necessary, purification can be performed using common methods such as chromatography and recrystallization.

[0420] The onium salt represented by formula (A) is an onium salt of an aromatic sulfonic acid, and therefore can produce an acid of appropriate strength upon irradiation with high-energy rays. Furthermore, it has one or more groups selected from branched alkyl groups, alicyclic groups, and aryl groups as R. 1 Various functional groups can be introduced into aryl groups. Therefore, R 1 When the aryl group is aryl, it should ideally possess a functional group. 1 When the aryl group has a hydrocarbon oxycarbonyl group as a functional group, acid diffusion can be reduced by having multiple heteroatoms originating from the ester bond. Also, R 1 When the functional group is aryl and contains halogen atoms, especially fluorine atoms, the solvent solubility of the onium salt itself is increased, thereby improving uniform dispersion. Simultaneously, the acidity of the generated sulfonic acid is enhanced, thus promoting the deprotection reaction of the protecting groups of the base polymer and potentially improving resolution. Furthermore, R... 1When the anion is aryl and has branched alkyl or alicyclic groups, the exclusion volume of the anion increases, resulting in a bulky structure. Therefore, the low diffusion rate (LER) can be improved by generating acids with low diffusion. Furthermore, the multiple aromatic rings in the anion improve compatibility through interactions (π-π stacking interactions) with the aromatic rings of the base polymer, and can be expected to suppress excessive acid diffusion. The nitrogen atom from the sulfonamide bond reduces basicity due to the electron-withdrawing effect of the adjacent sulfonyl bond. Although it does not trap the protons of the generated acid, the sulfonamide bond has multiple heteroatoms, which can form hydrogen bonds with the protons through lone pairs, thus suppressing excessive acid diffusion. Utilizing these effects, acid with controlled excessive strength and diffusion can be uniformly generated in the resist film. Therefore, even with fine patterns, patterns with good resolution and low LER can be obtained. In negative resist compositions using alkaline developers, patterns with good rectangularity can be obtained due to appropriate dissolution resistance.

[0421] In the chemically amplified negative resist composition of the present invention, the content of (A) the photoacid generator is preferably 0.1 to 40 parts by mass, and more preferably 1 to 20 parts by mass, relative to 80 parts by mass of the base polymer (B) described later. If the content of (A) the photoacid generator is within the aforementioned range, the amount of acid required for the deprotection of acid-unstable groups will be generated, and the storage stability will also be good. (A) The photoacid generator can be used alone or in combination of two or more.

[0422] [(B) Basic Polymer]

[0423] (B) The base polymer comprises a polymer (hereinafter also referred to as polymer B) containing a repeating unit represented by the following formula (B1) (hereinafter also referred to as repeating unit B1). Repeating unit B1 is a repeating unit that provides etching resistance, adhesion to the substrate, and solubility in alkaline developer.

[0424] [Chemistry 122]

[0425]

[0426] In formula (B1), a1 is 0 or 1. a2 is 0, 1, or 2, and has a benzene skeleton when it is 0, a naphthalene skeleton when it is 1, and an anthracene skeleton when it is 2. a3 is an integer satisfying 0 ≤ a3 ≤ 5 + 2(a2) - a4. a4 is 1, 2, or 3. When a2 is 0, it is preferable that a3 is 0, 1, 2, or 3, and a4 is 1, 2, or 3. When a2 is 1 or 2, it is preferable that a3 is 0, 1, 2, 3, or 4, and a4 is 1, 2, or 3.

[0427] In equation (B1), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0428] In equation (B1), R11 The saturated hydrocarbon group can be a halogen atom, nitro group, carboxyl group, or a saturated hydrocarbon group with 1 to 6 carbon atoms that can be substituted by a halogen atom; a saturated hydrocarbon oxy group with 1 to 6 carbon atoms that can be substituted by a halogen atom; or a saturated hydrocarbon carbonyl oxy group with 2 to 8 carbon atoms that can be substituted by a halogen atom. The saturated hydrocarbon group, saturated hydrocarbon oxy group, and saturated hydrocarbon carbonyl oxy group can be any of the following: linear, branched, or cyclic. Specific examples include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, and their structural isomers; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; and groups obtained by combining them. If the number of carbon atoms is below the upper limit, the solubility in alkaline developing solutions is good. When a3 is 2 or higher, each R... 11 They can be the same or different.

[0429] In equation (B1), A 1 It is a single bond or a saturated alkylene group with 1 to 10 carbon atoms, and part of the -CH2- of the saturated alkylene group may also be replaced by -O-. The aforementioned saturated alkylene group can be any of the following: linear, branched, or cyclic. Specific examples include: methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and their structural isomers, etc., which are alkyl diyl groups with 1 to 10 carbon atoms; cyclopropane diyl, cyclobutane diyl, cyclopentane diyl, cyclohexane diyl, etc., which are cyclic saturated alkylene groups with 3 to 10 carbon atoms; and groups obtained by combining them. When the aforementioned saturated alkylene group contains an ether bond, when a1 in formula (B1) is 1, it can also be inserted at any position other than between the carbon atom at the α-position and the carbon atom at the β-position relative to the ester oxygen atom. Furthermore, when a1 is 0, the atom bonded to the main chain becomes an ether oxygen atom, and a second ether bond can be inserted at any position other than between the carbon atom at the α-position and the carbon atom at the β-position relative to this ether oxygen atom. In addition, if the number of carbon atoms in the aforementioned saturated hydrocarbon group is 10 or less, sufficient solubility in alkaline developing solution can be obtained, which is ideal.

[0430] a1 is 0 and A 1 When it is a single bond, that is, the aromatic ring is directly bonded to the polymer backbone (i.e., it does not have a linking group (-C(=O)-OA)). 1 When -)), ideal examples of repeating unit B1 can be listed as units from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene, 6-hydroxy-2-vinylnaphthalene, etc. Repeating units represented by the following formula (B1-1) are particularly preferred.

[0431] [Chemistry 123]

[0432]

[0433] In the formula, R A a4 is the same as the above.

[0434] a1 is 1 (that is, it has -C(=O)-OA) 1 When R is used as a linking group, ideal examples of repeating unit B1 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[0435] [Chemistry 124]

[0436]

[0437] Repeating unit B1 can be used alone or in combination with two or more types.

[0438] Polymer B may also contain at least one of the repeating units represented by the following formula (B2) (hereinafter also referred to as repeating unit B2) and the repeating units represented by the following formula (B3) (hereinafter also referred to as repeating unit B3). (Polymer B containing at least one of repeating units B2 and repeating unit B3 is also referred to as polymer B').

[0439] [Chemistry 125]

[0440]

[0441] When repeating units B2 and B3 are irradiated with high-energy rays, they will be affected by the acid produced from the photoacid generator. 1 -OW 2 These repeating units can cause a detachment reaction and induce insolubility in alkaline developing solutions and cross-linking reactions between polymers. Utilizing the functions of repeating units B2 and B3 allows for more efficient negativeing ​​reactions, thus improving resolution.

[0442] In equation (B2), b1 is 0 or 1. b2 is 0, 1 or 2. b3 is an integer satisfying 0 ≤ b3 ≤ 5 + 2(b2) - b4. b4 is 1, 2 or 3.

[0443] In formula (B3), b5 is 0, 1, or 2, and should preferably be 0 or 1. b6 is 1 or 2, and should preferably be 1.

[0444] In equations (B2) and (B3), R A Each of these can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (B3), it is preferable to have a hydrogen atom or a methyl group, with hydrogen being more preferred.

[0445] In equation (B2), R 21 It is a hydrocarbon group with 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms. R 21 Specific examples of halogen atoms that can be represented include: fluorine, chlorine, bromine, and iodine atoms. R 21The hydrocarbon group representing 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated in the explanation of formula (A) as R. 2 The same example represents hydrocarbon groups. When b3 is 2 or more, each R 21 They can be the same or different.

[0446] In equation (B2), R 22 and R 23 Each of the following groups is independently composed of a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may also be substituted by a hydroxyl group or a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, and the aryl group may also have substituents. However, R 22 and R 23 It cannot simultaneously be a hydrogen atom. Also, R 22 and R 23 They can also bond to each other and form a ring with the carbon atoms they are bonded to, and part of the -CH2- in this ring can be replaced by -O- or -S-. R 22 and R 23 Ideal examples include: alkyl groups such as methyl, ethyl, propyl, butyl, their structural isomers, or those in which a portion of the hydrogen atom is replaced by a hydroxyl or saturated alkyl group. When b4 is 2 or 3, each R... 22 They can be the same or different. Also, when b4 is 2 or 3, each R... 23 They can be the same or different.

[0447] In formula (B3), R 31 It is a hydrocarbon group with 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms. R 31 Specific examples of halogen atoms that can be represented include: fluorine, chlorine, bromine, and iodine atoms. R 31 The hydrocarbon group representing 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated in the explanation of formula (A) as R. 2 The same example represents hydrocarbon groups. When b5 is 2, each R 31 They can be the same or different.

[0448] In formula (B3), R 32 and R 33 Each R is independently a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and this hydrocarbon group may also be substituted by a hydroxyl group or a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, and the aryl group may also have substituents. When b6 is 2, each R 32 They can be the same or different. Also, when b6 is 2, each R... 33 They can be the same or different.

[0449] R32 and R 33 The saturated hydrocarbon group representing 1 to 15 carbon atoms can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 22 and R 23 The same example represents saturated hydrocarbon groups.

[0450] R 32 and R 33 Specific examples of aryl groups with 6 to 15 carbon atoms include phenyl, naphthyl, anthracene, etc., among which phenyl is preferred. Furthermore, the aforementioned aryl groups may also have substituents, and specific examples of such substituents include halogen atoms, saturated hydrocarbon groups with 1 to 6 carbon atoms that may be substituted by halogen atoms, and saturated hydrocarbon oxygen groups with 1 to 6 carbon atoms that may be substituted by halogen atoms, etc.

[0451] Also, R 32 and R 33 It cannot be both a hydrogen atom and a hydrogen atom. R 32 and R 33 When either of the substituents is an aryl group that may also have substituents, the other substituent should preferably be a hydrogen atom.

[0452] R 32 and R 33 Ideally, they should be the same group, and it would be even better if they were both methyl groups.

[0453] Also, R 32 and R 33 They can also bond to each other and form a ring together with the carbon atoms they are bonded to, and part of the -CH2- in this ring can be replaced by -O- or -S-. Examples of such rings include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, norbornene ring, adamantane ring, tricyclic ring [5.2.1.0] 2,6 Decane ring, tetracyclic ring [6.2.1.1] 3,6 .0 2,7 Dodecane ring, oxanorcampane ring, thianorcampane ring, etc., but not limited to these.

[0454] In equation (B2), A 2It is a single bond or a saturated alkylene group with 1 to 10 carbon atoms, and part of the -CH2- of the saturated alkylene group may also be replaced by -O-. The aforementioned saturated alkylene group can be any of the following: linear, branched, or cyclic. Specific examples include: methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and their structural isomers, etc.; cyclic saturated alkylene groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; and groups obtained by combining them. When the aforementioned saturated alkylene group contains an ether bond, and b1 in formula (B2) is 1, it can also be inserted at any position other than between the carbon atom at the α-position and the carbon atom at the β-position relative to the ester oxygen atom. Furthermore, when b1 is 0, the atom bonded to the main chain becomes an ether oxygen atom, and a second ether bond can be inserted at any position other than between the carbon atom at the α position and the carbon atom at the β position relative to this ether oxygen atom.

[0455] In equations (B2) and (B3), W 1 and W 2 Each of the following groups is independently composed of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon carbonyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the aryl group may also have substituents.

[0456] W 1 and W 2 The aliphatic hydrocarbon groups representing 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms such as cyclopentyl and cyclohexyl; alkenyl groups with 2 to 10 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; and cyclic unsaturated hydrocarbon groups with 3 to 10 carbon atoms such as cyclohexenyl. 1 and W 2 The hydrocarbon group represented by the carbonyl group of an aliphatic hydrocarbon with 2 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be found among the aforementioned examples of aliphatic hydrocarbon groups with 1 to 10 carbon atoms, specifically those with 1 to 9 carbon atoms. 1 and W 2 Specific examples of aryl groups with 6 to 15 carbon atoms include phenyl, naphthyl, anthracene, etc., among which phenyl is preferred. Furthermore, the aforementioned aryl groups may also have substituents. Specific examples of substituents include halogen atoms, saturated hydrocarbon groups with 1 to 6 carbon atoms that can also be substituted by halogen atoms, and saturated hydrocarbon oxygen groups with 1 to 6 carbon atoms that can also be substituted by halogen atoms. When b4 is 2 or 3, each W... 1They can be the same or different. Also, when b6 is 2, each W... 2 They can be the same or different.

[0457] The repeating unit B2 should preferably be represented by the following formula (B2-1) or (B2-2).

[0458] [Chemistry 126]

[0459]

[0460] In the formula, b4 and R A R 22 and R 23 Same as above.

[0461] Ideal examples of repeating unit B2 can be listed below, but are not limited to these. Additionally, in the following formula, R... A As mentioned above, Me represents methyl and Ac represents acetyl.

[0462] [Chemistry 127]

[0463]

[0464] [Chemistry 128]

[0465]

[0466] [Chemistry 129]

[0467]

[0468] [Chemistry 130]

[0469]

[0470] [Chemistry 131]

[0471]

[0472] [Chemistry 132]

[0473]

[0474] [Chemistry 133]

[0475]

[0476] [Chemistry 134]

[0477]

[0478] [Chemistry 135]

[0479]

[0480] [Chemistry 136]

[0481]

[0482] [Chemistry 137]

[0483]

[0484] [Chemistry 138]

[0485]

[0486] [Chemistry 139]

[0487]

[0488] [Chemistry 140]

[0489]

[0490] [Chemistry 141]

[0491]

[0492] [Chemistry 142]

[0493]

[0494] [Chemistry 143]

[0495]

[0496] [Chemistry 144]

[0497]

[0498] [Chemistry 145]

[0499]

[0500] [Chemistry 146]

[0501]

[0502] Repeating unit B2 can be used alone or in combination with two or more types.

[0503] The repeating unit B3 should be represented by the following formula (B3-1).

[0504] [Chemistry 147]

[0505]

[0506] In the formula, b6 and R A R 32 and R33 Same as above.

[0507] Ideal examples of repeating unit B3 can be listed below, but are not limited to these. Additionally, in the following formula, R... A As mentioned above, Me represents methyl and Ac represents acetyl.

[0508] [Chemistry 148]

[0509]

[0510] [Chemistry 149]

[0511]

[0512] [Chemistry 150]

[0513]

[0514] [Chemistry 151]

[0515]

[0516] [Chemistry 152]

[0517]

[0518] [Chemistry 153]

[0519]

[0520] [Chemistry 154]

[0521]

[0522] [Chemistry 155]

[0523]

[0524] [Chemistry 156]

[0525]

[0526] [Chemistry 157]

[0527]

[0528] [Chemistry 158]

[0529]

[0530] [Chemistry 159]

[0531]

[0532] [Chemistry 160]

[0533]

[0534] [Chemistry 161]

[0535]

[0536] [Chemistry 162]

[0537]

[0538] [Chemistry 163]

[0539]

[0540] [Chemistry 164]

[0541]

[0542] [Chemistry 165]

[0543]

[0544] [Chemistry 166]

[0545]

[0546] [Chemistry 167]

[0547]

[0548] [Chemistry 168]

[0549]

[0550] [Chemistry 169]

[0551]

[0552] [Chemistry 170]

[0553]

[0554] [Chemistry 171]

[0555]

[0556] [Chemistry 172]

[0557]

[0558] [Chemistry 173]

[0559]

[0560] [Chemistry 174]

[0561]

[0562] [Chemistry 175]

[0563]

[0564] [Chemistry 176]

[0565]

[0566] [Chemistry 177]

[0567]

[0568] [Chemistry 178]

[0569]

[0570] [Chemistry 179]

[0571]

[0572] [Chemistry 180]

[0573]

[0574] Repeating unit B3 can be used alone or in combination with two or more types.

[0575] In order to improve etching resistance, polymers B and B' may also contain at least one of the repeating units represented by formula (B4) (hereinafter also referred to as repeating unit B4), the repeating unit represented by formula (B5) (hereinafter also referred to as repeating unit B5), and the repeating unit represented by formula (B6) (hereinafter also referred to as repeating unit B6).

[0576] [Chemistry 181]

[0577]

[0578] In equations (B4) and (B5), c and d are independently 0, 1, 2, 3 or 4, respectively.

[0579] In equations (B4) and (B5), R 41 and R 42 Each of the following can be independently a hydroxyl group, a halogen atom, a saturated hydrocarbon group with 1 to 8 carbon atoms that can be substituted by a halogen atom, a saturated hydrocarbon oxygen group with 1 to 8 carbon atoms that can be substituted by a halogen atom, or a saturated hydrocarbon carbonyl oxygen group with 2 to 8 carbon atoms that can be substituted by a halogen atom. The aforementioned saturated hydrocarbon group, saturated hydrocarbon oxygen group, and saturated hydrocarbon carbonyl oxygen group can be any of the following: linear, branched, or cyclic. When c is 2, 3, or 4, each R... 41They can be the same or different. When d is 2, 3, or 4, each R... 42 They can be the same or different.

[0580] In formula (B6), e1 is 0 or 1. e2 is 0, 1 or 2. When e2 is 0, it is a benzene skeleton; when it is 1, it is a naphthalene skeleton; and when it is 2, it is an anthracene skeleton. e3 is 0, 1, 2, 3, 4 or 5. When e2 is 0, e3 should preferably be 0, 1, 2 or 3; when e2 is 1 or 2, e3 should preferably be 0, 1, 2, 3 or 4.

[0581] In equation (B6), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0582] In equation (B6), R 43 The group can be a saturated hydrocarbon group (1-20 carbon atoms), a saturated hydrocarbon oxy group (1-20 carbon atoms), a saturated hydrocarbon carbonyl oxy group (2-20 carbon atoms), a saturated hydrocarbon oxyalkyl group (2-20 carbon atoms), a saturated hydrocarbon thioalkyl group (2-20 carbon atoms), a halogen atom, a nitro group, a cyano group, a saturated hydrocarbon sulfinyl group (1-20 carbon atoms), or a saturated hydrocarbon sulfonyl group (1-20 carbon atoms). The aforementioned saturated hydrocarbon group, saturated hydrocarbon oxy group, saturated hydrocarbon carbonyl oxy group, saturated hydrocarbon oxyalkyl group, saturated hydrocarbon thioalkyl group, saturated hydrocarbon sulfinyl group, and saturated hydrocarbon sulfonyl group can be any of the following: linear, branched, or cyclic. When e3 is 2, 3, 4, or 5, each R... 43 They can be the same or different.

[0583] R 43 Suitable hydroxyl groups include halogen atoms such as chlorine, bromine, and iodine; saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, and their structural isomers; and saturated hydrocarbon oxygen groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopentyloxy, cyclohexyloxy, and their hydrocarbon structural isomers. Among these, methoxy and ethoxy are particularly useful.

[0584] Furthermore, saturated hydrocarbon carbonyloxy groups can be easily introduced via chemical modification after polymer polymerization, which can be used to fine-tune the solubility of the base polymer in alkaline developers. Examples of such saturated hydrocarbon carbonyloxy groups include: methyl carbonyloxy, ethyl carbonyloxy, propyl carbonyloxy, butyl carbonyloxy, pentyl carbonyloxy, hexyl carbonyloxy, cyclopentyl carbonyloxy, cyclohexyl carbonyloxy, benzoyloxy, and their hydrocarbon isomers. If the carbon number is 20 or less, the effect of controlling and adjusting the solubility of the base polymer in alkaline developers (mainly the reduction effect) can be set appropriately, and the generation of residue (development defects) can be suppressed.

[0585] Among the aforementioned ideal substituents, those that are easy to prepare and can be used effectively in monomer form include: chlorine atom, bromine atom, iodine atom, methyl, ethyl, methoxy, etc.

[0586] In equation (B6), A 3 It is a single bond or a saturated alkylene group with 1 to 10 carbon atoms, and part of the -CH2- of the saturated alkylene group may also be replaced by -O-. The aforementioned saturated alkylene group can be any of the following: linear, branched, or cyclic. Specific examples include: methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and their structural isomers, etc., which are alkyl diyl groups with 1 to 10 carbon atoms; cyclopropane diyl, cyclobutane diyl, cyclopentane diyl, cyclohexane diyl, etc., which are cyclic saturated alkylene groups with 3 to 10 carbon atoms; and groups obtained by combining them. When the aforementioned saturated alkylene group contains an ether bond, and e1 in formula (B6) is 1, it can also be inserted at any position other than between the carbon atom at the α-position and the carbon atom at the β-position relative to the ester oxygen atom. Furthermore, when e1 is 0, the atom bonded to the main chain becomes an ether oxygen atom, and a second ether bond can be inserted at any position other than between the carbon atom at the α-position and the carbon atom at the β-position relative to this ether oxygen atom. In addition, if the number of carbon atoms in the aforementioned saturated hydrocarbon group is 10 or less, sufficient solubility in alkaline developing solution can be obtained, which is ideal.

[0587] e1 is 0 and A 3 When it is a single bond, that is, the aromatic ring is directly bonded to the polymer backbone (i.e., it does not have a linking group (-C(=O)-OA)). 3 When repeating unit B6, ideal examples can be listed from units such as styrene, 4-chlorostyrene, 4-methylstyrene, 4-methoxystyrene, 4-bromostyrene, 4-acetoxystyrene, 2-hydroxypropylstyrene, 2-vinylnaphthalene, 3-vinylnaphthalene, etc.

[0588] Furthermore, when e1 is 1 (that is, when it has -C(=O)-OA), 3 -When used as a linking group), ideal examples of repeating unit B6 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[0589] [Chemistry 182]

[0590]

[0591] [Chemistry 183]

[0592]

[0593] When at least one of repeating units B4 to B6 is used as a constituent unit of the aforementioned polymer, the etching resistance of the aromatic ring can be improved. In addition, the etching resistance caused by the addition of ring structures to the main chain and the EB irradiation resistance during pattern inspection can also be improved.

[0594] Repeating units B4 to B6 can be used individually or in combination of two or more.

[0595] Polymer B' may also contain at least one of the repeating units represented by formula (B7) (hereinafter also called repeating unit B7), the repeating unit represented by formula (B8) (hereinafter also called repeating unit B8), the repeating unit represented by formula (B9) (hereinafter also called repeating unit B9), the repeating unit represented by formula (B10) (hereinafter also called repeating unit B10), and the repeating unit represented by formula (B11) (hereinafter also called repeating unit B11).

[0596] [Chemistry 184]

[0597]

[0598] In equations (B7) to (B11), R A Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It is a single bond or may have substituents. Z 2 For single bonds, **-C(=O)-OZ 21 -、**-C(=O)-NH-Z 21 -or**-OZ 21 -. Z 21 It is a divalent group consisting of an aliphatic hydrocarbon group, a phenylene group, or a combination thereof, having 1 to 6 carbon atoms, and may also contain a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 3 It can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. 4 It is a single bond, or an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may also contain a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 5 Each can be a single bond, or may have substituents such as phenylene, naphthylene, or *-C(=O)-OZ. 51 -. Z 51 It is an aliphatic hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the aliphatic hydrocarbon group may also contain a halogen atom, a hydroxyl group, an ether bond, an ester bond, or an lactone ring. 6 It can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. 7 Each is independently a single bond, ***-Z71 -C(=O)-O-、***-C(=O)-NH-Z 71 -or ***-OZ 71 -. Z 71 It can also contain alkylene groups with 1 to 20 carbon atoms, which may also contain heteroatoms. Z 8 Each is independently a single bond, ****-Z 81 -C(=O)-O-、****-C(=O)-NH-Z 81 -or ****-OZ 81 -. Z 81 It can also contain alkylene groups with 1 to 20 carbon atoms, which may also contain heteroatoms. Z 9 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, *-C(=O)-OZ 91 -、*-C(=O)-N(H)-Z 91 -or *-OZ 91 -. Z 91 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group. * indicates an atomic bond with the carbon atom of the main chain. ** indicates a bond with Z. 1 The atomic bonds. *** indicates the relationship between Z and 6 Atomic bonds. **** represents the bond between Z and Z. 7 Atomic bonds.

[0599] Z 21 Z 51 and Z 91 The aliphatic alkyl sub-group can be any of the following: linear, branched, or cyclic. Specific examples include: methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, 1,1-dimethylethane-1,2-diyl, pentane-1,5-diyl, 2-methylbutane-1,2-diyl, hexane-1,6-diyl, etc.; cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, etc.; and groups obtained by combining them.

[0600] Z 71 and Z 81 The sub-hydrocarbon group represented may contain heteroatoms and can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples are listed below, but are not limited to these.

[0601] [Chemistry 185]

[0602]

[0603] In the formula, the dashed lines represent atomic bonds.

[0604] In equation (B7), R 51 and R 52 Each of the above-mentioned hydrocarbon groups can be independently a hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 20 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclohexenyl; aryl groups with 6 to 20 carbon atoms such as phenyl, naphthyl, and thiophene; aralkyl groups with 7 to 20 carbon atoms such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them, which are preferably aryl groups. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and a portion of the -CH2- group of the hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0605] Also, R 51 and R 52 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. Specific examples of the aforementioned rings can be shown in the following formulas, etc.

[0606] [Chemistry 186]

[0607]

[0608] In the formula, the dashed line represents Z. 4 Atomic bonds.

[0609] Specific examples of the cation in repeating unit B7 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[0610] [Chemistry 187]

[0611]

[0612] [Chem.188]

[0613]

[0614] [Chemistry 189]

[0615]

[0616] [Chemistry 190]

[0617]

[0618] [Chemistry 191]

[0619]

[0620] [Chemistry 192]

[0621]

[0622] [Chemistry 193]

[0623]

[0624] [Chemistry 194]

[0625]

[0626] [Chemistry 195]

[0627]

[0628] [Chemistry 196]

[0629]

[0630] In equation (B7), M - These are non-nucleophilic relative ions. The aforementioned non-nucleophilic relative ions are preferably halide ions, sulfonic acid anions, imide acid anions, and methylated acid anions. Specific examples of the aforementioned halide ions include chloride ions and bromide ions. Specific examples of the aforementioned sulfonic acid anions (sulfonate ions) include trifluoromethanesulfonate ions, 1,1,1-trifluoroethanesulfonate ions, nonafluorobutanesulfonate ions, and other fluoroalkyl sulfonate ions; toluenesulfonate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, 1,2,3,4,5-pentafluorobenzenesulfonate ions, and other aryl sulfonate ions; methanesulfonate ions, butanesulfonate ions, and other alkyl sulfonate ions, etc. Specific examples of the aforementioned imide acid anions (imide ions) include bis(trifluoromethylsulfonyl)imide ions, bis(perfluoroethylsulfonyl)imide ions, bis(perfluorobutylsulfonyl)imide ions, etc. Specific examples of the aforementioned methylated acid anions (methylated ions) include: tris(trifluoromethylsulfonyl) methylated ion, tris(perfluoroethylsulfonyl) methylated ion, etc.

[0631] Other examples of the aforementioned non-nucleophilic relative ions can be listed as anions represented by any of the formulas (B7-1) to (B7-4).

[0632] [Chemistry 197]

[0633]

[0634] In equation (B7-1), R fa The hydrocarbon group consists of fluorine atoms, or may contain heteroatoms, and has 1 to 40 carbon atoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in the following formula (B7-1-1). fa1 The same example represents hydrocarbon groups.

[0635] The anion represented by formula (B7-1) should preferably be represented by the following formula (B7-1-1).

[0636] [Chemistry 198]

[0637]

[0638] In formula (B7-1-1), Q 1 and Q 2 Each atom is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; to improve solvent solubility, at least one of them is preferably trifluoromethyl. m can be 0, 1, 2, 3, or 4, with 1 being particularly preferred. R fa1 It can also contain hydrocarbon groups with 1 to 35 carbon atoms that are heteroatoms. The aforementioned heteroatoms are preferably oxygen, nitrogen, sulfur, halogen, etc., with oxygen atoms being more preferred. Considering that the aforementioned hydrocarbon groups can obtain high resolution in the formation of fine patterns, those with 6 to 30 carbon atoms are particularly preferred.

[0639] In equation (B7-1-1), R fa1The hydrocarbon group represented by carbon number 1 to 35 can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 35 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecanyl, and eicosyl; cyclic saturated hydrocarbon groups with 3 to 35 carbon atoms, such as cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norcamphenyl, norcamphenylmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl; unsaturated aliphatic hydrocarbon groups with 2 to 35 carbon atoms, such as 2-propenyl and 3-cyclohexenyl; aryl groups with 6 to 35 carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, and 9-fluorenyl; aralkyl groups with 7 to 35 carbon atoms, such as benzyl and diphenylmethyl; and groups obtained by combining them.

[0640] 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 hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. This can result in the presence of hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Specific examples of hydrocarbon groups containing heteroatoms include: tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidemethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, 3-oxocyclohexyl, etc.

[0641] In formula (B7-1-1), L a1 The bonds can be single bonds, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, or carbamate bonds. From a synthetic point of view, ether bonds or ester bonds are preferred, with ester bonds being even better.

[0642] Specific examples of anions represented by equation (B7-1) are shown below, but are not limited to these. Additionally, in the following equation, Q... 1 As mentioned above, Ac is an acetyl group.

[0643] [Chemistry 199]

[0644]

[0645] [Chemistry 200]

[0646]

[0647] [Chemical Engineering 201]

[0648]

[0649] [Chemical Engineering 202]

[0650]

[0651] [Chemical Engineering 203]

[0652]

[0653] [Chemical 204]

[0654]

[0655] [Chemical Engineering 205]

[0656]

[0657] [Chemical Engineering 206]

[0658]

[0659] [Chemical 207]

[0660]

[0661] [Chemical Engineering 208]

[0662]

[0663] [Chemical Engineering 209]

[0664]

[0665] [Chemical 210]

[0666]

[0667] In equation (B7-2), R fb1 and R fb2 Each hydrocarbon group consists independently of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in formula (B7-1-1). fa1 The same example represents a hydrocarbon group. R fb1 and R fb2 It should preferably be a fluorine atom or a straight-chain fluorinated alkyl group having 1 to 4 carbon atoms. Also, R fb1 and R fb2 They can also bond to each other and to the groups they are bonded to (-CF2-SO2-N). - -SO2-CF2-) together form a ring, at which point Rfb1 and R fb2 The groups formed by mutual bonding should preferably be fluorinated ethylidene or fluorinated propyleneide.

[0668] In equation (B7-3), R fc1 R fc2 and R fc3 Each hydrocarbon group consists independently of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in formula (B7-1-1). fa1 The same example represents a hydrocarbon group. R fc1 R fc2 and R fc3 It should preferably be a fluorine atom or a straight-chain fluorinated alkyl group having 1 to 4 carbon atoms. Also, R fc1 and R fc2 They can also bond to each other and to the groups they are bonded to (-CF2-SO2-C). - -SO2-CF2-) together form a ring, at which point R fc1 and R fc2 The groups formed by mutual bonding should preferably be fluorinated ethylidene or fluorinated propyleneide.

[0669] In equation (B7-4), R fd It can be a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in formula (B7-1-1). fa1 The same example represents hydrocarbon groups.

[0670] Specific examples of anions represented by formula (B7-4) are listed below, but are not limited thereto.

[0671] [Chemistry 211]

[0672]

[0673] [Chemistry 212]

[0674]

[0675] Examples of the aforementioned non-nucleophilic relative ions can be further exemplified by anions with aromatic rings substituted by iodine or bromine atoms. Specific examples of such anions can be represented by the following formula (B7-5).

[0676] [Chemistry 213]

[0677]

[0678] In equation (B7-5), 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 should preferably be 1, 2, or 3, with 2 or 3 being even better. z should preferably be 0, 1, or 2.

[0679] In equation (B7-5), 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.

[0680] In formula (B7-5), L 11 It is a saturated hydrocarbon group with 1 to 6 carbon atoms, consisting of a single bond, ether bond, or ester bond, or may also contain ether or ester bonds. The aforementioned saturated hydrocarbon group may be linear, branched, or cyclic.

[0681] In formula (B7-5), L 12 When x is 1, it is a single bond or a divalent linker with 1 to 20 carbon atoms; when x is 2 or 3, it is a (x+1) valent linker with 1 to 20 carbon atoms, and the linker may also contain oxygen, sulfur or nitrogen atoms.

[0682] In equation (B7-5), R fe The carbon group may be a hydroxyl, carboxyl, fluorine, chlorine, bromine, or amino group, or may contain a fluorine, chlorine, bromine, hydroxyl, amino, or ether bond, and may be a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon oxy group having 1 to 20 carbon atoms, a hydrocarbon carbonyl group having 2 to 20 carbon atoms, a hydrocarbon oxycarbonyl group having 2 to 20 carbon atoms, or a hydrocarbon sulfonyl oxy group having 1 to 20 carbon atoms, or -N(R) feA (R) feB ), -N(R feC )-C(=O)-R feD or -N(R) feC )-C(=O)-OR feD R feA and R feB Each can be independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. R feC It is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms. R feDIt is an aliphatic hydrocarbon group with 1 to 16 carbon atoms, an aryl group with 6 to 12 carbon atoms, or an aralkyl group with 7 to 15 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxy group with 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group with 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl oxy group with 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group can be saturated or unsaturated, and can be straight-chain, branched, or cyclic. The aforementioned hydrocarbon group, hydrocarbon oxy group, hydrocarbon carbonyl group, hydrocarbon oxycarbonyl group, hydrocarbon carbonyl oxy group, and hydrocarbon sulfonyl oxy group can be straight-chain, branched, or cyclic. When x and / or z are 2 or more, each R fe They can be the same or different.

[0683] Among them, R fe It is advisable to use hydroxyl groups, -N(R) feC )-C(=O)-R feD -N(R) feC )-C(=O)-OR feD Fluorine atoms, chlorine atoms, bromine atoms, methyl groups, methoxy groups, etc.

[0684] In equation (B7-5), Rf 11 ~Rf 14 Each of these atoms can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of them must be a fluorine atom or a trifluoromethyl group. Also, Rf 11 With Rf 12 They can also combine to form carbonyl groups. Especially Rf 13 and Rf 14 Both are ideally composed of fluorine atoms.

[0685] Specific examples of anions represented by equation (B7-5) are shown below, but are not limited to these. Additionally, in the following equation, X... BI Same as above.

[0686] [Chemistry 214]

[0687]

[0688] [Chemical 215]

[0689]

[0690] [Chemistry 216]

[0691]

[0692] [Chemistry 217]

[0693]

[0694] [Chemistry 218]

[0695]

[0696] [Chemistry 219]

[0697]

[0698] [Chem.220]

[0699]

[0700] [Chemistry 221]

[0701]

[0702] [Chemistry 222]

[0703]

[0704] [Chemistry 223]

[0705]

[0706] [Chemistry 224]

[0707]

[0708] [Chemistry 225]

[0709]

[0710] [Chemistry 226]

[0711]

[0712] [Chemistry 227]

[0713]

[0714] [Chemistry 228]

[0715]

[0716] [Chemistry 229]

[0717]

[0718] [Chemistry 230]

[0719]

[0720] [Chemistry 231]

[0721]

[0722] [Chemistry 232]

[0723]

[0724] [Chemistry 233]

[0725]

[0726] [Chemistry 234]

[0727]

[0728] [Chemistry 235]

[0729]

[0730] [Chemistry 236]

[0731]

[0732] [Chemistry 237]

[0733]

[0734] The aforementioned non-nucleophilic relative ions may also include the fluorobenzenesulfonic acid anion bonded to an aromatic group containing an iodine atom as described in Japanese Patent No. 6648726, the anion with a mechanism of decomposition due to acid as described in International Publication No. 2021 / 200056 and Japanese Patent Application Publication No. 2021-70692, the anion with a cyclic ether group as described in Japanese Patent Application Publication No. 2018-180525 and Japanese Patent Application Publication No. 2021-35935, and the anion as described in Japanese Patent Application Publication No. 2018-92159.

[0735] The aforementioned non-nucleophilic relative ions may also be the bulky benzenesulfonic acid derivative anions without fluorine atoms described in Japanese Patent Application Publication No. 2006-276759, Japanese Patent Application Publication No. 2015-117200, Japanese Patent Application Publication No. 2016-65016 and Japanese Patent Application Publication No. 2019-202974, the benzenesulfonic acid anions without fluorine atoms bonded to aromatic groups containing iodine atoms, and the alkylsulfonic acid anions described in Japanese Patent Publication No. 6645464.

[0736] The aforementioned non-nucleophilic relative ions may also be the anions of disulfonic acid as described in Japanese Patent Application Publication No. 2015-206932, the anions of sulfonamides or sulfonamides that are different from sulfonic acid on one side as described in International Publication No. 2020 / 158366, and the anions of carboxylic acids that are different from sulfonic acid on the other side as described in Japanese Patent Application Publication No. 2015-24989.

[0737] In equations (B8) and (B9), f1 and f2 are independently 0, 1, 2 or 3, and should preferably be 1.

[0738] In equation (B10), g1 is 0 or 1. g2 is 0, 1, 2, 3 or 4. g3 is 0, 1, 2, 3 or 4. However, when g1 is 0, 0 ≤ g2 + g3 ≤ 4, and when g1 is 1, 0 ≤ g2 + g3 ≤ 6.

[0739] In equations (B8), (B9) and (B10), L 1 The bonds can be single bonds, ether bonds, ester bonds, carbonyl bonds, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. From a synthetic point of view, ether bonds, ester bonds, and carbonyl bonds are preferred, with ester bonds and carbonyl bonds being even more desirable.

[0740] In equation (B8), Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among them, Rf 1 and Rf 2 To increase the acid strength of the produced acid, it is preferable that all atoms be fluorine atoms. Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among them, Rf is used to improve solvent solubility. 3 and Rf 4 At least one of them should preferably be trifluoromethyl.

[0741] In equation (B9), Rf 5 and Rf 6 Each can be independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. However, all Rf 5 and Rf 6 They cannot all be hydrogen atoms simultaneously. Among them, Rf is used to improve solvent solubility. 5 and Rf 6 At least one of them should preferably be trifluoromethyl.

[0742] In formula (B10), Rf 7 It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated alkyl thio group having 1 to 6 carbon atoms. Rf 7 It is preferable to have a fluorine atom, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, or difluoromethylthio, with fluorine, trifluoromethyl, or trifluoromethoxy being more preferred. When g2 is 2, 3, or 4, each Rf 7 They can be the same or different.

[0743] In formula (B10), R 53It 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. Specific examples can be listed and illustrated in the description of formula (A) as R. 2 Examples of hydrocarbon groups are similar, but not limited to these. Also, when g3 is 2, 3, or 4, each R... 53 They can be the same or different.

[0744] Furthermore, when g3 is 2, 3, or 4, multiple R 53 They can also bond with each other and form rings together with the carbon atoms they are bonded to. Specific examples of the rings formed in this case include: cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, adamantane rings, etc. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0745] Specific examples of the anion of repeating unit B8 can be listed below, but are not limited to these. Additionally, in the following formula, R... A As mentioned above, Me is a methyl group.

[0746] [Chemistry 238]

[0747]

[0748] [Chemistry 239]

[0749]

[0750] [Chemistry 240]

[0751]

[0752] [Chemistry 241]

[0753]

[0754] [Chemistry 242]

[0755]

[0756] [Chemistry 243]

[0757]

[0758] [Chemistry 244]

[0759]

[0760] [Chemistry 245]

[0761]

[0762] [Chemistry 246]

[0763]

[0764] [Chemistry 247]

[0765]

[0766] [Chemistry 248]

[0767]

[0768] [Chemistry 249]

[0769]

[0770] [Chemistry 250]

[0771]

[0772] Specific examples of the anion of repeating unit B9 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[0773] [Chemistry 251]

[0774]

[0775] [Chemistry 252]

[0776]

[0777] [Chemistry 253]

[0778]

[0779] [Chemistry 254]

[0780]

[0781] [Chemistry 255]

[0782]

[0783] [Chemistry 256]

[0784]

[0785] [Chemistry 257]

[0786]

[0787] [Chemistry 258]

[0788]

[0789] [Chemistry 259]

[0790]

[0791] [Chemistry 260]

[0792]

[0793] [Chemistry 261]

[0794]

[0795] Specific examples of the anion of repeating unit B10 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[0796] [Chemistry 262]

[0797]

[0798] [Chemistry 263]

[0799]

[0800] [Chemistry 264]

[0801]

[0802] [Chemistry 265]

[0803]

[0804] [Chemistry 266]

[0805]

[0806] [Chemistry 267]

[0807]

[0808] [Chemistry 268]

[0809]

[0810] [Chemistry 269]

[0811]

[0812] [Chemistry 270]

[0813]

[0814] [Chemistry 271]

[0815]

[0816] [Chemistry 272]

[0817]

[0818] [Chemistry 273]

[0819]

[0820] [Chemistry 274]

[0821]

[0822] [Chemistry 275]

[0823]

[0824] [Chemistry 276]

[0825]

[0826] [Chemistry 277]

[0827]

[0828] [Chemistry 278]

[0829]

[0830] Specific examples of the anion of repeating unit B11 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[0831] [Chemistry 279]

[0832]

[0833] In equations (B8) to (B11), A +The cation is an onium cation. Examples of onium cations include: sulfonium cations, ferrophosphate cations, ammonium cations, etc., preferably sulfonium cations or ferrophosphate cations. Specific examples of the aforementioned sulfonium cations may be listed and illustrated as examples of sulfonium cations represented by formula (Z-1) and examples of sulfonium cations represented by formula (Z-3), but are not limited thereto. Specific examples of the aforementioned ferrophosphate cations may be listed and illustrated as examples of ferrophosphate cations represented by formula (Z-2), but are not limited thereto. Specific examples of the aforementioned ammonium cations may be listed and illustrated as examples of ammonium cations represented by the following formula (am-1), but are not limited thereto.

[0834] The specific structures of repeating units B7 to B11 can be listed as any combination of the aforementioned anions and cations.

[0835] Repeating units B7 to B11 are units that generate acid due to irradiation with high-energy rays. It is believed that by incorporating these units into the polymer, acid diffusion can be moderately suppressed, resulting in a pattern with reduced LER (Left-to-Rate) distortion. Furthermore, it is believed that by incorporating these units into the polymer, during vacuum baking, the phenomenon of acid evaporation from the exposed areas and re-adhesion to the unexposed areas is suppressed, thus effectively reducing LER and defects caused by suppressing undesirable negativeing ​​reactions in the unexposed areas.

[0836] Repeating units B7 to B11 can be used individually or in combination of two or more.

[0837] In order to achieve fine-tuning of the properties of the resist film, polymers B and B' may also contain (meth)acrylate units with close-knit groups such as hydroxyl groups other than lactone structures and phenolic hydroxyl groups, or other repeating units.

[0838] Examples of (meth)acrylate units with binding groups mentioned above include: repeating units represented by formula (B12) (hereinafter also referred to as repeating unit B12), repeating units represented by formula (B13) (hereinafter also referred to as repeating unit B13), and repeating units represented by formula (B14) (hereinafter also referred to as repeating unit B14). These units do not exhibit acidity and can be used auxiliaryly as units to provide adhesion to the substrate and to adjust solubility.

[0839] [Chemistry 280]

[0840]

[0841] In equations (B12) to (B14), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 61 It is -O- or methylene. R 62 It can be a hydrogen atom or a hydroxyl group. R 63It is a saturated hydrocarbon group with 1 to 4 carbon atoms. h is 0, 1, 2 or 3.

[0842] In polymer B, the content of repeating unit B1 is preferably 30–95 mol%, and more preferably 50–85 mol%, to obtain high resolution and to elicit high contrast between the negatively irradiated portion and the un-irradiated portion (unnegatively irradiated portion). Furthermore, the content of repeating units B2 and B3 is preferably 5–70 mol%, and more preferably 10–60 mol%, to promote the negativeing ​​reaction. The content of repeating units B4–B6 is preferably 0–30 mol%, and more preferably 3–20 mol%, to improve etching resistance. Additionally, other repeating units may be present in the amount of 0–30 mol%, and preferably 0–20 mol%.

[0843] When polymer B' does not contain repeating units B7 to B11, the content of repeating unit B1 in polymer B' is preferably 25 to 95 mol%, and more preferably 40 to 85 mol%. The content of repeating units B4 to B6 is preferably 0 to 30 mol%, and more preferably 3 to 20 mol%. The content of repeating units B2 and B3 is preferably 5 to 70 mol%, and more preferably 10 to 60 mol%. In addition, other repeating units may also contain 0 to 30 mol%, but preferably 0 to 20 mol%.

[0844] When polymer B' contains repeating units B7 to B11, the content of repeating unit B1 in polymer B' is preferably 25 to 94.5 mol%, more preferably 36 to 85 mol%. The content of repeating units B4 to B6 is preferably 0 to 30 mol%, more preferably 3 to 20 mol%. The content of repeating units B2 and B3 is preferably 5 to 70 mol%, more preferably 10 to 60 mol%. Furthermore, the total content of repeating units B1 to B6 is preferably 60 to 99.5 mol%. The content of repeating units B7 to B11 is preferably 0.5 to 20 mol%, more preferably 1 to 10 mol%. In addition, other repeating units may also be contained in the form of 0 to 30 mol%, preferably 0 to 20 mol%.

[0845] Furthermore, in all the repeating units constituting the aforementioned polymer, repeating units B1 to B6 preferably account for 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. This ensures that the necessary properties for the chemically amplified negative resist composition of the present invention can be reliably obtained.

[0846] Furthermore, at this time, polymer B' is preferably a repeating unit represented by the following formula (B1-1), repeating units represented by the following formulas (B2-1), (B2-2) or (B3-1), and repeating units represented by the following formula (B8-1).

[0847] [Chemistry 281]

[0848]

[0849] In the formula, a4, b4, b6, and R A R 22 R 23 R 32 R 33 and A + Same as above. R HF It can be a hydrogen atom or a trifluoromethyl group. Z 10 For single key or *****-Z 101 -C(=O)-O-。 Z 101 It can also contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. ***** represents the atomic bond of the oxygen atom in the formula.

[0850] When polymer B' is used as the base polymer (B), it is also possible to combine polymers without repeating units B7 to B14 and polymers containing repeating units B7 to B14. In this case, in the chemically amplified negative resist composition of the present invention, the content of the polymer without repeating units B7 to B14 relative to 100 parts by mass of the polymer containing repeating units B7 to B14 is preferably 2 to 5000 parts by mass, and more preferably 10 to 1000 parts by mass.

[0851] When using chemically amplified negative resist compositions in mask fabrication, the coating thickness in the most advanced generation is 150 nm or less, preferably 100 nm or less. The dissolution rate of the base polymer constituting the aforementioned chemically amplified negative resist composition relative to the alkaline developer (e.g., a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution) is generally determined by strong development to reduce defects caused by resist residue. For the formation of fine patterns, a dissolution rate of 80 nm / s or less, preferably 50 nm / s or less, is preferable. Furthermore, for example, when fabricating LSI wafers from wafers using EUV exposure and the chemically amplified negative resist composition of this invention, it is believed that fine lines such as 50 nm or less need to be patterned. Therefore, the coating thickness is often set to 100 nm or less. Because it is a thin film, pattern degradation occurs during development; therefore, the dissolution rate of the polymer used should preferably be 80 nm / s or less, preferably 50 nm / s or less.

[0852] The aforementioned polymer can be synthesized by copolymerizing monomers protected by protecting groups as needed using known methods, followed by deprotection reactions as required. There are no particular limitations on the copolymerization reaction; free radical polymerization and anionic polymerization are preferred. These methods can be referenced in International Patent Application Publication No. 2006 / 121096, Japanese Patent Application Publication No. 2008-102383, Japanese Patent Application Publication No. 2008-304590, and Japanese Patent Application Publication No. 2004-115630.

[0853] The weight-average molecular weight (Mw) of the aforementioned polymer is preferably between 1,000 and 50,000, and more preferably between 2,000 and 20,000. If Mw is above 1,000, there is no concern about the rounding of the pattern head leading to reduced resolution, as is the case with known phenomena, and the occurrence of LER degradation. On the other hand, if Mw is below 50,000, there is no concern about increased LER, especially when forming patterns with a linewidth of 100 nm or less. In addition, in this invention, Mw is a polystyrene equivalent value determined by gel permeation chromatography (GPC) using THF or DMF as a solvent.

[0854] The molecular weight distribution (Mw / Mn) of the aforementioned polymer is preferably 1.0 to 2.0, and a narrow dispersion of 1.0 to 1.8 is even better. With such a narrow dispersion, there will be no foreign matter generated on the pattern after development or the pattern shape will be deteriorated.

[0855] [(C) Crosslinking agent]

[0856] (B) When the base polymer does not contain polymer B', the chemically amplified negative resist composition of the present invention preferably contains a crosslinking agent as component (C). On the other hand, when the base polymer (B) contains polymer B', it may or may not contain a crosslinking agent.

[0857] Specific examples of crosslinking agents that can be used in this invention include: epoxy compounds substituted with at least one group selected from hydroxymethyl, alkoxymethyl, and acyloxymethyl; melamine compounds; guanidine compounds; glycourea compounds or urea compounds; isocyanate compounds; azide compounds; and compounds containing alkenyloxy groups or other double bonds. These can be used as additives or introduced into the polymer side chains as dangling groups. Furthermore, hydroxyl-containing compounds can also be used as crosslinking agents.

[0858] Examples of the aforementioned epoxy compounds include: tris(2,3-epoxypropyl)isocyanurate, trimethylolpropane triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, triethylolethane triepoxypropyl ether, etc.

[0859] Examples of the aforementioned melamine compounds include: compounds or mixtures thereof in which 1 to 6 hydroxymethyl groups are methoxymethylated from hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, etc.; and compounds or mixtures thereof in which 1 to 6 hydroxymethyl groups are acylmethylated from hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol melamine, etc.

[0860] Examples of the aforementioned guanidine compounds include: compounds of tetrahydroxymethylguanidine, tetramethoxymethylguanidine, tetrahydroxymethylguanidine, etc., in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof; and compounds of tetramethoxyethylguanidine, tetraacyloxyguanidine, tetrahydroxymethylguanidine, etc., in which 1 to 4 hydroxymethyl groups are acyloxymethylated, or mixtures thereof.

[0861] Examples of the aforementioned glycourea compounds include: compounds of tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, tetrahydroxymethylglycourea, etc., in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof; and compounds of tetrahydroxymethylglycourea in which 1 to 4 hydroxymethyl groups are acylmethylated, or mixtures thereof.

[0862] Examples of the aforementioned urea compounds include: tetrahydroxymethylurea, tetramethoxymethylurea, tetrahydroxymethylurea, and other compounds in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof, and tetramethoxyethylurea, etc.

[0863] Examples of the aforementioned isocyanate compounds include: toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, etc.

[0864] Examples of the aforementioned azide compounds include: 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylene bisazide, and 4,4'-oxy bisazide.

[0865] Examples of compounds containing alkenyloxy groups include: ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylenediol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, neopentyltetraethylenediol trivinyl ether, neopentyltetraethylenediol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, etc.

[0866] In the chemically amplified negative resist composition of the present invention, the content of (C) crosslinking agent relative to 80 parts by mass of (B) base polymer is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass. If it is within the aforementioned range, the patterns will be connected, reducing concerns about reduced resolution. (C) Crosslinking agent can be used alone or in combination of two or more types.

[0867] [(D) Polymers containing fluorine atoms]

[0868] The chemically amplified negative resist composition of the present invention may contain, for the purposes of high contrast, or suppression of chemical flare of acid under high-energy radiation, shielding of acid mixing from the antistatic film during the process of coating the antistatic film material onto the resist film, and suppression of unintended and unnecessary pattern degradation, at least one of the repeating units represented by formula (D1) (hereinafter also referred to as repeating unit D1), repeating units represented by formula (D2) (hereinafter also referred to as repeating unit D2), repeating units represented by formula (D3) (hereinafter also referred to as repeating unit D3), and repeating units represented by formula (D4) (hereinafter also referred to as repeating unit D4), and further contains a fluorine-containing polymer selected from at least one of the repeating units represented by formula (D5) (hereinafter also referred to as repeating unit D5) and repeating units represented by formula (D6) (hereinafter also referred to as repeating unit D6) as component (D). The aforementioned fluorine-containing polymers also function as surfactants, thus preventing insoluble substances that may be generated during the development process from re-attaching to the substrate, and therefore also playing a role in addressing development defects.

[0869] [Chemistry 282]

[0870]

[0871] In equations (D1) to (D6), j1 is 1, 2, or 3. j2 is an integer satisfying 0 ≤ j2 ≤ 5 + 2(j3) - j1. j3 is 0 or 1. k is 1, 2, or 3. R B Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R C Each can be independently a hydrogen atom or a methyl group. R 101 R 102 R 104 and R 105 Each can be independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. R 103 R 106 R 107 and R 108 Each of the following is independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a fluorinated hydrocarbon group having 1 to 15 carbon atoms, or an acid-unstable group, and R 103 R 106 R 107 and R 108 When the group is a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group can also be inserted between the carbon-carbon bonds. R 109 A linear or branched hydrocarbon group with 1 to 5 carbon atoms, consisting of hydrogen atoms or groups containing heteroatoms inserted between carbon-carbon bonds. When j1 is 2 or 3, each R 209 They can be the same or different. R 110It can also be a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms, in which heteroatoms are inserted between carbon-carbon bonds. When j2 is 2 or more, each R 210 They can be the same or different. R 111 It is a saturated hydrocarbon group with 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and a portion of the -CH2- of the aforementioned saturated hydrocarbon group may also be replaced by an ester bond or an ether bond. X 1 It is a (k+1) valence hydrocarbon group with 1 to 20 carbon atoms or a (k+1) valence fluorinated hydrocarbon group with 1 to 20 carbon atoms. X 2 It is a single bond, *-C(=O)-O-, or *-C(=O)-NH-. * represents an atomic bond with a carbon atom in the main chain. X 3 For single bonds, -O-, *-C(=O)-OX 31 -X 32 -or *-C(=O)-NH-X 31 -X 32 -. X 31 It is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms. X 32 These are single bonds, ester bonds, ether bonds, or sulfonamide bonds. * indicates an atomic bond with a carbon atom in the main chain.

[0872] In equations (D1) and (D2), R 101 R 102 R 104 and R 105 The saturated hydrocarbon groups representing 1 to 10 carbon atoms 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, saturated hydrocarbon groups with 1 to 6 carbon atoms are preferred.

[0873] In equations (D1) to (D4), R 103 R 106 R 107 and R 108 The hydrocarbon group representing 1 to 15 carbon atoms can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 15 carbon atoms, alkenyl groups with 2 to 15 carbon atoms, and alkynyl groups with 2 to 15 carbon atoms, with alkyl groups having 1 to 15 carbon atoms being preferable. In addition to the aforementioned alkyl groups, other examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, and n-pentadecanyl. Furthermore, fluorinated hydrocarbon groups can be groups in which some or all of the hydrogen atoms of the carbon atoms bonded to the aforementioned hydrocarbon groups are replaced by fluorine atoms.

[0874] In equation (D4), X 1 The (k+1) valence hydrocarbon groups representing 1 to 20 carbon atoms can be categorized as groups obtained by further removing k hydrogen atoms from alkyl groups having 1 to 20 carbon atoms or cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms. Also, X 1 The (k+1) valent fluorinated hydrocarbon groups representing carbon numbers from 1 to 20 can be groups formed by replacing at least one hydrogen atom of the aforementioned (k+1) valent hydrocarbon groups with a fluorine atom.

[0875] Specific examples of repeating units D1 to D4 can be listed below, but are not limited to these. Additionally, in the following formula, R... B Same as above.

[0876] [Chemistry 283]

[0877]

[0878] [Chemistry 284]

[0879]

[0880] [Chemistry 285]

[0881]

[0882] In equation (D5), R 109 and R 110 Examples of hydrocarbon groups representing 1 to 5 carbon atoms include alkyl, alkenyl, and ynyl groups, with alkyl being preferred. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and n-pentyl. Furthermore, heteroatoms such as oxygen, sulfur, and nitrogen atoms can be inserted between the carbon-carbon bonds of the aforementioned hydrocarbon groups.

[0883] In equation (D5), -OR 109 It should preferably be a hydrophilic group. In this case, R... 109 It is advisable to use hydrogen atoms, or alkyl groups with 1 to 5 carbon atoms that have oxygen atoms inserted between carbon-carbon bonds.

[0884] In equation (D5), X 2 It should be *-C(=O)-O- or *-C(=O)-NH-. Additionally, R C It should be methyl. Through X 2 The presence of a carbonyl group improves the acid capture ability of the antistatic membrane. Also, R D If the methyl group is used, it will become a rigid polymer with a higher glass transition temperature (Tg), thus inhibiting acid diffusion. As a result, it will become a resist film with good stability over time, and the resolution and pattern shape will not deteriorate.

[0885] Repeating unit D5 can be listed as shown below, but is not limited to these. Additionally, in the following formula, R... C Same as above.

[0886] [Chemistry 286]

[0887]

[0888] [Chemistry 287]

[0889]

[0890] In equation (D6), X 3 The saturated alkylene groups representing carbons 1 to 10 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, etc.

[0891] In equation (D6), R 111 The saturated hydrocarbon group with 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom can be any of the following: linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 20 carbon atoms or cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom.

[0892] Repeating unit D6 can be listed as shown below, but is not limited to these. Additionally, in the following formula, R... C Same as above.

[0893] [Chemistry 288]

[0894]

[0895] [Chemistry 289]

[0896]

[0897] [Chemistry 290]

[0898]

[0899] [Chemistry 291]

[0900]

[0901] The content of repeating units D1 to D4 in the aforementioned polymer containing fluorine atoms is preferably 15 to 95 mol%, and more preferably 20 to 85 mol%. The content of repeating units D5 and / or D6 in the aforementioned polymer containing fluorine atoms is preferably 5 to 85 mol%, and more preferably 15 to 80 mol%. Repeating units D1 to D6 can be used alone or in combination of two or more.

[0902] (D) The polymer containing fluorine atoms may also contain other repeating units besides the aforementioned repeating units. Examples of such repeating units include those described in paragraphs

[0046] to

[0078] of Japanese Patent Application Publication No. 2014-177407. (D) When the polymer containing fluorine atoms contains other repeating units, their content should preferably be 50 mol% or less among all the repeating units of the aforementioned polymer containing fluorine atoms.

[0903] (D) Fluorine-containing polymers can be synthesized by copolymerizing monomers protected by protecting groups as needed using known methods, followed by deprotection reactions as required. There are no particular limitations on the copolymerization reaction; free radical polymerization and anionic polymerization are preferred. These methods can be found in Japanese Patent Application Publication No. 2004-115630.

[0904] (D) The Mw of fluorine-containing polymers should preferably be between 2000 and 50000, with 3000 to 20000 being more preferred. If Mw is above 2000, acid will not diffuse, resolution will not deteriorate, and stability over time will not be compromised. If Mw is below 50000, solubility in solvents is sufficient, and coating defects will not occur. Furthermore, the Mw / Mn ratio of (D) fluorine-containing polymers should preferably be between 1.0 and 2.2, with 1.0 to 1.7 being more preferred.

[0905] When the chemically amplified negative resist composition of the present invention contains (D) a polymer containing fluorine atoms, its content relative to 80 parts by mass of the (B) base polymer is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass. The (D) polymer containing fluorine atoms can be used alone or in combination of two or more.

[0906] [(E) Quenching Agent]

[0907] The chemically amplified negative resist composition of the present invention preferably contains a quencher as component (E). Furthermore, in the present invention, the quencher refers to a material that prevents diffusion to unexposed areas by capturing acid generated from the photoacid generator in the chemically amplified resist composition, thereby forming a desired pattern.

[0908] The aforementioned quenching agents can be categorized as known basic compounds. Known basic compounds include: primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds with carboxyl groups, nitrogen-containing compounds with sulfonyl groups, nitrogen-containing compounds with hydroxyl groups, nitrogen-containing compounds with hydroxyl phenyl groups, alcoholic nitrogen-containing compounds, amides, imides, and carbamates. In particular, primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103, especially amine compounds with hydroxyl groups, ether bonds, ester bonds, lactone rings, cyano groups, or sulfonate bonds, or compounds with carbamate groups described in Japanese Patent No. 3790649, are particularly preferred. Ideal examples include: tris[2-(methoxymethoxy)ethyl]amine, tris[2-(methoxymethoxy)ethyl]amine-N-oxide, dibutylaminobenzoic acid, morpholine derivatives, imidazole derivatives, etc. By adding such basic compounds, the diffusion rate of acid in the resist film can be further suppressed, or the shape can be modified, for example.

[0909] Furthermore, examples of the aforementioned quenchers include onium salts such as sulfonium salts, uranium salts, and ammonium salts of α-unfluorinated carboxylic acids, as described in Japanese Patent Application Publication No. 2008-158339. α-fluorinated sulfonic acids, imine acids, or methylated acids require deprotection of unstable acid groups, and α-unfluorinated carboxylic acids are released through salt exchange with α-unfluorinated onium salts. Since α-unfluorinated carboxylic acids hardly undergo deprotection reactions, they function as quenchers.

[0910] Onium salts of carboxylic acids that are not fluorinated at the α-position can be listed as, for example, those represented by the following formula (E1).

[0911] [Chemistry 292]

[0912]

[0913] In equation (E1), R 201 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain hydrogen atoms or heteroatoms, but excludes those in which the hydrogen atom at the α-position of the carboxyl group is replaced by a fluorine atom or a fluoroalkyl group.

[0914] R 201 The hydrocarbon group represented can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, and other alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; alkenyl groups with 2 to 40 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated aliphatic hydrocarbon groups with 3 to 40 carbon atoms, such as cyclohexenyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, alkylphenyl (2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-n-butylphenyl, etc.), di- or trialkylphenyl (2,4-dimethylphenyl, 2,4,6-triisopropylphenyl, etc.), alkylnaphthyl (methylnaphthyl, ethylnaphthyl, etc.), and dialkylnaphthyl (dimethylnaphthyl, diethylnaphthyl, etc.); and aralkyl groups with 7 to 40 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl.

[0915] Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and a portion of the -CH2- group of the hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc. Examples of hydrocarbon groups containing heteroatoms include: heteroaryl groups such as thiophene; alkoxyphenyl groups such as 4-hydroxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4-tert-butoxyphenyl, and 3-tert-butoxyphenyl; alkoxynaphthyl groups such as methoxynaphthyl, ethoxynaphthyl, n-propoxynaphthyl, and n-butoxynaphthyl; dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl; aryloxoalkyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, and 2-(2-naphthyl)-2-oxoethyl; and aryloxoalkyl groups such as 2-aryl-2-oxoethyl.

[0916] In equation (E1), Mq A + The aforementioned onion cation is preferably a sulfonium cation, a monazine cation, or an ammonium cation, with sulfonium cation or monazine cation being more preferred. Specific examples of sulfonium cations include those described in paragraphs

[0102] to

[0125] of Japanese Patent Application Publication No. 2024-003744, those described in paragraphs

[0070] to

[0085] of Japanese Patent Application Publication No. 2023-169812, and specific examples of sulfonium cations represented by formula (Z-3), but are not limited thereto. Specific examples of monazine cations include those described in paragraph

[0181] of Japanese Patent Application Publication No. 2024-000259, but are not limited thereto.

[0917] The aforementioned ammonium cation should preferably be represented by the formula (am-1).

[0918] [Chemistry 293]

[0919]

[0920] In equation (am-1), R q11 ~R q14 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R q11 ~R q14 Any two atoms in the group can also bond to each other and form a ring together with the nitrogen atoms they are bonded to. Specific examples of the aforementioned hydrocarbon groups can be listed and illustrated in the description of formula (A) as R. 2 The same example represents hydrocarbon groups.

[0921] Specific examples of ammonium cations represented by formula (am-1) are listed below, but are not limited thereto.

[0922] [Chemistry 294]

[0923]

[0924] The anions of onium salts represented by formula (E1) can be listed below, but are not limited to these.

[0925] [Chemistry 295]

[0926]

[0927] [Chemistry 296]

[0928]

[0929] [Chemistry 297]

[0930]

[0931] The aforementioned quenching agent can also ideally be a sulfonium salt of a carboxylic acid containing an iodinated benzene ring, represented by the formula (E2).

[0932] [Chemistry 298]

[0933]

[0934] In equation (E2), s is 1, 2, 3, 4, or 5. t is 0, 1, 2, or 3. However, 1 ≤ s + t ≤ 5. u is 1, 2, or 3.

[0935] In equation (E2), R 211 The following groups are considered as radicals: hydroxyl, fluorine, chlorine, bromine, amino, nitro, cyano, saturated hydrocarbon group with 1 to 6 carbon atoms, saturated hydrocarbon oxy group with 1 to 6 carbon atoms, saturated hydrocarbon carbonyl oxy group with 2 to 6 carbon atoms, saturated hydrocarbon sulfonyl oxy group with 1 to 4 carbon atoms, -N(R) 211A )-C(=O)-R 211B or -N(R)211A )-C(=O)-OR 211B Furthermore, some or all of the hydrogen atoms of the saturated hydrocarbon group, saturated hydrocarbon oxygen group, saturated hydrocarbon carbonyl oxygen group, or saturated hydrocarbon sulfonyl oxygen group may be replaced by halogen atoms. 211A It consists of a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. R 211B It is a saturated hydrocarbon group with 1 to 6 carbon atoms or an unsaturated aliphatic hydrocarbon group with 2 to 8 carbon atoms. When t and / or u is 2 or more, each R 211 They can be the same or different.

[0936] In formula (E2), L 21 It is a single bond or a (u+1) valence linking group having 1 to 20 carbon atoms, and may also contain at least one selected from ether bonds, carbonyl groups, ester bonds, amide bonds, sulfonyl lactone rings, lactam rings, carbonate bonds, halogen atoms, hydroxyl groups, and carboxyl groups. The aforementioned saturated hydrocarbon groups, saturated hydrocarbon oxy groups, saturated hydrocarbon carbonyl oxy groups, and saturated hydrocarbon sulfonyl oxy groups may be linear, branched, or cyclic.

[0937] In equation (E2), R 212 R 213 and R 214 Each hydrocarbon group consists independently of a halogen atom or may contain heteroatoms and has 1 to 20 carbon atoms. 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, alkenyl groups with 2 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, and aralkyl groups with 7 to 20 carbon atoms. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be substituted with hydroxyl, carboxyl, halogen, oxo, cyano, nitro, sulfonyl lactone ring, sulfonyl, or groups containing sulfonium salts, and a portion of the -CH2- group may be substituted with ether, ester, carbonyl, amide, carbonate, or sulfonate bonds. Also, R... 212 and R 213 They can also bond to each other and form rings together with the sulfur atoms they are bonded to.

[0938] Specific examples of compounds represented by formula (E2) can be found in Japanese Patent Application Publication No. 2017-219836. Compounds represented by formula (E2) have high sensitization effects due to their high absorption and also have high acid diffusion control effects.

[0939] The aforementioned quenching agent can also be a carboxylate-type compound containing a nitrogen atom, represented by the formula (E3).

[0940] [Chemistry 299]

[0941]

[0942] In equation (E3), R 221 ~R224 Each is independently a hydrogen atom, -L 22 -CO2 - It may also contain hydrocarbon groups with 1 to 20 carbon atoms, or heteroatoms. R 221 With R 222 R 222 With R 223 、or R 223 With R 224 They can also bond to each other and form rings together with the carbon atoms they are bonded to. 22 It is a single bond or may contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. R 225 It consists of a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms.

[0943] In equation (E3), ring R r It is a ring containing carbon atoms and nitrogen atoms of 2 to 6 carbons, and some or all of the hydrogen atoms of the carbon atoms bonded to the ring may be replaced by hydrocarbon groups of 1 to 20 carbons, or -L 22 -CO2 - The ring can be substituted, and a portion of the -CH2- group can be replaced by a sulfur atom, an oxygen atom, or a nitrogen atom. The aforementioned ring can be an alicyclic or aromatic ring, and preferably a 5-membered or 6-membered ring. Specific examples include: pyridine ring, pyrrole ring, pyrrolidine ring, piperidine ring, pyrazole ring, imidazoline ring, pyridazine ring, pyrimidine ring, pyrazine ring, imidazoline ring, oxazole ring, thiazole ring, morpholine ring, thiazine ring, triazole ring, etc.

[0944] The carboxylic acid salt represented by formula (E3) has at least one -L 22 -CO2 - Base. That is, R 221 ~R 224 At least one of them is -L 22 -CO2 - and / or bonded to ring R r At least one of the hydrogen atoms in the carbon atom is a -L 22 -CO2 - Replacement.

[0945] In equation (E3), Mq B + The cation may be a sulfonium cation, a monazine cation, or an ammonium cation, and preferably a sulfonium cation. Specific examples of the aforementioned sulfonium cations may be listed in paragraphs

[0102] to

[0125] of Japanese Patent Application Publication No. 2024-003744, paragraphs

[0070] to

[0085] of Japanese Patent Application Publication No. 2023-169812, and examples of sulfonium cations represented by formula (Z-3), but are not limited thereto.

[0946] The anions of compounds represented by formula (E3) can be listed below, but are not limited to these.

[0947] [Chemical 300]

[0948]

[0949] [Chemical Engineering 301]

[0950]

[0951] [Chemical 302]

[0952]

[0953] [Chemical 303]

[0954]

[0955] [Chemical 304]

[0956]

[0957] [Chemical 305]

[0958]

[0959] Furthermore, the aforementioned quenching agents can also be betaine-type compounds of weak acids. Specific examples are listed below, but are not limited to these.

[0960] [Chemical 306]

[0961]

[0962] The aforementioned quenchers may further include polymer-type quenchers as described in Japanese Patent Application Publication No. 2008-239918. These quenchers improve the rectangularity of the resist pattern by aligning to the surface of the resist film. Polymer-type quenchers also reduce film loss and dome-shaped patterns when using protective films for immersion exposure.

[0963] When the chemically amplified negative resist composition of the present invention contains (E) quencher, its content relative to 80 parts by mass of (B) base polymer is preferably 0 to 50 parts by mass, and more preferably 0.1 to 40 parts by mass. (E) quencher can be used alone or in combination of two or more.

[0964] When the chemically amplified negative resist composition of the present invention contains a photoacid generator (component A) and a quencher (component E), the content ratio of the photoacid generator to the quencher ((A) / (E)) is preferably less than 6 by mass, more preferably less than 5, and even more preferably less than 4. If the content ratio of the photoacid generator to the quencher in the aforementioned chemically amplified negative resist composition is within the aforementioned range, acid diffusion can be sufficiently suppressed, and excellent resolution and dimensional uniformity can be obtained.

[0965] [(F) Organic solvents]

[0966] The chemically amplified negative resist composition of the present invention may also contain an organic solvent as component (F). There are no particular limitations on the organic solvent being capable of dissolving each component. Examples of such organic solvents include, for instance, ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone 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, 1-ethoxy-2-propanol, and diacetone alcohol; and propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether. Ethers such as propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate (EL), 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 γ-butyrolactone; and their mixed solvents, etc.

[0967] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, PGME, cyclohexanone, EL, γ-butyrolactone, and their mixed solvents are preferred.

[0968] When the chemically amplified negative resist composition of the present invention contains (F) organic solvent, its content relative to 80 parts by mass of (B) base polymer is preferably 200 to 10,000 parts by mass, and more preferably 400 to 6,000 parts by mass. (F) organic solvent may be used alone or in combination with two or more types.

[0969] [(G) Other photoacid generating agents]

[0970] The chemically amplified negative resist composition of the present invention may also contain photoacid generators other than those composed of onium salts represented by formula (A) (hereinafter also referred to as other photoacid generators) as component (G). There are no particular limitations on the aforementioned other photoacid generators if they are compounds that generate acid upon irradiation by high-energy rays. Ideal photoacid generators include: sulfonium salts, sulfonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type photoacid generators, etc.

[0971] Specific examples of other photoacid generators mentioned above include: nonafluorobutane sulfonate, partially fluorinated sulfonates described in paragraphs

[0247] to

[0251] of Japanese Patent Application Publication No. 2012-189977, partially fluorinated sulfonates described in paragraphs

[0261] to

[0265] of Japanese Patent Application Publication No. 2013-101271, partially fluorinated sulfonates described in paragraphs

[0122] to

[0142] of Japanese Patent Application Publication No. 2008-111103, and those described in paragraphs

[0080] to

[0081] of Japanese Patent Application Publication No. 2010-215608. Among the aforementioned specific examples, aromatic sulfonate type or alkane sulfonate type photoacid generators are more desirable because they generate an acid of appropriate strength that deprotects the acid-unstable group of repeating unit B2.

[0972] The aforementioned photoacid generator is preferably a salt compound containing anion with the structure shown below.

[0973] [Chemical 307]

[0974]

[0975] [Chemical 308]

[0976]

[0977] [Chemical 309]

[0978]

[0979] [Chemical 310]

[0980]

[0981] [Chemistry 311]

[0982]

[0983] [Chemistry 312]

[0984]

[0985] [Chemistry 313]

[0986]

[0987] [Chemical 314]

[0988]

[0989] [Chemical 315]

[0990]

[0991] [Chemistry 316]

[0992]

[0993] [Chemistry 317]

[0994]

[0995] Furthermore, the aforementioned photoacid generator should also be a salt compound containing an anion represented by the following formula (G1).

[0996] [Chemistry 318]

[0997]

[0998] In equation (G1), p is 1, 2, or 3. q is 1, 2, 3, 4, or 5. r is 0, 1, 2, or 3. s1 is 0 or 1.

[0999] In formula (G1), L 31 It can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond.

[1000] In formula (G1), L 32 It can be an ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond.

[1001] In formula (G1), L C When p is 1, it is a single bond or a hydrocarbon group with 1 to 20 carbon atoms; when p is 2 or 3, it is a (p+1) valence hydrocarbon group with 1 to 20 carbon atoms. The hydrocarbon group and the (p+1) valence hydrocarbon group may also contain at least one of the following: ether bond, carbonyl group, ester bond, amide bond, sulcinolone ring, lactam ring, carbonate bond, halogen atom, hydroxyl group and carboxyl group.

[1002] L CThe alkylene groups representing carbons 1 to 20 can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl diyl groups with 1 to 20 carbon atoms, such as methane-diyl, 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; cyclic saturated alkylene groups with 3 to 20 carbon atoms, such as cyclopentane-diyl, cyclohexane-diyl, norcamphene-diyl, and adamantane-diyl; unsaturated aliphatic alkylene groups with 2 to 20 carbon atoms, such as vinylene and propylene-1,3-diyl; aryl groups with 6 to 20 carbon atoms, such as phenylene and naphthylene; and groups obtained by combining these. Also, L C The (p+1) valence hydrocarbon group representing 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given by further removing one or two hydrogen atoms from the aforementioned examples of hydrocarbon groups representing 1 to 20 carbon atoms.

[1003] In equation (G1), Rf 21 and Rf 22 Each is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom, but at least one of them is a fluorine atom or a trifluoromethyl atom.

[1004] In equation (G1), R 301 It can be a hydroxyl group, a carboxyl group, a saturated hydrocarbon group with 1 to 6 carbon atoms, a saturated hydrocarbon oxygen group with 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl oxygen group with 2 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, or a -N(R) group. 301A (R) 301B ), -N(R 301C )-C(=O)-R 301D or -N(R) 301C )-C(=O)-OR 301D R 301A and R 301B Each can be independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. R 301C It consists of a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. R 301D It is a saturated hydrocarbon group with 1 to 6 carbon atoms or an unsaturated aliphatic hydrocarbon group with 2 to 8 carbon atoms.

[1005] R 301 R 301A R 301B R 301C and R 301DThe saturated hydrocarbon groups representing 1 to 6 carbon atoms can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl; and cyclic saturated hydrocarbon groups with 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Also, R... 301 The saturated hydrocarbon base of the saturated hydrocarbon group representing carbon 1 to 6 can be given as examples as the specific examples of the aforementioned saturated hydrocarbon groups, R 301 The saturated hydrocarbon base of the carbonyl group representing 2 to 6 carbon atoms can be exemplified by the 1 to 5 carbon atoms in the specific examples of the aforementioned saturated hydrocarbon groups with 1 to 6 carbon atoms.

[1006] R 301D The unsaturated aliphatic hydrocarbon groups with 2 to 8 carbon atoms can be linear, branched, or cyclic. Specific examples include: alkenyl groups with 2 to 8 carbon atoms such as vinyl, propenyl, butenyl, and hexenyl; alkynyl groups with 2 to 8 carbon atoms such as ethynyl, propynyl, and butynyl; and cyclic unsaturated aliphatic hydrocarbon groups with 3 to 8 carbon atoms such as cyclohexenyl and norcamphenyl.

[1007] In equation (G1), R 302 It is a saturated hydrocarbon group with 1 to 20 carbon atoms or an aryl group with 6 to 20 carbon atoms, and some or all of the hydrogen atoms of the saturated hydrocarbon group may be replaced by halogen atoms other than fluorine atoms, and some or all of the hydrogen atoms of the aryl group may be replaced by substituents selected from saturated hydrocarbon groups with 1 to 20 carbon atoms, saturated hydrocarbon oxygen groups with 1 to 20 carbon atoms, aryl groups with 6 to 14 carbon atoms, halogen atoms and hydroxyl groups.

[1008] R 302 The saturated alkylene groups with 1 to 20 carbon atoms can be linear, branched, or cyclic. Specific examples include: alkylene dimethyl, ethane-1,1-dimethyl, ethane-1,2-dimethyl, propane-1,3-dimethyl, butane-1,4-dimethyl, pentane-1,5-dimethyl, hexane-1,6-dimethyl, heptane-1,7-dimethyl, octane-1,8-dimethyl, nonane-1,9-dimethyl, decane-1,10-dimethyl, undecane-1,11-dimethyl, dodecane-1,12-dimethyl, etc., which are alkylene dimethyl groups with 1 to 20 carbon atoms; and cyclic saturated alkylene groups with 3 to 20 carbon atoms, such as cyclopentane dimethyl, cyclohexane dimethyl, norcamphene dimethyl, and adamantane dimethyl.

[1009] R 302Examples of arylene groups with 6 to 20 carbon atoms include: phenylene, naphthylene, phenanthrenediyl, anthracenediyl, etc. The saturated hydrocarbon group with 1 to 20 carbon atoms and the hydrocarbon group with 1 to 20 carbon atoms that are substituents of the aforementioned arylene groups 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, eicosyl, etc.; and cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, adamantyl, etc. Specific examples of arylene groups with 6 to 14 carbon atoms that serve as substituents for the aforementioned arylene groups include: phenylene, naphthylene, phenanthrenediyl, anthracenediyl, etc.

[1010] The anion represented by formula (G1) should preferably be the anion represented by formula (G2).

[1011] [Chemistry 319]

[1012]

[1013] In equation (G2), p, q, r, L 31 L C and R 301 Same as above. s2 is 1, 2, 3, or 4. R 302A It can be a saturated hydrocarbon group with 1 to 14 carbon atoms, a saturated hydrocarbon oxygen group with 1 to 14 carbon atoms, an aryl group with 6 to 14 carbon atoms, a halogen atom, or a hydroxyl group. Additionally, when s2 is 2, 3, or 4, each R... 302A They can be the same or different.

[1014] Specific examples of anions represented by formula (G1) are listed below, but are not limited to these.

[1015] [Chem.320]

[1016]

[1017] [Chemistry 321]

[1018]

[1019] [Chemistry 322]

[1020]

[1021] [Chemistry 323]

[1022]

[1023] [Chemistry 324]

[1024]

[1025] [Chemistry 325]

[1026]

[1027] [Chemistry 326]

[1028]

[1029] [Chemistry 327]

[1030]

[1031] [Chemistry 328]

[1032]

[1033] [Chemistry 329]

[1034]

[1035] [Chemistry 330]

[1036]

[1037] [Chemistry 331]

[1038]

[1039] [Chemistry 332]

[1040]

[1041] [Chemistry 333]

[1042]

[1043] [Chemistry 334]

[1044]

[1045] [Chemistry 335]

[1046]

[1047] [Chemistry 336]

[1048]

[1049] [Chemistry 337]

[1050]

[1051] [Chemistry 338]

[1052]

[1053] [Chemistry 339]

[1054]

[1055] [Transformation 340]

[1056]

[1057] [Chemistry 341]

[1058]

[1059] [Chemistry 342]

[1060]

[1061] [Chemistry 343]

[1062]

[1063] [Chemistry 344]

[1064]

[1065] [Chemistry 345]

[1066]

[1067] [Chemistry 346]

[1068]

[1069] [Chemistry 347]

[1070]

[1071] (G) In other photoacid generating agents, the cation paired with the aforementioned anion is preferably a sulfonium cation or a monazine cation. Specific examples of the aforementioned sulfonium cation may be listed and illustrated as examples of sulfonium cations represented by formula (Z-1) and examples of sulfonium cations represented by formula (Z-3), but are not limited thereto. Specific examples of the aforementioned monazine cations may be listed and illustrated as examples of monazine cations represented by formula (Z-2), but are not limited thereto.

[1072] The acids produced by the aforementioned photoacid generators should preferably have a pKa of -2.0 or higher, and more preferably -1.0 or higher. Furthermore, the upper limit of the pKa should preferably be 2.0. The pKa values ​​were calculated using the pKa DB function in ACD / Chemsketch ver: 9.04, software developed by Advanced Chemistry Development, Inc.

[1073] When the chemically amplified negative resist composition of the present invention contains (G) other photoacid generating agents, their content relative to 80 parts by weight of the aforementioned base polymer is preferably 1 to 10 parts by weight, and more preferably 1 to 5 parts by weight. By containing other photoacid generating agents, the amount of acid generated in the exposed portion and the solubility inhibition of the unexposed portion can be appropriately adjusted. (G) Other photoacid generating agents can be used alone or in combination of two or more.

[1074] [(H) surfactant]

[1075] In the chemically amplified negative resist composition of the present invention, a conventional surfactant may be included as the (H) component to improve the coating properties to the substrate. Examples of such surfactants include PF-636 (manufactured by OMNOVA SOLUTIONS) and FC-4430 (manufactured by 3M Corporation). Furthermore, many other examples are known, as described in Japanese Patent Application Publication No. 2004-115630, and can be referenced and selected from these. When the chemically amplified negative resist composition of the present invention contains the (H) surfactant, its content is preferably 0 to 5 parts by mass relative to 80 parts by mass of the (B) base polymer. The (H) surfactant may be used alone or in combination of two or more types.

[1076] [Resist Pattern Formation Method]

[1077] The resist pattern forming method of the present invention comprises the following steps:

[1078] A resist film is formed on a substrate using the aforementioned chemically amplified negative resist composition.

[1079] The pattern is irradiated onto the aforementioned resist film using high-energy rays (i.e., the aforementioned resist film is exposed using high-energy rays), and

[1080] The resist film that has been irradiated with the aforementioned pattern is developed using an alkaline developer.

[1081] The aforementioned substrate can be, for example, substrates used in integrated circuit manufacturing (Si, SiO, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective films, etc.) or substrates used in transmissive or reflective mask circuit manufacturing (Cr, CrO, CrON, MoSi2, Si, SiO, SiO2, SiON, SiONC, CoTa, NiTa, TaBN, SnO2, etc.). The aforementioned chemically amplified negative resist composition is coated onto the substrate using methods such as spin coating to achieve a film thickness of 0.03–2 μm. The substrate is then pre-baked on a hot plate, preferably at 60–150°C for 1–20 minutes, and more preferably at 80–140°C for 1–10 minutes, to form a resist film.

[1082] Then, the aforementioned resist film is exposed to high-energy radiation to irradiate the pattern. Examples of such high-energy radiation include: ultraviolet light, far-ultraviolet light, excimer lasers (KrF, ArF, etc.), EUV with wavelengths of 3–15 nm, X-rays, gamma rays, synchrotron radiation, and EB. In this invention, EUV or EB is preferably used for exposure.

[1083] When using ultraviolet light, far ultraviolet light, excimer lasers, EUV, X-rays, gamma rays, or synchrotron radiation for the aforementioned high-energy rays, the exposure dose should preferably be 1–500 mJ / cm² to form the desired pattern using a mask. 2 And preferably, it should be 10–400 mJ / cm 2 Irradiation is performed in this manner. When using EB, in order to form the desired pattern, the exposure dose should be 1–500 μC / cm. 2 And preferably, it should be 10–400 μC / cm 2 Irradiation is performed in this manner.

[1084] In addition to the usual exposure methods, wetting methods can also be used depending on the situation, such as wetting between a mask and a resist film. In this case, a water-insoluble protective film can also be used.

[1085] Then, perform post-exposure baking (PEB) on a heating plate, preferably at 60–150°C for 1–20 minutes and more preferably at 80–140°C for 1–10 minutes.

[1086] Subsequently, a developer solution, preferably 0.1-5% by mass and more preferably 2-3% by mass, such as an alkaline aqueous solution of TMAH, is used to develop the substrate using common methods such as dip, immersion, and spray for 0.1-3 minutes and more preferably 0.5-2 minutes, thereby forming the desired pattern on the substrate.

[1087] Furthermore, the chemically amplified negative resist composition of the present invention is particularly useful for forming patterns with good resolution and low LER. Also, the chemically amplified negative resist composition of the present invention is particularly useful for pattern formation on substrates made of materials whose surfaces are prone to pattern peeling and pattern breakage due to difficulty in achieving good adhesion of the resist pattern. Examples of such substrates include: substrates in which metallic chromium is sputtered on the outermost surface; substrates containing a chromium compound of one or more light elements selected from oxygen, nitrogen, and carbon; and substrates containing SiO2 or SiO2 in the outermost layer. x Substrates containing tantalum compounds, molybdenum compounds, cobalt compounds, nickel compounds, tungsten compounds, tin compounds, etc. The chemically amplified negative resist composition of the present invention is particularly useful in pattern formation using a blank photomask as the substrate. In this case, the blank photomask can be either transmissive or reflective.

[1088] Regarding transmissive blank photomasks, blank photomasks with a chromium-based material as the light-shielding film can be blank photomasks for binary masks or blank photomasks for phase-shifting masks. When used as a blank photomask for binary masks, the light-shielding film can consist of an anti-reflection layer and a light-shielding layer made of a chromium-based material. Alternatively, the anti-reflection film on the surface side can be entirely made of a chromium-based material, or only the outermost layer of the anti-reflection film on the surface side can be made of a chromium-based material, with the remaining portion being, for example, a silicon-based compound material that may also contain transition metals. Furthermore, when used as a blank photomask for phase-shifting masks, a blank photomask for phase-shifting masks with a chromium-based light-shielding film on the phase-shifting film can be considered.

[1089] The aforementioned blank photomasks with chromium-based materials as the outermost layer, such as those described in Japanese Patent Application Publication No. 2008-26500, Japanese Patent Application Publication No. 2007-302873, or examples thereof, are well known as current technology and will be omitted in detail. For example, when a light-shielding film with an anti-reflective layer and a light-shielding layer is constructed using chromium-based materials, a film structure as described below can be used.

[1090] When forming a light-shielding film with an anti-reflective layer and a light-shielding layer using chromium-based materials, the layer structure can be constructed by sequentially stacking the anti-reflective layer and the light-shielding layer from the surface side, or by sequentially stacking the anti-reflective layer, the light-shielding layer, and the anti-reflective layer. Furthermore, the anti-reflective layer and the light-shielding layer can each be multi-layered, and the composition of the layers with different compositions can vary discontinuously or continuously. The chromium-based materials used can be metallic chromium or materials containing light elements such as oxygen, nitrogen, and carbon. Specifically, materials that can be used include: metallic chromium, chromium oxide, chromium nitride, chromium carbide, chromium nitride oxide, chromium carbide oxide, chromium carbide nitride, and chromium carbide nitride oxide.

[1091] Furthermore, a reflective blank mask comprises: a substrate, and a multilayer reflective film formed on one of the main surfaces (outer surface side) of the substrate, specifically a multilayer reflective film that reflects exposure light such as EUV light, and an absorber film formed on the multilayer reflective film, specifically an absorber film that absorbs exposure light such as EUV light and reduces reflectivity. From the reflective blank mask (EUV reflective blank mask), a reflective mask (EUV reflective mask) with an absorber pattern (pattern of absorber film) formed by patterning the absorber film can be manufactured. The wavelength of EUV light used in EUV lithography is 13-14 nm, typically about 13.5 nm.

[1092] The multilayer reflective film is typically disposed in contact with one of the main surfaces of the substrate. However, without compromising the effectiveness of the invention, a base film may also be disposed between the substrate and the multilayer reflective film. The absorber film may be formed in contact with the multilayer reflective film, or a protective film (protective film of the multilayer reflective film) may be disposed between the multilayer reflective film and the absorber film, preferably in contact with the multilayer reflective film. The protective film can be used to protect the multilayer reflective film during cleaning, correction, and other processing. Furthermore, the protective film preferably has the function of protecting the multilayer reflective film and preventing oxidation of the multilayer reflective film when the absorber film is patterned by etching. Alternatively, a conductive film for electrostatically holding the reflective mask in the exposure apparatus may be disposed on the surface opposite to one of the main surfaces of the substrate, i.e., the other main surface (the inner surface side), preferably in contact with the other main surface. Furthermore, here, one main surface of the substrate is defined as the outer surface side and the upper side, and the other main surface is defined as the inner surface side and the lower side. However, the outer and inner surfaces, as well as the upper and lower sides, are defined for ease of explanation. One main surface and the other main surface can be either of the two main surfaces (film forming surfaces) in the substrate, and the outer and inner surfaces, as well as the upper and lower sides, can be interchanged. More specifically, it can be formed using Japanese Patent Application Publication No. 2021-139970 or by a method exemplified therein as a conventional art.

[1093] According to the resist patterning method of the present invention, even when using a substrate (e.g., a transmissive or reflective blank mask) whose outermost surface is made of a material that easily affects the shape of the resist pattern, such as a material containing chromium, silicon, or tantalum, a pattern with extremely high resolution, low LER, excellent rectangularity, and excellent pattern fidelity can still be obtained.

[1094] Example

[1095] The present invention will now be specifically described with reference to synthetic examples, embodiments, and comparative examples, but the present invention is not limited to the embodiments described below. Furthermore, the apparatus used is described below.

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

[1097] [1] Synthesis of onium salts

[1098] [Example 1-1] Synthesis of onium salt PAG-1

[1099] [Chemistry 348]

[1100]

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

[1102] Under nitrogen atmosphere, 14.5 g of starting material SM-1 and 0.2 g of N,N-dimethylformamide were dissolved in 100 g of dichloromethane in a reaction vessel, and the temperature of the reaction vessel was raised to 40 °C. Then, 9.5 g of oxaloyl chloride was added dropwise. After the addition, the temperature of the reaction vessel was maintained at 40 °C while the reaction proceeded for 2 hours. After maturation, the reaction solution was cooled, and 50 g of water was added to stop the reaction. Another 50 g of dichloromethane was added to extract the target compound. After a standard aqueous work-up and solvent distillation, hexane was added for recrystallization, thereby obtaining 13.7 g of intermediate In-1 (95% yield) as white crystals.

[1103] (2) Synthesis of onium salt PAG-1

[1104] Under nitrogen atmosphere, intermediate In-1 (5.8 g) and starting material SM-2 (5.0 g) were suspended in dichloromethane (70 g) in a reaction vessel. Triethylamine (1.4 g) was added dropwise, and the mixture was matured at room temperature for 10 hours. After maturity, water (30 g) was added to stop the reaction. Dichloromethane (30 g) was added to extract the target compound, followed by a standard aqueous work-up. After distillation off the solvent, the compound was purified by silica gel chromatography to obtain 8.6 g of ononium salt PAG-1 (83% yield) as white crystals.

[1105] The TOF-MS results for PAG-1 are shown below.

[1106] MALDI TOF-MS:POSITIVE M + 277 (equivalent to C) 18 H 13 OS + )

[1107] NEGATIVE M - 764 (equivalent to C) 40 H 30 NO 11 S2 -)

[1108] [Examples 1-2 to 1-8] Synthesis of onium salts PAG-2 to PAG-8

[1109] Using the corresponding raw materials and known organic synthesis reactions, onium salts PAG-2 to PAG-8 represented by the following formulas were synthesized.

[1110] [Chemistry 349]

[1111]

[1112] [Chemical 350]

[1113]

[1114] [2] Preparation of chemically amplified negative resist composition

[1115] [Examples 1-1 to 1-54, Comparative Examples 1-1 to 1-10]

[1116] The components shown in Tables 1-3 below were dissolved in organic solvents, and the resulting solutions were filtered through UPE filters and / or nylon filters with sizes of 10 nm, 5 nm, 3 nm, and 1 nm to prepare chemically amplified negative resist compositions (R-1 to R-54, CR-1 to CR-10). The aforementioned organic solvents were a mixture of 790 parts by mass of PGMEA, 1580 parts by mass of EL, and 1580 parts by mass of PGME. Furthermore, a portion of the compositions was supplemented with fluorine-containing polymers (polymers FP-1 to FP-5) as additives, tetramethoxymethyl glycourea (TMGU) as a crosslinking agent, and PF-636 (manufactured by OMNOVA SOLUTIONS) as a surfactant.

[1117] [Table 1]

[1118]

[1119]

[1120] [Table 2]

[1121]

[1122]

[1123] [Table 3]

[1124]

[1125]

[1126] The structures of polymers P-1 to P-30 in Tables 1 to 3 are shown in Table 4 below. Additionally, Mw is the polystyrene conversion value determined by GPC using THF or DMF as a solvent.

[1127] [Table 4]

[1128]

[1129]

[1130] The structure of each unit in Table 4 is as follows.

[1131] [Chemistry 351]

[1132]

[1133] [Chemistry 352]

[1134]

[1135] [Chemistry 353]

[1136]

[1137] [Chemistry 354]

[1138]

[1139] [Chemistry 355]

[1140]

[1141] [Chemistry 356]

[1142]

[1143] The other photoacid generators PAG-A, the comparative photoacid generators cPAG-1 to cPAG-4, the quenchers Q-1 to Q-4, and the fluorine-containing polymers FP-1 to FP-5 are described in Tables 1 to 3 as follows.

[1144] [Chemistry 357]

[1145]

[1146] [Chemistry 358]

[1147]

[1148] [Chemistry 359]

[1149]

[1150] [Hua360]

[1151]

[1152] [3] Evaluation of EB lithography

[1153] [Examples 2-1 to 2-54, Comparative Examples 2-1 to 2-10]

[1154] Various chemically amplified negative resist compositions (R-1 to R-54, CR-1 to CR-10) were spin-coated onto a 152 mm square blank mask with a silicon oxide film on the outermost surface after hexamethyldisilazane (HMDS) vapor prime treatment using ACT-M. The mask was then pre-baked at 110°C for 600 seconds on a heated plate to obtain a resist film with a thickness of 80 nm. The thickness of the obtained resist film was measured using an optical measuring instrument, NANOSPEC (Nanometrics). Measurements were performed at 81 locations within the plane of the blank substrate, excluding the outer edge portion extending 10 mm inward from the outer perimeter. The average film thickness and the film thickness range were calculated.

[1155] Exposure was performed using an electron beam exposure apparatus (EBM-5000plus manufactured by NuFlare Technology, with an accelerating voltage of 50kV), PEB was applied at 120°C for 600 seconds, and development was carried out with a 2.38% by mass TMAH aqueous solution to obtain a negative pattern.

[1156] The obtained resist pattern was evaluated as follows. The patterned blank mask was observed using an overhead SEM (scanning electron microscope). The optimal exposure (μC / cm²) was determined by resolving the 1:1 line-to-space (LS) ratio at 200 nm. 2 The resolution (limit resolution) was determined by setting the smallest size among the exposures with a 1:1 resolution for the 200nm LS pattern. For the 200nm LS pattern obtained with optimal exposure, edge detection was performed using SEM on 80 points of each of the 32 edges of the 200nm LS pattern. The variation (standard deviation, σ) was calculated as three times the value of LER (nm). The pattern shape was visually determined to be rectangular. Furthermore, for pattern fidelity evaluation, when configuring a square dot pattern with a density of 36% and a size of 120nm, the area loss (%) value at one corner of the dot pattern was calculated. A smaller value indicates better rectangularity of the dot shape. The results are shown in Tables 5-7.

[1157] [Table 5]

[1158]

[1159]

[1160] [Table 6]

[1161]

[1162] [Table 7]

[1163]

[1164] The chemically amplified negative resist compositions (R-1 to R-54) of the present invention all exhibit good resolution, LER, pattern rectangularity, and pattern fidelity. On the other hand, the resist compositions of the comparative examples (CR-1 to CR-10) have insufficient design of photoacid generators, resulting in inadequate performance in terms of resolution, LER, and pattern rectangularity.

[1165] The resist patterning method using the chemically amplified negative resist composition of the present invention is useful in the manufacture of semiconductor devices, especially in the optical lithography of transmissive or reflective blank photomasks.

Claims

1. A chemically amplified negative resist composition, comprising: (A) A photoacid generator, composed of an onium salt represented by formula (A), and (B) Basic polymer, comprising a polymer containing repeating units represented by the following formula (B1); In the formula, n1 is 0 or 1; n2 is 1, 2, 3, 4 or 5 when n1 is 0, and 1, 2, 3, 4, 5, 6 or 7 when n1 is 1; n3 is 0 or 1; n4 is 0, 1, 2, 3 or 4; n5 is 0, 1, 2, 3 or 4; however, when n3 is 0, 0 ≤ n4 + n5 ≤ 4, and when n3 is 1, 0 ≤ n4 + n5 ≤ 6; R 1 Each of the following is an iodine atom, or may contain heteroatoms, a branched or cyclic hydrocarbon group having 3 to 20 carbon atoms, and at least one R. 1 It is bonded to the carbon atom adjacent to the carbon atom bonded to S; when n2 is 2 or more, each R 1 They can be the same or different, and there are multiple Rs. 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to; R 2 The hydrocarbon group consisting of 1 to 20 carbon atoms other than fluorine atoms, or possibly containing heteroatoms other than fluorine atoms; when n4 is 2, 3, or 4, each R 2 They can be the same or different, and there are multiple Rs. 2 They can also bond to each other and form rings together with the carbon atoms they are bonded to; R F It is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated alkyl thio group having 1 to 6 carbon atoms; when n5 is 2, 3, or 4, each R F They can be the same or different; Z + It is a ium cation; In the formula, a1 is 0 or 1; a2 is 0, 1 or 2; a3 is an integer that satisfies 0≤a3≤5+2(a2)-a4; a4 is 1, 2 or 3; R A It consists of hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups; R 11 It can be a halogen atom, nitro group, carboxyl group, a saturated hydrocarbon group with 1 to 6 carbons that can also be substituted by a halogen atom, a saturated hydrocarbon carbonyl group with 1 to 6 carbons that can also be substituted by a halogen atom, or a saturated hydrocarbon carbonyl group with 2 to 8 carbons that can also be substituted by a halogen atom; when a3 is 2 or more, each R 11 They can be the same or different; A 1 It is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms, and part of the -CH2- of the saturated hydrocarbon group can also be replaced by -O-.

2. The chemically amplified negative resist composition according to claim 1, wherein, The onium salt is represented by the following formula (A1); In the formula, n2, n3, n4, n5, R 1 R 2 R F and Z + Same as above.

3. The chemically amplified negative resist composition according to claim 2, wherein, The onium salt is represented by the following formula (A2); In the formula, n3, n4, n5, R 1 R 2 R F and Z + Same as above.

4. The chemically amplified negative resist composition according to claim 1, wherein, Z + It is a sulfonium cation represented by formula (Z-1) or a monazine cation represented by formula (Z-2); In the formula, R ct1 ~R ct5 Each is an independent hydrocarbon group consisting of halogen atoms or may contain heteroatoms, having 1 to 30 carbon atoms; also, R ct1 and R ct2 They can also bond to each other and form rings together with the sulfur atoms they are bonded to.

5. The chemically amplified negative resist composition according to claim 1, wherein, Z + The sulfonium cation is represented by the following formula (Z-3); In the formula, m1 is 0 or 1; m2 is 0 or 1; m3 is 0 or 1; m4 is 0, 1, 2, 3 or 4; m5 is 0, 1, 2, 3 or 4; m6 is 0, 1, 2, 3, 4, 5 or 6; m7 is 0, 1, 2, 3, 4, 5 or 6; m8 is 0, 1 or 2; m9 is 0, 1 or 2; m10 is 0, 1 or 2; m11 is 0 or 1; m12 is 0, 1, 2, 3 or 4; m13 is 0, 1 or 2; m14 is 0, 1 or 2. However, when m1 is 0, 0 ≤ m6 + m9 ≤ 4; when m1 is 1, 0 ≤ m6 + m9 ≤ 6; when m2 is 0, 0 ≤ m7 + m10 ≤ 4; when m2 is 1, 0 ≤ m7 + m10 ≤ 6; when m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4; when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6; when m11 is 0, 0 ≤ m12 + m13 ≤ 4; when m11 is 1, 0 ≤ m12 + m13 ≤ 6; and m4 + m12 ≥ 1. R F1 ~R F3 Each R is independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; when m5 is 2, 3, or 4, each R F1 They can be the same or different; when m6 is 2, 3, 4, 5 or 6, each R F2 They can be the same or different; when m7 is 2, 3, 4, 5 or 6, each R F3 They can be the same or different; R ct6 ~R ct9 It can be a halogen atom other than iodine and fluorine atoms, a nitro group, a cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; when m8 is 2, there are 2 R groups. ct6 They can be the same or different, and there are 2 Rs. ct6 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when m9 is 2, the two R atoms... ct7 They can be the same or different, and there are 2 Rs. ct7 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when m10 is 2, the two R atoms... ct8 They can be the same or different, and there are 2 Rs. ct8 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when m13 is 2, the two R atoms... ct9 They can be the same or different, and there are 2 Rs. ct9 They can also bond to each other and form rings together with the carbon atoms they are bonded to; Furthermore, S directly bonded to the sulfonium cation + The aromatic rings can also bond with each other and with S + Together they form a ring; L A and L B Each bond can be independently a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond; X L It is a single bond, or may contain a heteroatom and a hydrocarbon group with 1 to 40 carbon atoms.

6. The chemically amplified negative resist composition according to claim 1, wherein, The polymer also contains at least one repeating unit selected from the repeating units represented by formula (B2) and formula (B3); In the formula, b1 is 0 or 1; b2 is 0, 1 or 2; b3 is an integer that satisfies 0 ≤ b3 ≤ 5 + 2(b2) - b4; b4 is 1, 2 or 3; b5 is 0, 1 or 2; b6 is 1 or 2; R A Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R 21 It is a hydrocarbon group with 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms; when b3 is 2 or more, each R 21 They can be the same or different; R 22 and R 23 Each of the following is independently a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may also be substituted by a hydroxyl group or a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, and the aryl group may also have substituents; however, R 22 and R 23 It cannot be both a hydrogen atom and a hydrogen atom; also, R 22 and R 23 They can also bond to each other and form a ring together with the carbon atoms they are bonded to, and part of the -CH2- in this ring can be replaced by -O- or -S-; when b4 is 2 or 3, each R 22 They can be the same or different; also, when b4 is 2 or 3, each R 23 They can be the same or different; R 31 It is a hydrocarbon group with 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms; when b5 is 2, each R 31 They can be the same or different; R 32 and R 33 Each of the following is independently a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may also be substituted by a hydroxyl group or a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, and the aryl group may also have substituents; however, R 32 and R 33 It cannot be both a hydrogen atom and a hydrogen atom; also, R 32 and R 33 They can also bond to each other and form a ring together with the carbon atoms they are bonded to, and part of the -CH2- in this ring can be replaced by -O- or -S-; when b6 is 2, each R 32 They can be the same or different; also, when b6 is 2, each R 33 They can be the same or different; A 2 It is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms, and part of the -CH2- of the saturated hydrocarbon group can also be replaced by -O-; W 1 and W 2 Each of the following groups is independently composed of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon carbonyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the aryl group may also have substituents; when b4 is 2 or 3, each W 1 They can be the same or different; also, when b6 is 2, each W 2 They can be the same or different.

7. The chemically amplified negative resist composition according to claim 1, wherein, The polymer also contains at least one repeating unit selected from the repeating unit represented by formula (B4), the repeating unit represented by formula (B5), and the repeating unit represented by formula (B6); In the formula, c and d are 0, 1, 2, 3 or 4 independently; e1 is 0 or 1; e2 is 0, 1 or 2; e3 is 0, 1, 2, 3, 4 or 5; R A It consists of hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups; R 41 and R 42 Each R is independently a hydroxyl group, a halogen atom, a saturated hydrocarbon group with 1 to 8 carbons that can also be substituted by a halogen atom, a saturated hydrocarbon carbonyl group with 1 to 8 carbons that can also be substituted by a halogen atom, or a saturated hydrocarbon carbonyl group with 2 to 8 carbons that can also be substituted by a halogen atom; when c is 2, 3, or 4, each R 41 They can be the same or different; when d is 2, 3 or 4, each R 42 They can be the same or different; R 43 It can be a saturated hydrocarbon group with 1 to 20 carbon atoms, a saturated hydrocarbon oxy group with 1 to 20 carbon atoms, a saturated hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms, a saturated hydrocarbon oxy hydrocarbon group with 2 to 20 carbon atoms, a saturated hydrocarbon thioalkyl hydrocarbon group with 2 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, a saturated hydrocarbon sulfinyl group with 1 to 20 carbon atoms, or a saturated hydrocarbon sulfonyl group with 1 to 20 carbon atoms; when e3 is 2, 3, 4, or 5, each R 43 They can be the same or different; A 3 It is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms, and part of the -CH2- of the saturated hydrocarbon group can also be replaced by -O-.

8. The chemically amplified negative resist composition according to claim 6, wherein, The polymer contains at least one repeating unit selected from the repeating unit represented by formula (B7), the repeating unit represented by formula (B8), the repeating unit represented by formula (B9), the repeating unit represented by formula (B10), and the repeating unit represented by formula (B11). In the formula, f1 and f2 are 0, 1, 2 or 3 independently; g1 is 0 or 1; g2 is 0, 1, 2, 3 or 4; g3 is 0, 1, 2, 3 or 4; however, when g1 is 0, 0≤g2+g3≤4, and when g1 is 1, 0≤g2+g3≤6; R A Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z 1 It is a single bond or may have substituents; Z 2 For single bonds, **-C(=O)-OZ 21 -、**-C(=O)-NH-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, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond; Z 4 It is a single bond, or an aliphatic alkylene group with 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups; Z 5 Each can be a single bond, or may have substituents such as phenylene, naphthylene, or *-C(=O)-OZ. 51 -;Z 51 It is an aliphatic alkylene group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the aliphatic alkylene group may also contain a halogen atom, hydroxyl group, ether bond, ester bond, or lactone ring; Z 6 It can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond; Z 7 Each is independently a single bond, ***-Z 71 -C(=O)-O-、***-C(=O)-NH-Z 71 -or ***-OZ 71 -;Z 71 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; Z 8 Each is independently a single bond, ****-Z 81 -C(=O)-O-、****-C(=O)-NH-Z 81 -or ****-OZ 81 -;Z 81 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; Z 9 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, *-C(=O)-OZ 91 -、*-C(=O)-N(H)-Z 91 -or *-OZ 91 -;Z 91 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or phenylene substituted with trifluoromethyl, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; * indicates an atomic bond with a carbon atom in the main chain; ** indicates an atomic bond with a Z atom. 1 atomic bonds; *** indicates and Z 6 atomic bonds; **** represents the bond between Z and Z. 7 atomic bonds; L 1 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; however, all Rf 5 and Rf 6 It cannot be both 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, or a fluorinated alkyl thio group having 1 to 6 carbon atoms; when g2 is 2, 3, or 4, each Rf 7 They can be the same or different; R 51 and R 52 Each can be independently a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms; also, R 51 and R 52 They can also bond to each other and form rings together with the sulfur atoms they are bonded to; R 53 It can be a halogen atom other than fluorine, or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms; when g3 is 2, 3 or 4, each R 53 They can be the same or different, and there are multiple Rs. 53 They can also bond to each other and form rings together with the carbon atoms they are bonded to; M - It is a non-nucleophilic relative ion; A + It is a ium cation.

9. The chemically amplified negative resist composition according to claim 8, wherein, The polymer contains repeating units represented by formula (B1-1), repeating units represented by formula (B2-1), (B2-2) or (B3-1), and repeating units represented by formula (B8-1). In the formula, a4, b4, b6, and R A R 22 R 23 R 32 R 33 and A + Same as above; R HF It can be a hydrogen atom or a trifluoromethyl group; Z 10 For single key or *****-Z 101 -C(=O)-O-;Z 101 It can also contain heteroatoms and has 1 to 20 carbon atoms as a hydrocarbon group; ***** represents the atomic bond of the oxygen atom in the formula.

10. The chemically amplified negative resist composition according to claim 8, wherein, (B) The base polymer contains repeating units represented by formula (B1) and repeating units represented by formula (B2) or (B3), but does not contain repeating units represented by formulas (B7) to (B11).

11. The chemically amplified negative resist composition according to claim 1, wherein, Of all the repeating units in the base polymer, the content of repeating units with an aromatic ring skeleton is more than 60 mol%.

12. The chemically amplified negative resist composition according to claim 1 further contains (C) a crosslinking agent.

13. The chemically amplified negative resist composition according to claim 1, wherein it does not contain a crosslinking agent.

14. The chemically amplified negative resist composition according to claim 1, further comprising (D) a fluorine-containing polymer, the (D) fluorine-containing polymer comprising at least one repeating unit selected from the repeating units represented by formula (D1), formula (D2), formula (D3), and formula (D4), and may also further comprise at least one repeating unit selected from the repeating units represented by formula (D5) and formula (D6); In the formula, j1 is 1, 2 or 3; j2 is an integer that satisfies 0≤j2≤5+2(j3)-j1; j3 is 0 or 1; k is 1, 2 or 3; R B Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R C Each can be independently a hydrogen atom or a methyl group; R 101 R 102 R 104 and R 105 Each is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms; R 103 R 106 R 107 and R 108 Each of the following is independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a fluorinated hydrocarbon group having 1 to 15 carbon atoms, or an acid-unstable group, and R 103 R 106 R 107 and R 108 When the group is a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group can also be inserted between the carbon-carbon bonds; R 109 A straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms, which may be hydrogen atoms or may also have heteroatom-containing groups inserted between carbon-carbon bonds; R 110 It can also be a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms, in which heteroatoms are inserted between carbon-carbon bonds; R 111 It is a saturated hydrocarbon group with 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and part of the -CH2- of the saturated hydrocarbon group may also be replaced by an ester bond or an ether bond; X 1 It is a (k+1) valence hydrocarbon group with 1 to 20 carbon atoms or a (k+1) valence fluorinated hydrocarbon group with 1 to 20 carbon atoms; X 2 * represents a single bond, *-C(=O)-O-, or *-C(=O)-NH-; * represents an atomic bond with a carbon atom in the main chain; X 3 For single bonds, -O-, *-C(=O)-OX 31 -X 32 -or *-C(=O)-NH-X 31 -X 32 -;X 31 It is a single bond or a saturated alkylene group with 1 to 10 carbon atoms; X 32 * represents a single bond, ester bond, ether bond, or sulfonamide bond; * represents an atomic bond with a carbon atom in the main chain.

15. The chemically amplified negative resist composition according to claim 1, further comprising (E) a quencher.

16. The chemically amplified negative resist composition according to claim 15, wherein, The ratio of (A) photoacid generator to (E) quencher, by mass, did not reach 6.

17. The chemically amplified negative resist composition according to claim 1 further contains (F) an organic solvent.

18. The chemically amplified negative resist composition according to claim 1 further contains a photoacid generator other than component (G)(A).

19. A method for forming a resist pattern, comprising the following steps: A resist film is formed on a substrate using the chemically amplified negative resist composition according to any one of claims 1 to 18. The resist film was irradiated with high-energy rays to form a pattern, and The resist film that has been irradiated with the pattern is developed using an alkaline developer.

20. The method for forming a resist pattern according to claim 19, wherein, The high-energy rays are extreme ultraviolet rays or electron beams with wavelengths of 3–15 nm.

21. The method for forming a resist pattern according to claim 19, wherein, The outermost surface of the substrate is composed of a material selected from chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten and tin.

22. The method for forming a resist pattern according to claim 19, wherein, The substrate is a transmissive or reflective blank mask.

23. A transmissive or reflective blank mask coated with a chemically amplified negative resist composition according to any one of claims 1 to 18.

Images