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 provides a chemically amplified negative resist composition capable of obtaining a resist pattern having improved resolution during pattern formation and good LER and pattern loyalty, and a method for forming a resist pattern. A chemically amplified negative resist composition includes (A) a photoacid generator composed of an onium salt represented by the following formula (A), and (B) a base polymer including 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 progressed rapidly. Among them, the processing of patterns below 0.2 μm mainly uses chemically amplified resist compositions with acid as a catalyst. Furthermore, high-energy rays such as ultraviolet light, far-ultraviolet light, and electron beams (EB) are used as exposure sources. Especially in EB lithography, which is used as an ultra-micro processing technology, the processing method of blank photomasks when fabricating photomasks for semiconductor manufacturing has become indispensable.

[0003] Polymers with a high proportion of aromatic backbones containing acidic side chains, such as polyhydroxystyrene, are useful as resist compositions for KrF lithography using KrF excimer lasers. However, they have high light absorption around 200 nm, making them unsuitable as resist compositions for ArF lithography using ArF excimer lasers. Nevertheless, they are important materials for achieving high etch resistance in powerful techniques for forming patterns with smaller processing limits than those achieved using ArF excimer lasers, namely resist compositions for EB lithography and extreme ultraviolet (EUV) lithography.

[0004] In the processing of blank photomasks, surface materials such as chromium compound films, primarily chromium oxide, which are deposited on the photomask substrate, can easily affect the pattern shape of the chemically amplified resist film. To achieve high resolution and maintain the etched shape, preserving the rectangular pattern outline of the resist film regardless of the substrate type has become a crucial performance characteristic. Furthermore, in recent years, to achieve miniaturization, blank photomask processing sometimes employs MBMW (Multi-Beam Mask Writing) techniques. In this case, low-sensitivity resist compositions that are advantageous for roughness (high-dose areas) are used, and the optimization of resist compositions for these high-dose areas is increasingly gaining attention.

[0005] Photoresist compositions used in optical lithography include positive types that dissolve the exposed areas to form patterns and negative types that leave the exposed areas exposed to form patterns. The choice between these types depends on the desired shape of the resist pattern and is easier for the user to determine. 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 the polymers and renders the polymers insoluble in the aforementioned developer (in some cases, the polymer and crosslinking agent are integrated). Furthermore, a quencher is usually added to control the diffusion of acid generated during exposure.

[0006] Examples of alkali-soluble units constituting the polymer dissolved in the aforementioned aqueous alkaline developer include units derived from phenols. Previously, negative resist compositions of this type have been developed, particularly for exposure using KrF excimer lasers. However, because the phenol-derived units are not transparent at exposure wavelengths of 150–220 nm, they cannot be used for ArF excimer laser applications. In recent years, however, negative resist compositions for short-wavelength exposure methods such as EB and EUV, which aim to obtain finer patterns, have regained attention, as reported in patent documents 1, 2, and 3.

[0007] Furthermore, as one type of acid generating agent, Patent Document 4 describes a sulfonate salt that generates an aromatic group containing an iodine atom. Its purpose is to enhance the sensitivity of EUV lithography. Its main function is as a quencher against fluorinated alkyl sulfonic acid. However, it has not been explored as an acid generating agent, and in particular, it has not been explored as an acid generating agent that uses polyhydroxystyrene, which is used in the EB lithography process during blank masking, as a negative resist composition of the base polymer.

[0008] In optical lithography, various improvements have been made to control sensitivity and pattern contours by altering the selection and combination of materials used in the resist composition and processing conditions. One of the focal points of these improvements is the problem of acid diffusion, which significantly impacts the resolution of chemically amplified resist compositions.

[0009] Quenching agents, which inhibit acid diffusion, are essential components for improving the performance of resist compositions, especially resolution. Various quenching agents have been explored to date, generally using amines and weak acid onium salts. Regarding weak acid onium salts, Patent Document 5 describes how the addition of triphenylsulfonium acetate can create resist patterns with no T-top formation, reduced linewidth difference between isolated and dense patterns, and improved 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, resulting in excellent resolution, improved exposure latitude, and improved depth-of-focus processing tolerance. Moreover, Patent Document 8 describes a resist composition for F2 lithography using an F2 laser containing a photoacid generator that produces fluorine-containing carboxylic acids, resulting in excellent line edge roughness (LER) and improved trailing problems. They 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 are formed by the exchange of strong acid (sulfonic acid) and weak acid onium salts generated from a photoacid generator during exposure, resulting in the replacement of the highly acidic strong acid (sulfonic acid) with the weak acid (carboxylic acid). This process inhibits the acid decomposition reaction of unstable acid groups and reduces (controls) the acid diffusion distance, thus acting as a macroscopic quencher.

[0011] However, in recent years, there has been a demand not only for further improvements in roughness, but also for resist compositions with excellent line-to-spacing (LS), isolated lines (IL), isolated spacing (IS), and dot pattern shape. Patent Document 10 describes a photoresist generating agent that produces large-volume acid and suppresses acid diffusion, achieving patterns with good resolution and roughness, but it suffers from the drawback of rounded corners in the dot patterns. Patent Document 11 proposes a scheme for generating a photoresist generating non-fluorinated aromatic sulfonic acids with multiple large-volume norbornen groups; Patent Document 12 proposes a photoresist generating agent with a triarylbenzenesulfonic acid anionic structure; and Patent Document 13 proposes a scheme for generating a photoresist generating non-fluorinated aromatic sulfonic acids incorporating iodine-containing aromatic rings. Due to the multiple alkyl substituents, aromatic rings, and iodine atoms, the molecular weight of the generated acid increases, thus reducing acid diffusion. However, when forming fine patterns, the suppression of acid diffusion is not yet ideal and further improvement is needed.

[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 the invention aims to solve)

[0028] In view of the foregoing, the present invention aims to provide a chemically amplified negative resist composition that can obtain resist patterns with improved resolution during pattern formation and good LER and pattern fidelity, and a method for forming resist patterns.

[0029] (Methods for solving problems)

[0030] In order to achieve the aforementioned objective, the inventors of this application have diligently explored and discovered that when an onium salt, which is a photoacid generator that produces benzenesulfonic acid derivatives and has a substituent on the carbon atom adjacent to the sulfonium group of the anion and thus contains a triarylbenzene structure or a diarylbenzene structure, is introduced as an acid generator into a negative resist composition for alkaline development, the acid generated therefrom has a moderate acidity, and the excessive diffusion of the acid is suppressed. This allows for the acquisition of patterns with good resolution and low LER, and also provides moderate dissolution inhibition, thus enabling the acquisition of patterns with good rectangularity. This completes the present invention.

[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 (A) a photoacid generator consisting of an onium salt represented by formula (A), and (B) a base polymer comprising a polymer containing repeating units represented by formula (B1).

[0033] [Chemistry 1]

[0034]

[0035] In the formula, n1 is 0 or 1, n2 is 0, 1, 2, 3 or 4, n3 is 1, 2, 3 or 4, n4 is 0 or 1, n5 is 0, 1, 2, 3 or 4, and n6 is 0, 1, 2, 3 or 4. However, when n1 is 0, 1 ≤ n2 + n3 ≤ 5; when n1 is 1, 1 ≤ n2 + n3 ≤ 7.

[0036] R 1 It is a hydrocarbon group with 1 to 20 carbon atoms.

[0037] R 2 The radical can be a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxycarbonyl group with 1 to 20 carbon atoms containing heteroatoms. When n2 is 2, 3, or 4, each R... 2 They can be the same or different, multiple Rs 2 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0038] R 3 The radical can be a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxycarbonyl group with 1 to 20 carbon atoms containing heteroatoms; or a hydrocarbon carbonyloxy group with 1 to 20 carbon atoms containing heteroatoms. When n5 is 2, 3, or 4, each R... 3 They can be the same or different, multiple Rs 3 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0039] R 4 The radical can be a halogen atom, nitro group, cyano group, hydroxyl 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 n6 is 2, 3, or 4, each R... 4 They can be the same or different, but multiple Rs 4 They do not bond with each other and form rings with the carbon atoms they are bonded to.

[0040] L A L B and L C Each bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0041] X L1 It is a single bond, or may contain a heteroatom, consisting of a hydrocarbon group with 1 to 40 carbon atoms.

[0042] Z + It is a ium cation.

[0043] [Chemistry 2]

[0044]

[0045] In the formula, a1 is 0 or 1, a2 is 0, 1 or 2, a3 is an integer satisfying 0 ≤ a3 ≤ 5 + 2(a2) - a4, and a4 is 1, 2 or 3.

[0046] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0047] R 11 It can be a halogen atom, a nitro group, a carboxyl group, or a 1-6 carbon saturated hydrocarbon group that can be substituted with a halogen atom, or a 2-8 carbon saturated hydrocarbon carbonyl group that can be substituted with a halogen atom.

[0048] 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 may also be replaced by -O-.

[0049] 2. A chemically amplified negative resist composition as described in 1, wherein the onium salt is represented by the following formula (A1).

[0050] [Chemistry 3]

[0051]

[0052] In the formula, n2, n3, n5, n6, R 1 ~R 4 L A L B L C X L1 and Z + As mentioned above.

[0053] 3. A chemically amplified negative resist composition as described in 2, wherein the onium salt is represented by the following formula (A2).

[0054] [Chemistry 4]

[0055]

[0056] In the formula, n2, n3, n5, n6, R 1 ~R 4 L A and Z + As mentioned above.

[0057] 4. A chemically amplified negative resist composition as described in any of 1. to 3, wherein Z + The sulfonium cation is represented by formula (Z-1) or the monazine cation is represented by formula (Z-2).

[0058] [Chemistry 5]

[0059]

[0060] In the formula, R ct1 ~R ct5Each is an independent hydrocarbon group with 1 to 30 carbon atoms, which may also contain heteroatoms; and R ct1 and R ct2 They can also bond to each other and form rings together with the sulfur atoms they are bonded to.

[0061] 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).

[0062] [Chemistry 6]

[0063]

[0064] 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, and 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.

[0065] R F 1 ~R F3 Each R is independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms. When m5 is 2 or more, each R F 1 They can be the same or different. When m6 is 2 or more, each R F2 They can be the same or different. When m7 is 2 or more, each R F3 They can be the same or different.

[0066] R ct6 ~R ct9 The radical can be a halogen atom other than iodine and fluorine, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms, a hydrocarbon oxygen group with 1 to 20 carbon atoms that may contain heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms that may contain heteroatoms. When m8 is 2, there are 2 R radicals. ct6 They can be the same or different, 2 Rs ct6They 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, 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, 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, 2 Rs ct9 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0067] Furthermore, the direct bond S in the sulfonium cation + The aromatic rings can also bond with each other and with S + Together they form a ring.

[0068] L D and L E Each bond can be independently a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0069] X L2 It is a single bond, or may contain heteroatoms, and is a hydrocarbon group with 1 to 40 carbon atoms.

[0070] 6. A chemically amplified negative resist composition as described in any one of 1. to 5, wherein the polymer further contains at least one repeating unit selected from the repeating units represented by formula (B2) and formula (B3).

[0071] [Chemistry 7]

[0072]

[0073] 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, and b6 is 1 or 2.

[0074] R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0075] R 21 It is a hydrocarbon group with 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms.

[0076] R 22 and R 23 Each group 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. This hydrocarbon group may also be substituted by a hydroxyl group or a saturated hydroxyl group having 1 to 6 carbon atoms. The aryl group may also have substituents, but R...22 and R 23 They are not both hydrogen atoms, and 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. A portion of the -CH2- in this ring can also be replaced by -O- or -S-.

[0077] R 31 It is a hydrocarbon group with 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms.

[0078] R 32 and R 33 Each group 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. This hydrocarbon group may also be substituted by a hydroxyl group or a saturated hydroxyl group having 1 to 6 carbon atoms. The aryl group may also have substituents, but R... 32 and R 33 They are not both hydrogen atoms, and 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. A portion of the -CH2- in this ring can also be replaced by -O- or -S-.

[0079] A 2 It is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms, and part of the -CH2- of this saturated hydrocarbon group may also be replaced by -O-.

[0080] W 1 and W 2 Each of the following groups is independently 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. The aryl group may also have substituents.

[0081] 7. A chemically amplified negative resist composition as described in any one of 1. to 6, wherein the polymer further contains at least one repeating unit selected from the repeating units represented by formula (B4), formula (B5), and formula (B6).

[0082] [Chemistry 8]

[0083]

[0084] In the formula, c and d are each independently 0, 1, 2, 3 or 4, e1 is 0 or 1, e2 is 0, 1 or 2, and e3 is 0, 1, 2, 3, 4 or 5.

[0085] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0086] R 41 and R 42Each can be independently a hydroxyl group, a halogen atom, a saturated hydrocarbon group with 1 to 8 carbon atoms that can be substituted with a halogen atom, a saturated hydrocarbon oxygen group with 1 to 8 carbon atoms that can be substituted with a halogen atom, or a saturated hydrocarbon carbonyl group with 2 to 8 carbon atoms that can be substituted with a halogen atom.

[0087] R 43 It can be a saturated hydrocarbon group with 1 to 20 carbon atoms, a saturated hydrocarbon oxygen group with 1 to 20 carbon atoms, a saturated hydrocarbon carbonyl group with 2 to 20 carbon atoms, a saturated hydrocarbon sulfonyl 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.

[0088] 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 may also be replaced by -O-.

[0089] 8. As in 6., a chemically amplified negative resist composition, wherein,

[0090] The polymer contains at least one repeating unit selected from the following formula (B7), the following formula (B8), the following formula (B9), the following formula (B10), and the following formula (B11).

[0091] [Chemistry 9]

[0092]

[0093] In the formula, f1 and f2 are each independently 0, 1, 2 or 3, g1 is 0 or 1, g2 is 0, 1, 2, 3 or 4, and g3 is 0, 1, 2, 3 or 4. However, when g1 is 0, 0 ≤ g2 + g3 ≤ 4; when g1 is 1, 0 ≤ g2 + g3 ≤ 6.

[0094] R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0095] Z 1 It can be a single bond or may have substituents, phenylene

[0096] Z 2 For single bonds, **-C(=O)-OZ 21 -、**-C(=O)-NH-Z 21 -or**-OZ 21 -, Z 21 It is a divalent group obtained by aliphatic hydrocarbon groups, phenylene groups, or combinations thereof having 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups.

[0097] Z 3The bonds can be single bonds, ether bonds, ester bonds, amide bonds, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds.

[0098] Z 4 It is a single bond, or a divalent group obtained by aliphatic alkylene groups, phenylene groups, or combinations thereof having 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups.

[0099] 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 hydrocarbon group, phenylene, or naphthylene group having 1 to 10 carbon atoms. This aliphatic hydrocarbon group may also contain a halogen atom, hydroxyl group, ether bond, ester bond, or lactone ring.

[0100] Z 6 The bonds can be single bonds, ether bonds, ester bonds, amide bonds, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds.

[0101] 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, which may also contain heteroatoms.

[0102] Z 8 Each is independently a single key, ****-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, which may also contain heteroatoms.

[0103] Z 9 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, *-C(=O)-OZ 91 -、*-C(=O)-N(H)-Z 91 -or *-OZ 91 -, Z 91 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms. It may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group.

[0104] * indicates an atomic bond with a carbon atom in the main chain, ** indicates an atomic bond with a Z atom. 1 atomic bonds, *** represents the bond between Z and 6atomic bonds, **** represents the bond between Z and 7 atomic bonds,

[0105] L 1 The bonds can be single bonds, ether bonds, ester bonds, carbonyl groups, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds.

[0106] Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms.

[0107] 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.

[0108] Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, but all Rf 5 and Rf 6 They are not both hydrogen atoms.

[0109] 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.

[0110] R 51 and R 52 Each can be an independent hydrocarbon group with 1 to 20 carbon atoms, and 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.

[0111] R 53 When g3 is 2, 3, or 4, each R 53 They can be the same or different, multiple Rs 53 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0112] M - It is a non-nucleophilic relative ion.

[0113] A + It is a ium cation.

[0114] 9. As in 8., a chemically amplified negative resist composition, wherein,

[0115] The polymer contains repeating units represented by formula (B1-1), repeating units represented by formulas (B2-1), (B2-2) or (B3-1), and repeating units represented by formula (B8-1).

[0116] [Chemistry 10]

[0117]

[0118] In the formula, a4, b4, b6, and R A R 22 R 23 R 32 R 33 and A + As mentioned above,

[0119] R HF It is a hydrogen atom or a trifluoromethyl group.

[0120] 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, and ***** represents the atomic bond of the oxygen atom in the formula.

[0121] 10. The chemically amplified negative resist composition of 8, wherein the base polymer (B) further comprises a polymer containing repeating units represented by formula (B1) and repeating units represented by formula (B2) or (B3) but not repeating units represented by formulas (B7) to (B11).

[0122] 11. A chemically amplified negative resist composition as described in any of 1. to 10, wherein,

[0123] Of all the repeating units contained in this base polymer, the content of repeating units with an aromatic ring skeleton is more than 60 mol%.

[0124] 12. Any chemically amplified negative resist composition as described in 1 to 11, further contains (C) a crosslinking agent.

[0125] 13. Chemically amplified negative resist composition as described in any of 1. to 12, without crosslinking agents.

[0126] 14. The chemically amplified negative resist composition of any one of 1. to 13, further comprising (D) a polymer containing fluorine atoms, wherein the (D) fluorine-containing polymer contains at least one repeating unit selected from the following formula (D1), the following formula (D2), the following formula (D3), and the following formula (D4), and may also further contain at least one repeating unit selected from the following formula (D5) and the following formula (D6).

[0127] [Chemistry 11]

[0128]

[0129] 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; and k is 1, 2, or 3.

[0130] R B Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0131] R C Each can be independently a hydrogen atom or a methyl group.

[0132] 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.

[0133] R 103 R 106 R 107 and R 108 Each 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-labile group, 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.

[0134] R 109 A straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms, which may also have heteroatom-containing groups inserted between hydrogen atoms or carbon-carbon bonds.

[0135] R 110 It consists of straight-chain or branched hydrocarbon groups with 1 to 5 carbon atoms, into which heteroatoms may be inserted between carbon-carbon bonds.

[0136] R 111 A saturated hydrocarbon group with 1 to 20 carbon atoms, in which at least one hydrogen atom is replaced by a fluorine atom. A portion of the -CH2- group of this saturated hydrocarbon group may also be replaced by an ester or ether bond.

[0137] 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.

[0138] X 2 It is a single bond, *-C(=O)-O- or *-C(=O)-NH-, where * represents an atomic bond with a carbon atom in the main chain.

[0139] X 3 For single bonds, -O-, *-C(=O)-OX 31 -X32 -or *-C(=O)-NH-X 31 -X 32 -, X 31 X is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms. 32 It is a single bond, ester bond, ether bond, or sulfonamide bond, and * is an atomic bond with a carbon atom in the main chain.

[0140] 15. A chemically amplified negative resist composition as described in any of 1. to 14, further comprising (E) a quencher.

[0141] 16. As in 15, a chemically amplified negative resist composition, wherein the ratio of (A) acid generator to (E) quencher by mass is less than 6.

[0142] 17. A chemically amplified negative resist composition as described in any of 1. to 16, further comprising (F) an organic solvent.

[0143] 18. A chemically amplified negative resist composition as described in any of 1. to 17, further comprising a photoacid generator other than component (G)(A).

[0144] 19. A method for forming a resist pattern, comprising the following steps:

[0145] A resist film is formed on a substrate using a chemically amplified negative resist composition as described in any of 1. to 18. The resist film is then irradiated with a pattern using high-energy rays, and the irradiated resist film is developed using an alkaline developer.

[0146] 20. The method for forming a resist pattern as described in 19, wherein the high-energy ray is extreme ultraviolet light or an electron beam with a wavelength of 3 to 15 nm.

[0147] 21. A method for forming a resist pattern as described in 19 or 20, wherein the outermost surface of the substrate is composed of a material containing at least one selected from chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten, and tin.

[0148] 22. A method for forming a resist pattern as described in any one of 19 to 21, wherein the substrate is a transmissive or reflective blank mask.

[0149] 23. A transmissive or reflective blank mask coated with a chemically amplified negative resist composition as described in any one of 1. to 18.

[0150] (The effect of the invention)

[0151] The chemically amplified negative photoresist composition of the present invention can provide patterns with extremely high resolution and low LER in microfabrication technologies, especially EB lithography and EUV lithography. Furthermore, it has moderate solubility inhibition, thus providing patterns with good rectangularity, making it suitable as a chemically amplified negative photoresist material. Attached Figure Description

[0152] Figure 1 The nuclear magnetic resonance spectrum of the onium salt PAG-1 synthesized in Example 1-1 is shown. 1 H-NMR / DMSO-d6). Detailed Implementation

[0153] The present invention will now be described in detail. Furthermore, in the following description, depending on the structure represented by the chemical formula, there may be asymmetric carbon and mirror-image isomers and non-mirror-image isomers; in such cases, a single formula will be used to represent these isomers. These isomers may be used individually or in mixtures of two or more.

[0154] [Chemical amplification negative resist composition]

[0155] The chemically amplified negative resist composition of the present invention is characterized by comprising (A) a photoacid generator consisting of an onium salt that generates a predetermined benzenesulfonic acid derivative, and (B) a base polymer containing a predetermined polymer.

[0156] [(A) Photoacid generator]

[0157] The onium salt of the photoacid generator that is component (A) is represented by the following formula (A).

[0158] [Chemistry 12]

[0159]

[0160] In formula (A), n1 is 0 or 1. When n1 is 0, it is a benzene ring; when n1 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with n1 of 0 is preferred. n2 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, n2 of 0 or 1 is preferred. n3 is 1, 2, 3, or 4. Considering the availability of raw materials, n3 of 1, 2, or 3 is preferred. Considering acid diffusion control, n3 of 2 or 3 is preferred. n4 is 0 or 1. When n4 is 0, it is a benzene ring; when n4 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with n4 of 0 is preferred. n5 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, n5 of 0, 1, 2, or 3 is preferred. n6 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, n6 of 1 or 2 is preferred. However, when n1 is 0, the result is 1≤n4+n5≤5, and when n1 is 1, the result is 1≤n4+n5≤7.

[0161] In formula (A), R1 These are hydrocarbon groups with 1 to 20 carbon atoms. 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, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, and tricyclic [5.2.1.0]. 2,6 [Decyl, adamantyl, and other aliphatic cyclic hydrocarbon groups with 3 to 20 carbon atoms; aryl groups with 6 to 20 carbon atoms such as phenyl, naphthyl, and anthracene; groups obtained by combining them, etc., but not limited to these. R] 1 It is preferred to use branched alkyl groups with 3 to 20 carbons, such as isopropyl, sec-butyl, tert-butyl, tert-pentyl, and 2-ethylhexyl; aliphatic cyclic hydrocarbon groups with 3 to 20 carbons, such as cyclopentyl and cyclohexyl; or aryl groups with 6 to 20 carbons, such as phenyl and naphthyl.

[0162] In formula (A), R 2 The halogen atom can be a nitro group, cyano group, hydroxyl group, carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxycarbonyl group with 1 to 20 carbon atoms containing heteroatoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, but fluorine or iodine atoms are preferred. The hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl; cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl; alkenyl groups with 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclohexenyl and other cyclounsaturated hydrocarbon groups with 3 to 20 carbon atoms; aryl groups with 6 to 20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms. Similarly, a portion of the -CH2- group constituting the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. Consequently, it may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride, or haloalkyl groups. When n2 is 2, 3, or 4, multiple R... 2 They can be the same or different.

[0163] Furthermore, when n² is 2, 3, or 4, multiple R... 2They can also bond to each other and form rings together with the carbon atoms they are bonded to. In this case, 5- to 8-membered rings are preferred.

[0164] In formula (A), R 3 It can be a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxycarbonyl group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyloxy group with 1 to 20 carbon atoms containing heteroatoms. R 3 Specific examples of halogen atoms and hydrocarbon groups, hydrocarbon oxygen groups, hydrocarbon thio groups, hydrocarbon oxygen carbonyl groups, and hydrocarbon carbonyl oxygen groups can be given and described in relation to R. 2 The specific examples of halogen atoms and hydrocarbon groups shown are the same, but not limited to these. When n5 is 2, 3, or 4, multiple R... 3 They can be the same or different.

[0165] Furthermore, when n5 is 2, 3, or 4, multiple R 3 They can also bond to each other and form rings together with the carbon atoms they are bonded to. In this case, 5- to 8-membered rings are preferred.

[0166] In formula (A), R 4 It can be a halogen atom, nitro group, cyano group, hydroxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; or it can be a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. R 4 Specific examples can be given and R 2 For the same, but not limited to these. R 4 A hydrocarbon group with 1 to 20 carbon atoms is preferred, with alkyl groups having 1 to 20 carbon atoms, aliphatic cyclic hydrocarbon groups having 3 to 20 carbon atoms, or aryl groups having 6 to 20 carbon atoms being more desirable. Also, R... 4 It is advisable to bond in -SO3 - Adjacent or intermediate positions are preferred. R 4 Bonding in -SO3 - When R is adjacent to the neighbor, 4 It is preferred to have a branched alkyl group with 3 to 20 carbon atoms, an aliphatic cyclic hydrocarbon group with 3 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms.

[0167] In formula (A), L A L B and L C Each bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. Among these, L... A Single bonds, ether bonds, ester bonds, and sulfonate bonds are preferred, with ester bonds and sulfonate bonds being even more ideal. LB Single bonds, ether bonds, ester bonds, and sulfonate bonds are preferred, with single bonds, ester bonds, and sulfonate bonds being even more ideal. L C Single bonds, ether bonds, ester bonds, and sulfonate bonds are preferred, with single bonds, ester bonds, and sulfonate bonds being even more ideal. L B It is advisable to bond in -SO3 - The alignment is better.

[0168] In formula (A), X L1 It is a single-bonded or heteroatom-containing hydrocarbon group with 1 to 40 carbon atoms. The aforementioned hydrocarbon group can be linear, branched, or cyclic; specific examples include alkyldiyl groups and cyclic saturated hydrocarbon groups. Specific examples of the aforementioned heteroatom include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0169] X L1 Specific examples of hydrocarbon groups with 1 to 40 carbon atoms that may also contain heteroatoms are listed below, but are not limited to these. Furthermore, in the following formula, * represents each of the following: A and L B Atomic bonds.

[0170] [Chemistry 13]

[0171]

[0172] [Chemistry 14]

[0173]

[0174] [Chemistry 15]

[0175]

[0176] [Chemistry 16]

[0177]

[0178] In the above, X L -0~X L -22 and X L -47~X L -58 is preferred. The onium salt represented by formula (A) is preferably represented by formula (A1).

[0179] [Chemistry 17]

[0180]

[0181] In the formula, n2, n3, n5, n6, R 1 ~R 4 L A L B L C X L1 and Z+ As previously stated, the onium salt represented by formula (A1) is preferably represented by formula (A2).

[0182] [Chemistry 18]

[0183]

[0184] In the formula, n2, n3, n5, n6, R 1 ~R 4 L A and Z + As mentioned above.

[0185] Particularly desirable examples of onium salt anions represented by formula (A) are listed below, but are not limited to these.

[0186] [Chemistry 19]

[0187]

[0188] [Chemistry 20]

[0189]

[0190] [Chemistry 21]

[0191]

[0192] [Chemistry 22]

[0193]

[0194] [Chemistry 23]

[0195]

[0196] [Chemistry 24]

[0197]

[0198] [Chemistry 25]

[0199]

[0200] [Chemistry 26]

[0201]

[0202] [Chemistry 27]

[0203]

[0204] [Chemistry 28]

[0205]

[0206] [Chemistry 29]

[0207]

[0208] [Chemistry 30]

[0209]

[0210] [Chemistry 31]

[0211]

[0212] [Chemistry 32]

[0213]

[0214] [Chemistry 33]

[0215]

[0216] [Chemistry 34]

[0217]

[0218] [Chemistry 35]

[0219]

[0220] [Chemistry 36]

[0221]

[0222] [Chemistry 37]

[0223]

[0224] [Chemistry 38]

[0225]

[0226] [Chemistry 39]

[0227]

[0228] [Chemistry 40]

[0229]

[0230] [Chemistry 41]

[0231]

[0232] [Chemistry 42]

[0233]

[0234] [Chemistry 43]

[0235]

[0236] [Chemistry 44]

[0237]

[0238] [Chemistry 45]

[0239]

[0240] [Chemistry 46]

[0241]

[0242] [Chemistry 47]

[0243]

[0244] [Chemistry 48]

[0245]

[0246] [Chemistry 49]

[0247]

[0248] [Transformation 50]

[0249]

[0250] [Chemistry 51]

[0251]

[0252] [Chemistry 52]

[0253]

[0254] [Chemistry 53]

[0255]

[0256] [Chemistry 54]

[0257]

[0258] [Chemistry 55]

[0259]

[0260] [Chemistry 56]

[0261]

[0262] [Chemistry 57]

[0263]

[0264] [Chem.58]

[0265]

[0266] [Chemistry 59]

[0267]

[0268] [Transformation 60]

[0269]

[0270] [Chemistry 61]

[0271]

[0272] [Chemistry 62]

[0273]

[0274] [Chemistry 63]

[0275]

[0276] [Chemistry 64]

[0277]

[0278] [Chemistry 65]

[0279]

[0280] [Chemistry 66]

[0281]

[0282] [Chemistry 67]

[0283]

[0284] [Chemistry 68]

[0285]

[0286] [Chemistry 69]

[0287]

[0288] [Chemistry 70]

[0289]

[0290] [Chemistry 71]

[0291]

[0292] [Chemistry 72]

[0293]

[0294] [Chemistry 73]

[0295]

[0296] [Chemistry 74]

[0297]

[0298] [Chemistry 75]

[0299]

[0300] [Chemistry 76]

[0301]

[0302] [Chemistry 77]

[0303]

[0304] [Chemistry 78]

[0305]

[0306] [Chemistry 79]

[0307]

[0308] [Chemistry 80]

[0309]

[0310] [Chemistry 81]

[0311]

[0312] [Chemistry 82]

[0313]

[0314] [Chemistry 83]

[0315]

[0316] [Chemistry 84]

[0317]

[0318] [Chemistry 85]

[0319]

[0320] [Chemistry 86]

[0321]

[0322] [Chemistry 87]

[0323]

[0324] [Chemistry 88]

[0325]

[0326] [Chemistry 89]

[0327]

[0328] [Chemistry 90]

[0329]

[0330] [Chemistry 91]

[0331]

[0332] [Chemistry 92]

[0333]

[0334] [Chemistry 93]

[0335]

[0336] [Chemistry 94]

[0337]

[0338] [Chemistry 95]

[0339]

[0340] [Chemistry 96]

[0341]

[0342] [Chemistry 97]

[0343]

[0344] [Chem. 98]

[0345]

[0346] In formula (A), Z + The cation is a sulfonium cation. Preferably, the sulfonium cation represented by formula (Z-1) or the sulfonium cation represented by formula (Z-2) is a sulfonium cation.

[0347] [Chemistry 99]

[0348]

[0349] In equations (Z-1) and (Z-2), R ct1 ~R ct5 Each is an independent hydrocarbon group consisting of halogen atoms or may contain heteroatoms, and has 1 to 30 carbon atoms.

[0350] R ct1 ~R ct5 Specific examples of halogen atoms that can be represented include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0351] R ct1 ~R ct5 The hydrocarbon group 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; 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; cyclohexenyl and other cyclounsaturated hydrocarbon groups with 3 to 30 carbon atoms; 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, with aryl groups being preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also 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.

[0352] 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.

[0353] [Chemistry 100]

[0354]

[0355] In the formula, the dashed line represents R. ct3 Atomic bonds.

[0356] Specific examples of sulfonium cations represented by formula (Z-1) may be found 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, but are not limited to these.

[0357] Specific examples of citric acid represented by formula (Z-2) can be found in paragraph

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

[0358] Z + The onium cation represented by the following formula (Z-3) is also ideal.

[0359] [Chemistry 101]

[0360]

[0361] 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, a benzene ring with m1 = 0 is preferred. 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, a benzene ring with m2 = 0 is preferred. 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, a benzene ring with m3 = 0 is preferred.

[0362] In formula (Z-3), m4 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption for EUV, but the less solvent-soluble it becomes, raising concerns about precipitation in the resist composition. Therefore, m4 is preferred to be 0, 1, 2, or 3, with 0, 1, or 2 being even better.

[0363] 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 even better. 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 even better. 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 even better.

[0364] In formula (Z-3), m8 is 0, 1, or 2. Considering the availability of raw materials, m8 being 0 or 1 is preferred. m9 is 0, 1, or 2. Considering the availability of raw materials, m9 being 0 or 1 is preferred. m10 is 0, 1, or 2. Considering the availability of raw materials, m10 being 0 or 1 is preferred.

[0365] 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, a benzene ring with m11 of 0 is preferred.

[0366] In formula (Z-3), m12 is 0, 1, 2, 3, or 4. The more iodine atoms in the cation structure, the higher the absorption, especially for EUV, but the less solvent solubility there will be concerns about precipitation in the resist composition. Therefore, m12 is better if it is 0, 1, 2, or 3, with 0, 1, or 2 being even better.

[0367] In formula (Z-3), m13 is 0, 1, or 2. Considering the availability of raw materials, m13 being 0 or 1 is preferred. m14 is 0, 1, or 2. Considering the synthesis aspect, m14 being 0 or 1 is preferred.

[0368] 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.

[0369] In equation (Z-3), R F1 ~R F3 Each of the following is independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms. Among the above, trifluoromethyl, trifluoromethoxy, and trifluorothiomethoxy are preferred. When m5 is 2 or more, each R F1 They can be the same or different. When m6 is 2 or more, each R F2 They can be the same or different. When m7 is 2 or more, each R F3 They can be the same or different.

[0370] In equation (Z-3), R ct6 ~R ct9 The group may contain halogen atoms other than iodine and fluorine atoms, nitro, cyano, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. The hydrocarbon group, hydrocarbon oxy group, and hydrocarbon thio group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples can be given and described in the explanation of formula (A) regarding R. 1The examples of the hydrocarbon groups are the same. Furthermore, some or all of the hydrogen atoms in the hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon sulfide group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0371] Also, when m8 is 2, there are 2 Rs. ct6 They can be the same or different, 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, 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, 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, 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 rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0372] Furthermore, the direct bond S in the sulfonium cation represented by formula (Z-3) + The aromatic rings can also bond with each other and with S + Together they form a ring. Specific examples of the aforementioned ring structure can be represented by the following formulas, etc.

[0373] [Chemistry 102]

[0374]

[0375] In equation (Z-3), L D and L EEach bond can be independently a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Among these, L... D Single bonds, ether bonds, ester bonds, or sulfonate bonds are preferred, with ester bonds or sulfonate bonds being even more preferred. L E Single bonds, ether bonds, or ester bonds are preferred, with single bonds being even better.

[0376] In equation (Z-3), X L2 It is a single bond, or may contain heteroatoms, of a hydrocarbon group having 1 to 40 carbon atoms. Specific examples of the aforementioned hydrocarbon groups having 1 to 40 carbon atoms that may also contain heteroatoms can be given and are described in the explanation of formula (A) regarding X. L1 The examples shown are similar to those of the 1 to 40 carbon-containing hydrocarbon groups that may also contain heteroatoms, but are not limited to these.

[0377] The sulfonium cation represented by formula (Z-3) is preferably represented by formula (Z-3-1).

[0378] [Chemistry 103]

[0379]

[0380] In the formula, m4~m10, m12~m14, R F 1 ~R F3 R ct6 ~R ct9 L D L E and X L2 As mentioned above.

[0381] The cation represented by formula (Z-3-1) is preferably represented by formula (Z-3-2).

[0382] [Chemistry 104]

[0383]

[0384] In the formula, m4~m10, R F1 ~R F3 and R ct6 ~R ct8 As mentioned above.

[0385] Specific examples of sulfonium cations represented by formula (Z-3) are listed below, but are not limited to these. Also, in the following formula, Me is a methyl group.

[0386] [Chemistry 105]

[0387]

[0388] [Chemistry 106]

[0389]

[0390] [Chemistry 107]

[0391]

[0392] [Chemistry 108]

[0393]

[0394] [Chemistry 109]

[0395]

[0396] [Chemical 110]

[0397]

[0398] [Chemistry 111]

[0399]

[0400] [Chemistry 112]

[0401]

[0402] [Chemistry 113]

[0403]

[0404] [Chemistry 114]

[0405]

[0406] [Chemistry 115]

[0407]

[0408] [Chemistry 116]

[0409]

[0410] [Chemistry 117]

[0411]

[0412] [Chemistry 118]

[0413]

[0414] [Chemistry 119]

[0415]

[0416] [Chemistry 120]

[0417]

[0418] [Chemistry 121]

[0419]

[0420] [Chemistry 122]

[0421]

[0422] [Chemistry 123]

[0423]

[0424] [Chemistry 124]

[0425]

[0426] [Chemistry 125]

[0427]

[0428] [Chemistry 126]

[0429]

[0430] [Chemistry 127]

[0431]

[0432] [Chemistry 128]

[0433]

[0434] [Chemistry 129]

[0435]

[0436] [Chemistry 130]

[0437]

[0438] [Chemistry 131]

[0439]

[0440] [Chemistry 132]

[0441]

[0442] Specific examples of the onium salts of the present invention can be any combination of the aforementioned anions and cations.

[0443] The onium salts of the present invention can be synthesized using known methods. An example of the method for manufacturing an onium salt represented by the following formula (PAG-1-ex) will be described.

[0444] [Chemistry 133]

[0445]

[0446] In the formula, n1~n6, R 1 ~R 4 L C and Z + As mentioned before. M + It is an alkali metal cation.

[0447] Step 1 involves reacting a commercially available or known synthetic sulfonate anion salt SM-1 with oxaloyl chloride or thionyl chloride to obtain the aromatic sulfonyl chloride intermediate In-1. The reaction can be carried out using known organic synthesis methods. Specifically, the starting material SM-1 is dissolved in a halogenated solvent such as dichloromethane or chloroform, and oxaloyl chloride or thionyl chloride is added dropwise and the reaction proceeds. The reaction can be accelerated by adding a catalyst amount of N,N-dimethylformamide. Heating may be performed if necessary. The reaction temperature is ideally carried out from room temperature to approximately the boiling point of the solvent used, and heating results in a smoother reaction. The ideal reaction time, typically about 2 to 10 hours, is from a yield perspective, if the reaction is monitored by silica gel thin-layer chromatography (TLC) to ensure completion. The reaction is then stopped with water, and the target product is extracted from the reaction mixture and subjected to a standard aqueous work-up to obtain intermediate In-1. The obtained intermediate In-1 can be purified by conventional methods such as chromatography and recrystallization if necessary.

[0448] Step 2 involves the sulfonation reaction of intermediate In-1 with hydroxy aromatic sulfonate SM-2 to obtain the aromatic sulfonate onium salt PAG-1-ex. The reaction can be carried out using conventional methods. Solvents that can be used in the reaction include water; 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. The solvents mentioned above can be selected appropriately according to the reaction conditions; one or more solvents can be used alone or in combination. In the solvents mentioned above, intermediate In-1, hydroxy aromatic sulfonate SM-2, and the base are added sequentially or simultaneously, and the reaction is carried out under cooling or heating as necessary. Bases that can be used in the reaction include: ammonia; amines such as triethylamine, pyridine, dimethylpyridine, colinine, and N,N-dimethylaniline; hydroxides such as sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide; and carbonates such as potassium carbonate and sodium bicarbonate. One or more of these bases can be used alone or in combination. Confirmation of the reaction by TLC is ideal from a yield perspective. The ononium salt PAG-1-ex can be obtained from the resulting reaction solution through conventional aqueous work-up. Purification can be performed by conventional methods such as chromatography and recrystallization if necessary.

[0449] The onnnage salt represented by formula (A) is an onnnage salt of sulfonic acid without fluorine atom substitution, and therefore can produce an acid of moderate strength upon irradiation with high-energy rays. Furthermore, it has a triarylbenzene or diarylbenzene structure and various functional groups can be introduced into the aryl group. Therefore, aryl groups with functional groups are preferred. When a hydrocarbon carbonyl group is present as a functional group, the presence of multiple heteroatoms from the ester bond reduces acid diffusion. Moreover, regarding halogen atoms, especially when a fluorine-containing functional group is present, the solvent solubility of the onnnage salt itself is increased, thus improving uniform dispersion and increasing the acidity of the generated sulfonic acid. This promotes the deprotection reaction of the protecting groups of the base polymer, and can be expected to improve resolving power. Furthermore, when branched alkyl or alicyclic groups are present, the anion removal volume increases, resulting in a large-volume structure, thus producing a low-diffusion acid, thereby improving LER (Leaves Effect Rate), etc. Furthermore, the multiple aromatic rings in the anion, through their interaction (π-π stacking interaction) with the aromatic rings of the base polymer, enhance compatibility and are expected to suppress excessive acid diffusion. Due to these effects, an acid with uniform excessive strength and controlled acid diffusion can be uniformly generated within the resist film. Therefore, even fine patterns can be obtained with good resolution and low LER. The negative resist composition using alkaline developer exhibits moderate solubility inhibition, thus enabling the acquisition of patterns with good rectangularity.

[0450] In the chemically amplified negative resist composition of the present invention, the content of (A) photoacid generator is ideally 0.1 to 40 parts by mass relative to 80 parts by mass of the base polymer (B) described later, and more ideally 1 to 20 parts by mass. If the content of (A) photoacid generator is within the aforementioned range, it will generate an amount of acid necessary for deprotection of acid-instable groups, and also exhibit good storage stability. (A) Photoacid generator can be used alone or in combination of two or more.

[0451] [(B) Basic Polymer]

[0452] (B) The base polymer is a polymer (hereinafter also referred to as polymer B) containing repeating units represented by the following formula (B1). Repeating unit B1 is a repeating unit that provides etch resistance, adhesion to the substrate, and solubility in alkaline developer.

[0453] [Chemistry 134]

[0454]

[0455] In formula (B1), a1 is 0 or 1. a2 is 0, 1, or 2; 0 represents the benzene skeleton, 1 represents the naphthalene skeleton, and 2 represents the anthracene skeleton. 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.

[0456] In equation (B1), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0457] In equation (B1), R 11 The saturated hydrocarbon group can be a halogen atom, nitro group, carboxyl group, or a 1-6 carbon saturated hydrocarbon group that can be substituted with a halogen atom; a 1-6 carbon saturated hydrocarbon oxygen group that can be substituted with a halogen atom; or a 2-8 carbon saturated hydrocarbon carbonyl oxygen group that can be substituted with a halogen atom. The saturated hydrocarbon group, saturated hydrocarbon oxygen group, and saturated hydrocarbon carbonyl oxygen group can be linear, branched, or cyclic. Specific examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, and their structural isomers; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and other cycloalkyl groups; 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 more, each R... 11 They can be the same or different.

[0458] In equation (B1), A 1The saturated alkylene group is a single bond or a saturated alkylene group with 1 to 10 carbon atoms, and a portion of the -CH2- of the saturated alkylene group may be replaced by -O-. The aforementioned saturated alkylene group can be linear, branched, or cyclic, and specific examples include alkyl dimethyl groups with 1 to 10 carbon atoms such as 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; cyclic saturated alkylene groups with 3 to 10 carbon atoms such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; and groups obtained by combining these. When the aforementioned saturated alkylene group contains an ether bond, when a1 in formula (B1) is 1, it 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 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. Also, if the number of carbon atoms in the aforementioned saturated hydrocarbon group is 10 or less, sufficient solubility in alkaline developing solutions can be obtained, which is ideal.

[0459] a1 is 0 and A 1 When it is a single bond, that is, the aromatic ring and the polymer backbone are directly bonded (i.e., there is no linking group (-C(=O)-OA)). 1 When repeating unit B1, ideal examples include units from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene, 6-hydroxy-2-vinylnaphthalene, etc. The repeating unit represented by the following formula (B1-1) is particularly preferred.

[0460] [Chemistry 135]

[0461]

[0462] In the formula, R A And a4 is as described above.

[0463] 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. Also, in the following formula, R... A As mentioned above.

[0464] [Chemistry 136]

[0465]

[0466] Repeating unit B1 can be used alone or in combination of two or more types.

[0467] Polymer B may also contain at least one of the repeating units represented by formula (B2) (hereinafter also referred to as repeating unit B2.) and the repeating units represented by formula (B3) (hereinafter also referred to as repeating unit B3.) (Hereinafter, polymer B that also contains at least one of repeating unit B2 and repeating unit B3 is also referred to as polymer B'.).

[0468] [Chemistry 137]

[0469]

[0470] Repeating units B2 and B3, when exposed to high-energy radiation, will cause -OW due to the action of acid produced from the acid-generating agent. 1 -OW 2 The repeating units initiate a separation reaction and induce insolubility in alkaline developing solutions and cross-linking reactions between polymers. Due to the action of repeating units B2 and B3, the negativeing ​​reaction is carried out more efficiently, thereby improving resolution.

[0471] 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.

[0472] In formula (B3), b5 can be 0, 1, or 2, with 0 or 1 being preferred. b6 can be 1 or 2, but 1 is preferred.

[0473] In equations (B2) and (B3), R A Each of the above can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (B3), among the above, a hydrogen atom or a methyl group is preferred, with a hydrogen atom being even more preferred.

[0474] In equation (B2), R 21 A hydrocarbon group consisting of 1 to 20 carbon atoms, which may be a halogen atom or may also contain heteroatoms. R 21 Specific examples of halogen atoms that can be represented include fluorine, chlorine, bromine, and iodine atoms. R 21 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 found in the explanation of formula (A) regarding R. 1 The examples representing hydrocarbon groups are the same. When b3 is 2 or more, each R 21 They can be the same or different.

[0475] In equation (B2), R 22 and R 23 Each group 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. This hydrocarbon group may also be substituted by a hydroxyl group or a saturated hydroxyl group having 1 to 6 carbon atoms. The aryl group may also have substituents. However, R... 22 and R23 They are not both hydrogen atoms. 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 Preferably, the alkyl group is methyl, ethyl, propyl, butyl, or their structural isomers, and the hydrogen atoms thereof are partially replaced by hydroxyl or saturated alkyl groups.

[0476] In formula (B3), R 31 A hydrocarbon group consisting of 1 to 20 carbon atoms, which may be a halogen atom or may also contain 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 given and described in the explanation of formula (A) regarding R. 1 The examples representing hydrocarbon groups are the same. When b5 is 2 or more, each R 31 They can be the same or different.

[0477] In formula (B3), 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. The hydrocarbon group may also be replaced by a hydroxyl group or a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms. The aryl group may also have substituents.

[0478] R 32 and R 33 The saturated hydrocarbon group representing 1 to 15 carbon atoms can be linear, branched, or cyclic. Specific examples can be given for R. 22 and R 23 The saturated hydrocarbon group is an example of the same.

[0479] R 32 and R 33 Specific examples of aryl groups having 6 to 15 carbon atoms include phenyl, naphthyl, and anthracene, 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 having 1 to 6 carbon atoms that may be substituted with halogen atoms, and saturated hydrocarbon oxygen groups having 1 to 6 carbon atoms that may be substituted with halogen atoms.

[0480] Also, R 32 and R 33 They are not both hydrogen atoms. R 32 and R 33 When either of the two groups is an aryl group that can also have substituents, it is preferable that the other substituent is a hydrogen atom.

[0481] R 32 and R 33 It is better if they are all the same group, and even better if they are all methyl groups.

[0482] Also, R 32 and R 33 They can also bond to each other and form rings with the carbon atoms they are bonded to, and a portion of the -CH2- in this ring can be replaced by -O- or -S-. Examples of such rings include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, adamantane rings, and tricyclic rings [5.2.1.0]. 2,6 Decane ring, tetracyclic ring [6.2.1.1] 3,6 .0 2,7 Dodecane ring, oxanorcampane ring, thianorcampane ring, etc., but not limited to these.

[0483] In equation (B2), A 2 The saturated alkylene group is a single bond or has 1 to 10 carbon atoms, and a portion of the -CH2- group may be replaced by -O-. The aforementioned saturated alkylene group can be linear, branched, or cyclic. Specific examples include alkyl dimethyl groups such as methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl, and their structural isomers; cyclic saturated alkylene groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; and groups obtained by combining these groups. When the aforementioned saturated alkylene group contains an ether bond, and b1 in formula (B2) is 1, it can be inserted anywhere except 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.

[0484] In equations (B2) and (B3), W 1 and W 2 Each of the following groups is independently 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. The aryl group may also have substituents.

[0485] W 1 and W 2The 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 representing the carbonyl group of aliphatic hydrocarbons with 2 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be found in the aforementioned examples of aliphatic hydrocarbon groups with 1 to 9 carbon atoms. 1 and W 2 Specific examples of aryl groups having 6 to 15 carbon atoms include phenyl, naphthyl, and anthracene, 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 having 1 to 6 carbon atoms that may be substituted with halogen atoms, and saturated hydrocarbon oxygen groups having 1 to 6 carbon atoms that may be substituted with halogen atoms.

[0486] It is preferable that the repeating unit B2 is represented by the following formula (B2-1) or (B2-2).

[0487] [Chemistry 138]

[0488]

[0489] In the formula, b4 and R A R 22 and R 23 As mentioned above.

[0490] Ideal examples of repeating unit B2 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned before, Me is methyl and Ac is acetyl.

[0491] [Chemistry 139]

[0492]

[0493] [Chemistry 140]

[0494]

[0495] [Chemistry 141]

[0496]

[0497] [Chemistry 142]

[0498]

[0499] [Chemistry 143]

[0500]

[0501] [Chemistry 144]

[0502]

[0503] [Chemistry 145]

[0504]

[0505] [Chemistry 146]

[0506]

[0507] [Chemistry 147]

[0508]

[0509] [Chemistry 148]

[0510]

[0511] [Chemistry 149]

[0512]

[0513] Repeating unit B2 can be used alone or in combination of two or more types. Repeating unit B3 is preferably represented by the following formula (B3-1).

[0514] [Chemistry 150]

[0515]

[0516] In the formula, b6 and R A R 32 and R 33 As mentioned above.

[0517] Ideal examples of repeating unit B3 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned before, Me is methyl and Ac is acetyl.

[0518] [Chemistry 151]

[0519]

[0520] [Chemistry 152]

[0521]

[0522] [Chemistry 153]

[0523]

[0524] [Chemistry 154]

[0525]

[0526] [Chemistry 155]

[0527]

[0528] [Chemistry 156]

[0529]

[0530] [Chemistry 157]

[0531]

[0532] [Chemistry 158]

[0533]

[0534] [Chemistry 159]

[0535]

[0536] [Chemistry 160]

[0537]

[0538] [Chemistry 161]

[0539]

[0540] [Chemistry 162]

[0541]

[0542] [Chemistry 163]

[0543]

[0544] [Chemistry 164]

[0545]

[0546] [Chemistry 165]

[0547]

[0548] [Chemistry 166]

[0549]

[0550] [Chemistry 167]

[0551]

[0552] [Chemistry 168]

[0553]

[0554] [Chemistry 169]

[0555]

[0556] [Chemistry 170]

[0557]

[0558] [Chemistry 171]

[0559]

[0560] [Chemistry 172]

[0561]

[0562] [Chemistry 173]

[0563]

[0564] [Chemistry 174]

[0565]

[0566] [Chemistry 175]

[0567]

[0568] [Chemistry 176]

[0569]

[0570] [Chemistry 177]

[0571]

[0572] [Chemistry 178]

[0573]

[0574] [Chemistry 179]

[0575]

[0576] [Chemistry 180]

[0577]

[0578] [Chemistry 181]

[0579]

[0580] [Chemistry 182]

[0581]

[0582] [Chemistry 183]

[0583]

[0584] Repeating unit B3 can be used alone or in combination of two or more types.

[0585] 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 units represented by formula (B5) (hereinafter also referred to as repeating unit B5.), and the repeating units represented by formula (B6) (hereinafter also referred to as repeating unit B6.).

[0586] [Chemistry 184]

[0587]

[0588] In equations (B4) and (B5), c and d are each independently 0, 1, 2, 3 or 4.

[0589] In equations (B4) and (B5), R 41 and R 42 Each R is independently a hydroxyl group, a halogen atom, a saturated hydrocarbon group with 1 to 8 carbon atoms that may be substituted with a halogen atom, a saturated hydroxyl group with 1 to 8 carbon atoms that may be substituted with a halogen atom, or a saturated carbonyl group with 2 to 8 carbon atoms that may be substituted with a halogen atom. The aforementioned saturated hydrocarbon group, saturated hydroxyl group, and saturated carbonyl group can be linear, branched, or cyclic. When c is 2 or more, each R... 41 They can be the same or different. When d is 2 or higher, each R... 42 They can be the same or different.

[0590] In formula (B6), e1 is 0 or 1. e2 is 0, 1, or 2. When e is 0, it is a benzene skeleton; when e is 1, it is a naphthalene skeleton; and when e is 2, it is an anthracene skeleton. e3 is 0, 1, 2, 3, 4, or 5. When e2 is 0, e3 is preferably 0, 1, 2, or 3; when e2 is 1 or 2, e3 is preferably 0, 1, 2, 3, or 4.

[0591] In equation (B6), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0592] In equation (B6), R 43The group can be a saturated hydrocarbon group (1-20 carbon atoms), a saturated hydrocarbon oxygen group (1-20 carbon atoms), a saturated hydrocarbon carbonyl 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 oxygen group, saturated hydrocarbon carbonyl group, saturated hydrocarbon oxyalkyl group, saturated hydrocarbon thioalkyl group, saturated hydrocarbon sulfinyl group, and saturated hydrocarbon sulfonyl group can be linear, branched, or cyclic. When e3 is 2 or more, each R... 43 They can be the same or different.

[0593] R 43 The preferred groups are 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, pentoxy, hexoxy, cyclopentoxy, cyclohexoxy, and their structural isomers. Among these, methoxy and ethoxy are particularly useful.

[0594] Furthermore, saturated hydrocarbon carbonyl groups can be easily introduced via chemical modification even after polymer polymerization, allowing for fine-tuning of the solubility of the base polymer in alkaline developers. Examples of such saturated hydrocarbon carbonyl groups include methyl carbonyl group, ethyl carbonyl group, propyl carbonyl group, butyl carbonyl group, pentyl carbonyl group, hexyl carbonyl group, cyclopentyl carbonyl group, cyclohexyl carbonyl group, benzoyloxy group, and structural isomers of the aforementioned hydrocarbon groups. If the carbon number is 20 or less, the effect of controlling / adjusting (mainly reducing) the solubility of the base polymer in alkaline developers can be appropriately achieved, suppressing the occurrence of residue (development defects).

[0595] Among the aforementioned ideal substituents, those that are easy to prepare and useful for monomers include chlorine atoms, bromine atoms, iodine atoms, methyl, ethyl, and methoxy atoms.

[0596] In equation (B6), A 3The saturated alkylene group is a single bond or a saturated alkylene group with 1 to 10 carbon atoms, and a portion of the -CH2- of the saturated alkylene group may be replaced by -O-. The aforementioned saturated alkylene group can be linear, branched, or cyclic, and specific examples include alkyl dimethyl groups with 1 to 10 carbon atoms such as 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; cyclic saturated alkylene groups with 3 to 10 carbon atoms such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; and groups obtained by combining these. When the aforementioned saturated alkylene group contains an ether bond, when e1 in formula (B6) is 1, it can be inserted anywhere except 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. Also, if the number of carbon atoms in the aforementioned saturated hydrocarbon group is 10 or less, sufficient solubility in alkaline developing solutions can be obtained, which is ideal.

[0597] 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., there is no linking group (-C(=O)-OA)). 3 When -)), ideal examples of repeating unit B6 can be units from styrene, 4-chlorostyrene, 4-methylstyrene, 4-methoxystyrene, 4-bromostyrene, 4-acetoxystyrene, 2-hydroxypropylstyrene, 2-vinylnaphthalene, 3-vinylnaphthalene, etc.

[0598] Furthermore, when e1 is 1 (that is, 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. Also, in the following formula, R... A As mentioned above.

[0599] [Chemistry 185]

[0600]

[0601] [Chemistry 186]

[0602]

[0603] When at least one of repeating units B4 to B6 is used as a constituent unit of the aforementioned polymer, it is possible to obtain improved etching resistance and EB irradiation resistance during pattern inspection, in addition to the etching resistance of the aromatic ring, due to the additional ring structure of the main chain.

[0604] Repeating units B4 to B6 can be used individually or in combination of two or more.

[0605] Polymer B' may also contain at least one selected from the following formula (B7) (hereinafter also called repeating unit B7), the following formula (B8) (hereinafter also called repeating unit B8), the following formula (B9) (hereinafter also called repeating unit B9), the following formula (B10) (hereinafter also called repeating unit B10), and the following formula (B11) (hereinafter also called repeating unit B11).

[0606] [Chemistry 187]

[0607]

[0608] In equations (B7) to (B11), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It is a single bond or may have substituents. Z 2 For single bonds, **-C(=O)-OZ 21 -、**-C(=O)-NH-Z 21 -or**-OZ 21 -. Z 21 It is a divalent group obtained by aliphatic hydrocarbon groups, phenylene groups, or combinations thereof having 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups. 3 It can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. 4 It is a single bond, or a divalent group obtained by aliphatic alkylene groups, phenylene groups, or combinations thereof with 1 to 6 carbon atoms, and may also contain halogen atoms, carbonyl groups, ester bonds, ether bonds, or hydroxyl groups. 5 Each can be a single bond, or 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 having 1 to 10 carbon atoms. This aliphatic alkylene group may also contain a halogen atom, hydroxyl group, ether bond, ester bond, or 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, ***-Z 71 -C(=O)-O-、***-C(=O)-NH-Z 71 -or ***-OZ 71 -。 。 Z 71 It can also contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. Z 8 Each is independently a single key, ****-Z 81-C(=O)-O-、****-C(=O)-NH-Z 81 -or ****-OZ 81 -. Z 81 It can also contain heteroatoms and is 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 trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms. It 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.

[0609] Z 21 Z 51 and Z 91 The aliphatic alkyl sub-groups can be linear, branched, or cyclic. Specific examples include alkyl diyl groups such as methane-diyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, 1,1-dimethylethane-1,2-diyl, pentane-1,5-diyl, 2-methylbutane-1,2-diyl, and hexane-1,6-diyl; cycloalkyl diyl groups such as cyclopropane-diyl, cyclobutane-diyl, cyclopentane-diyl, and cyclohexane-diyl; and groups obtained by combining them.

[0610] Z 71 and Z 81 The alkylene group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples are listed below, but are not limited to these.

[0611] [Chem.188]

[0612]

[0613] In the formula, the dashed lines represent atomic bonds.

[0614] In equation (B7), R 51 and R 52Each group can be an independent hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; 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; cyclohexenyl 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, with aryl groups being preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0615] 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.

[0616] [Chemistry 189]

[0617]

[0618] In the formula, the dashed line represents Z. 4 Atomic bonds.

[0619] Specific examples of cations in repeating unit B7 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above.

[0620] [Chemistry 190]

[0621]

[0622] [Chemistry 191]

[0623]

[0624] [Chemistry 192]

[0625]

[0626] [Chemistry 193]

[0627]

[0628] [Chemistry 194]

[0629]

[0630] [Chemistry 195]

[0631]

[0632] [Chemistry 196]

[0633]

[0634] [Chemistry 197]

[0635]

[0636] [Chemistry 198]

[0637]

[0638] [Chemistry 199]

[0639]

[0640] In equation (B7), M - These are non-nucleophilic relative ions. Preferred non-nucleophilic relative ions are halide ions, sulfonic acid anions, imide acid anions, and methylated acid anions. Specific examples of halide ions include chloride ions and bromide ions. Specific examples of sulfonic acid anions (sulfonate ions) include trifluoromethanesulfonate ions, 1,1,1-trifluoroethanesulfonate ions, nonafluorobutanesulfonate ions, and other fluoroalkyl sulfonate ions; toluenesulfonate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, 1,2,3,4,5-pentafluorobenzenesulfonate ions, and other aryl sulfonate ions; methanesulfonate ions, butanesulfonate ions, and other alkyl sulfonate ions. Specific examples of imide acid anions (imide ions) include bis(trifluoromethylsulfonyl)imide ions, bis(perfluoroethylsulfonyl)imide ions, and bis(perfluorobutylsulfonyl)imide ions. Specific examples of the aforementioned methylated acid anions (methylated ions) include tris(trifluoromethylsulfonyl) methylated ions and tris(perfluoroethylsulfonyl) methylated ions.

[0641] Other examples of the aforementioned non-nucleophilic relative ions can be exemplified by anions represented by any of the formulas (B7-1) to (B7-4).

[0642] [Chem.200]

[0643]

[0644] In equation (B7-1), R fa It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain fluorine atoms or heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given by R in the following formula (B7-1-1). fa1 The hydrocarbon group shown is an example of the same.

[0645] The anion represented by formula (B7-1) is preferably represented by the following formula (B7-1-1).

[0646] [Chemical Engineering 201]

[0647]

[0648] 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 atom is preferably trifluoromethyl. m can be 0, 1, 2, 3, or 4, with 1 being particularly preferred. R fa1 Hydrocarbon groups with 1 to 35 carbon atoms that may contain heteroatoms are preferred. Ideal heteroatoms include oxygen, nitrogen, sulfur, and halogen atoms, with oxygen atoms being even more desirable. From the viewpoint of achieving high resolution in the formation of fine patterns, hydrocarbon groups with 6 to 30 carbon atoms are particularly advantageous.

[0649] In equation (B7-1-1), R fa1 The hydrocarbon groups represented by carbon numbers 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 icosyl; 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.

[0650] Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, it may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Specific examples of hydrocarbon groups containing heteroatoms include tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidemethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, 3-oxocyclohexyl, etc.

[0651] 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 more ideal.

[0652] Specific examples of anions represented by equation (B7-1) are listed below, but are not limited to these. Furthermore, in the following equation, Q... 1 As mentioned above, Ac represents the acetyl group.

[0653] [Chemical Engineering 202]

[0654]

[0655] [Chemical Engineering 203]

[0656]

[0657] [Chemical 204]

[0658]

[0659] [Chemical Engineering 205]

[0660]

[0661] [Chemical Engineering 206]

[0662]

[0663] [Chemical 207]

[0664]

[0665] [Chemical Engineering 208]

[0666]

[0667] [Chemical Engineering 209]

[0668]

[0669] [Chemical 210]

[0670]

[0671] [Chemistry 211]

[0672]

[0673] 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. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given by R in formula (B7-1-1). fa1 The hydrocarbon group represented is an example of the same. R fb1 and R fb2 Preferably, it is a straight-chain fluorinated alkyl group having fluorine atoms or 1 to 4 carbon atoms. Also, R fb1 and R fb2 They can also bond to each other and to the groups they are bonded to (-CF2-SO2-N). - -SO2-CF2-) together form a ring, in which case R fb1 and R fb2 The groups obtained by mutual bonding are preferably fluorinated ethylidene or fluorinated propyleneide.

[0674] 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. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given by R in formula (B7-1-1). fa1 The hydrocarbon group represented is an example of the same. R fc1 R fc2 and R fc3 Preferably, it is a straight-chain fluorinated alkyl group having fluorine atoms or 1 to 4 carbon atoms. Also, R fc1 and R fc2 They can also bond to each other and to the groups they are bonded to (-CF2-SO2-C). - -SO2-CF2-) together form a ring, in which case R fc1 and R fc2 The groups obtained by mutual bonding are preferably fluorinated ethylidene or fluorinated propyleneide.

[0675] In equation (B7-4), R fdIt can be a hydrocarbon group with 1 to 40 carbon atoms, and may also contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given by R in formula (B7-1-1). fa1 The hydrocarbon group shown is an example of the same.

[0676] Specific examples of anions represented by formula (B7-4) are listed below, but are not limited to these.

[0677] [Chemistry 212]

[0678]

[0679] [Chemistry 213]

[0680]

[0681] The aforementioned examples of non-nucleophilic relative ions can be further illustrated by anions having aromatic rings substituted with iodine or bromine atoms. Specific examples of such anions can be exemplified by those represented by the following formula (B7-5).

[0682] [Chemistry 214]

[0683]

[0684] 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 being 1, 2, or 3 is ideal, with 2 or 3 being even more ideal. z being 0, 1, or 2 is preferable.

[0685] In equation (B7-5), X BI When x and / or y are 2 or more, they can be the same or different from each other.

[0686] 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.

[0687] 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. This linker may also contain oxygen, sulfur, or nitrogen atoms.

[0688] In equation (B7-5), R feIt can be a hydroxyl, carboxyl, fluorine, chlorine, bromine, or amino group, or may contain a fluorine, chlorine, bromine, hydroxyl, amino, or ether bond, and can be a hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbon oxygen group with 1 to 20 carbon atoms, a hydrocarbon carbonyl group with 2 to 20 carbon atoms, a hydrocarbon carbonyl group with 2 to 20 carbon atoms, or a hydrocarbon sulfonyl group with 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 is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. R feC It is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms. R feD It can be an aliphatic hydrocarbon group with 1 to 16 carbon atoms, an aryl group with 6 to 12 carbon atoms, or an aralkyl group with 7 to 15 carbon atoms. It may also contain a halogen atom, a hydroxyl group, a saturated alkyloxy group with 1 to 6 carbon atoms, a saturated alkylcarbonyl group with 2 to 6 carbon atoms, or a saturated alkylcarbonyloxy group with 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned hydrocarbon group, alkyloxy group, alkylcarbonyl group, alkyloxycarbonyl group, alkylcarbonyloxy group, and alkylsulfonyloxy group can be any of linear, branched, or cyclic. When x and / or z are 2 or more, each R... fe They can be the same or different.

[0689] Of the above, R fe Hydroxyl group, -N(R) feC )-C(=O)-R feD -N(R) feC )-C(=O)-OR feD Fluorine atoms, chlorine atoms, bromine atoms, methyl groups, and methoxy groups are preferred.

[0690] In equation (B7-5), Rf 11 ~Rf 14 Each is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, with at least one of these being 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 preferred if they contain fluorine atoms.

[0691] Specific examples of anions represented by equation (B7-5) are listed below, but are not limited to these. Furthermore, in the following equation, X... BI As mentioned above.

[0692] [Chemical 215]

[0693]

[0694] [Chemistry 216]

[0695]

[0696] [Chemistry 217]

[0697]

[0698] [Chemistry 218]

[0699]

[0700] [Chemistry 219]

[0701]

[0702] [Chem.220]

[0703]

[0704] [Chemistry 221]

[0705]

[0706] [Chemistry 222]

[0707]

[0708] [Chemistry 223]

[0709]

[0710] [Chemistry 224]

[0711]

[0712] [Chemistry 225]

[0713]

[0714] [Chemistry 226]

[0715]

[0716] [Chemistry 227]

[0717]

[0718] [Chemistry 228]

[0719]

[0720] [Chemistry 229]

[0721]

[0722] [Chemistry 230]

[0723]

[0724] [Chemistry 231]

[0725]

[0726] [Chemistry 232]

[0727]

[0728] [Chemistry 233]

[0729]

[0730] [Chemistry 234]

[0731]

[0732] [Chemistry 235]

[0733]

[0734] [Chemistry 236]

[0735]

[0736] [Chemistry 237]

[0737]

[0738] The aforementioned non-nucleophilic relative ions can also include the fluorobenzenesulfonic acid anion with an aromatic group bonded by an iodine atom as described in Japanese Patent No. 6648726, the anion with an acid decomposition mechanism 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.

[0739] The aforementioned non-nucleophilic relative ions can also be further described in Japanese Patent Application Publication Nos. 2006-276759, 2015-117200, 2016-65016 and 2019-202974 as sterically hindered benzenesulfonic acid derivatives without fluorine atoms, and Japanese Patent No. 6645464 as benzoylsulfonic acid anions with aromatic groups bonded to iodine atoms without fluorine atoms and alkylsulfonic acid anions.

[0740] The aforementioned non-nucleophilic relative ions may also include the anions of disulfonic acid as described in Japanese Patent Application Publication No. 2015-206932, the anions of sulfonamides and sulfonamides as described in International Publication No. 2020 / 158366, which are sulfonic acid on one side and different from sulfonamides or sulfonamides on the other side, and the anions of sulfonic acid and carboxylic acid as described in Japanese Patent Application Publication No. 2015-24989.

[0741] In equations (B8) and (B9), f1 and f2 are each independently 0, 1, 2 or 3, with 1 being preferred.

[0742] 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.

[0743] In equations (B8), (B9), and (B10), L 1 The bonds can be single bonds, ether bonds, ester bonds, carbonyl groups, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. From a synthetic perspective, ether bonds, ester bonds, and carbonyl groups are more ideal, with ester bonds and carbonyl groups being even more desirable.

[0744] 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. Of the above, regarding Rf... 1 and Rf 2 In order to increase the acid strength, fluorine atoms are preferred. Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among the above, to improve solvent solubility, Rf... 3 and Rf 4 At least one of them is preferably trifluoromethyl.

[0745] In equation (B9), 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 Rf6 They are not both hydrogen atoms. Of the above, in order to improve solvent solubility, Rf... 5 and Rf 6 At least one of them is preferably trifluoromethyl.

[0746] 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 The most desirable components are fluorine atom, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, or difluoromethylthio, with fluorine atom, trifluoromethyl, or trifluoromethoxy being even more desirable. When g2 is 2, 3, or 4, each Rf... 7 They can be the same or different.

[0747] In formula (B10), R 53 It is a hydrocarbon group with 1 to 20 carbon atoms, other than fluorine atoms, or it may contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given and described in the explanation of formula (A) regarding R. 1 Examples of hydrocarbon groups are shown, but not limited to these. Also, when g3 is 2, 3, or 4, each R... 53 They can be the same or different.

[0748] 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 rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0749] Specific examples of the anions of repeating unit B8 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above, Me is a methyl group.

[0750] [Chemistry 238]

[0751]

[0752] [Chemistry 239]

[0753]

[0754] [Chemistry 240]

[0755]

[0756] [Chemistry 241]

[0757]

[0758] [Chemistry 242]

[0759]

[0760] [Chemistry 243]

[0761]

[0762] [Chemistry 244]

[0763]

[0764] [Chemistry 245]

[0765]

[0766] [Chemistry 246]

[0767]

[0768] [Chemistry 247]

[0769]

[0770] [Chemistry 248]

[0771]

[0772] [Chemistry 249]

[0773]

[0774] [Chemistry 250]

[0775]

[0776] Specific examples of the anions of repeating unit B9 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above.

[0777] [Chemistry 251]

[0778]

[0779] [Chemistry 252]

[0780]

[0781] [Chemistry 253]

[0782]

[0783] [Chemistry 254]

[0784]

[0785] [Chemistry 255]

[0786]

[0787] [Chemistry 256]

[0788]

[0789] [Chemistry 257]

[0790]

[0791] [Chemistry 258]

[0792]

[0793] [Chemistry 259]

[0794]

[0795] [Chemistry 260]

[0796]

[0797] [Chemistry 261]

[0798]

[0799] Specific examples of the anions of repeating unit B10 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above.

[0800] [Chemistry 262]

[0801]

[0802] [Chemistry 263]

[0803]

[0804] [Chemistry 264]

[0805]

[0806] [Chemistry 265]

[0807]

[0808] [Chemistry 266]

[0809]

[0810] [Chemistry 267]

[0811]

[0812] [Chemistry 268]

[0813]

[0814] [Chemistry 269]

[0815]

[0816] [Chemistry 270]

[0817]

[0818] [Chemistry 271]

[0819]

[0820] [Chemistry 272]

[0821]

[0822] [Chemistry 273]

[0823]

[0824] [Chemistry 274]

[0825]

[0826] [Chemistry 275]

[0827]

[0828] [Chemistry 276]

[0829]

[0830] [Chemistry 277]

[0831]

[0832] [Chemistry 278]

[0833]

[0834] Specific examples of the anion of repeating unit B11 can be listed below, but are not limited to these. Also, in the following formula, R... A As mentioned above.

[0835] [Chemistry 279]

[0836]

[0837] In equations (B8) to (B11), A + The cation is an onium cation. Examples of onium cations include sulfonium cations, ferrophosphate cations, and ammonium cations, with sulfonium cations or ferrophosphate cations being preferred. Specific examples of the aforementioned sulfonium cations may be the same as those shown in formula (Z-1) and formula (Z-3), but are not limited to these. Specific examples of the aforementioned ferrophosphate cations may be the same as those shown in formula (Z-2), but are not limited to these. Specific examples of the aforementioned ammonium cations may be the same as those shown in formula (am-1), but are not limited to these.

[0838] The specific structures of repeating units B7 to B11 can be any combination of the aforementioned anions and cations.

[0839] Repeating units B7 to B11 are units that generate acid upon irradiation with high-energy rays. It is believed that by containing these units in the polymer, acid diffusion is moderately suppressed, resulting in a pattern with reduced LER (Left-to-Rate) density. Furthermore, by containing these units in the polymer, the phenomenon of acid generation from the exposed areas and re-attachment to the unexposed areas during vacuum baking is suppressed. This is believed to be effective in reducing LER, suppressing undesirable negative reactions in the unexposed areas, and thus reducing defects.

[0840] Repeating units B7 to B11 can be used individually or in combination of two or more.

[0841] Polymers B and B' may also contain (meth)acrylate units with close-knit groups such as lactone structures, hydroxyl groups other than phenolic hydroxyl groups, or other repeating units, in order to fine-tune the properties of the resist film.

[0842] Examples of the aforementioned (meth)acrylate units with binding groups 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 are not acidic and can be used as auxiliary units to provide adhesion to the substrate and to adjust solubility.

[0843] [Chemistry 280]

[0844]

[0845] 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 63 It is a saturated hydrocarbon group with 1 to 4 carbon atoms. h is 0, 1, 2 or 3.

[0846] In polymer B, to obtain high resolution and elicit a high contrast between the negatively irradiated portion and the un-irradiated portion (unnegative portion), the content of repeating unit B1 is ideally 30–95 mol%, and more preferably 50–85 mol%. Furthermore, to promote the negativeing ​​reaction, the content of repeating units B2 and B3 is ideally 5–70 mol%, and more preferably 10–60 mol%. To improve etching resistance, the content of repeating units B4–B6 is ideally 0–30 mol%, and more preferably 3–20 mol%. Other repeating units may also be present in the range of 0–30 mol%, preferably 0–20 mol%.

[0847] When polymer B' does not contain repeating units B7 to B11, the content of repeating unit B1 in polymer B' is ideally 25–95 mol%, and more ideally 40–85 mol%. The content of repeating units B4 to B6 is ideally 0–30 mol%, and more ideally 3–20 mol%. The content of repeating units B2 and B3 is ideally 5–70 mol%, and more ideally 10–60 mol%. Alternatively, it may contain other repeating units at 0–30 mol%, preferably 0–20 mol%.

[0848] When polymer B' contains repeating units B7 to B11, the content of repeating unit B1 in polymer B' is ideally 25 to 94.5 mol%, and more ideally 36 to 85 mol%. The content of repeating units B4 to B6 is ideally 0 to 30 mol%, and more ideally 3 to 20 mol%. The content of repeating units B2 and B3 is ideally 5 to 70 mol%, and more ideally 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 B8 to B11 is ideally 0.5 to 20 mol%, and more ideally 1 to 10 mol%. It may also contain other repeating units at 0 to 30 mol%, preferably 0 to 20 mol%.

[0849] Furthermore, among 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.

[0850] Furthermore, it is preferable that polymer B' 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).

[0851] [Chemistry 281]

[0852]

[0853] In the formula, a4, b4, b6, and R A R 22 R 23 R 32 R 33 and A + As mentioned before. 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.

[0854] When polymer B' is used as the base polymer (B), polymers without repeating units B7 to B14 and those containing repeating units B7 to B14 can be used together. 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 is preferably 2 to 5000 parts by mass relative to 100 parts by mass of the polymer containing repeating units B7 to B14, and more preferably 10 to 1000 parts by mass.

[0855] When chemically amplified negative resist compositions are used in mask fabrication, the most advanced generation has a coating thickness of 150 nm or less, preferably 100 nm or less. The dissolution rate of the base polymer constituting the aforementioned chemically amplified negative resist composition in an alkaline developer (e.g., a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution) is generally 80 nm / s or less, more preferably 50 nm / s or less, to further reduce defects caused by resist residue and to form fine patterns. Furthermore, for example, when fabricating LSI wafers from wafers, when using the chemically amplified negative resist composition of the present invention for EUV exposure processing, it is necessary to pattern fine lines of 50 nm or less. Therefore, the coating thickness is usually 100 nm or less. Because it is a thin film, it is believed that the pattern will deteriorate due to development; therefore, the dissolution rate of the polymer used is preferably 80 nm / s or less, more preferably 50 nm / s or less.

[0856] The aforementioned polymer can be synthesized by copolymerizing monomers, which are protected by protecting groups as needed, using known methods, followed by deprotection reactions as required. The copolymerization reaction is not particularly limited, but free radical polymerization or anionic polymerization is preferred. For reference to the above methods, see International Patent 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.

[0857] For the aforementioned polymer, a weight-average molecular weight (Mw) of 1000 to 50000 is preferred, and 2000 to 20000 is more ideal. If Mw is 1000 or higher, as previously known, there is no risk of pattern top rounding, reduced resolution, or LER degradation. On the other hand, if Mw is 50000 or lower, especially when forming patterns with a linewidth of 100 nm or less, there is no risk of increased LER. Furthermore, in this invention, Mw is a polystyrene equivalent value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or dimethylformamide (DMF) as a solvent.

[0858] The aforementioned polymers have a molecular weight distribution (Mw / Mn) of 1.0–2.0, with narrow dispersion of 1.0–1.8 being particularly desirable. Such narrow dispersion prevents foreign matter from forming on the pattern or deterioration of the pattern shape after development.

[0859] [(C) Crosslinking agent]

[0860] When the base polymer (B) 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.

[0861] 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 groups; melamine compounds; guanidine compounds; glycourea compounds or urea compounds; isocyanate compounds; azide compounds; and compounds containing double bonds such as olefinic groups. These can be used as additives or introduced into the polymer side chain as suspending groups. Furthermore, compounds containing hydroxyl groups can also be used as crosslinking agents.

[0862] Examples of the aforementioned epoxy compounds include tris(2,3-epoxypropyl)isocyanurate, trimethylolpropane triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, and triethylolethane triepoxypropyl ether.

[0863] Examples of the aforementioned melamine compounds include compounds or mixtures thereof in which 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine, hexamethoxymethyl melamine, hexahydroxymethyl melamine, etc. are methoxymethylated, as well as compounds or mixtures thereof in which 1 to 6 hydroxymethyl groups of hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexahydroxymethyl melamine, etc. are acyloxymethylated.

[0864] Examples of the aforementioned guanidine compounds include compounds or mixtures thereof in which one to four hydroxymethyl groups of tetrahydroxymethylguanidine, tetramethoxymethylguanidine, tetrahydroxymethylguanidine, etc. are methoxymethylated, as well as compounds or mixtures thereof in which one to four hydroxymethyl groups of tetramethoxyethylguanidine, tetraacyloxyguanidine, tetrahydroxymethylguanidine, etc. are acyloxymethylated.

[0865] Examples of the aforementioned glycourea compounds include tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, tetrahydroxymethylglycourea, and tetrahydroxymethylglycourea, compounds or mixtures thereof in which 1 to 4 hydroxymethyl groups are methoxymethylated, and compounds or mixtures thereof in which 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycourea are acylmethylated.

[0866] Examples of the aforementioned urea compounds include tetrahydroxymethylurea, tetramethoxymethylurea, tetrahydroxymethylurea, compounds or mixtures thereof in which 1 to 4 hydroxymethyl groups are methoxymethylated, and tetramethoxyethylurea, etc.

[0867] Examples of the aforementioned isocyanate compounds include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

[0868] Examples of the aforementioned azide compounds include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylene bisazide, and 4,4'-oxybisazide.

[0869] Examples of compounds containing olefinic groups include ethylene glycol diethylene ether, triethylene glycol diethylene ether, 1,2-propanediol diethylene ether, 1,4-butanediol diethylene ether, tetramethylene glycol diethylene ether, neopentyl glycol diethylene ether, trimethylolpropane triethylene ether, hexanediol diethylene ether, 1,4-cyclohexanediol diethylene ether, neopentyl tetraethylene ether, neopentyl tetraethylene ether, sorbitol tetraethylene ether, sorbitol pentaethylene ether, and trimethylolpropane triethylene ether.

[0870] In the chemically amplified negative resist composition of the present invention, the content of (C) crosslinking agent is ideally 0.1 to 50 parts by mass relative to 80 parts by mass of (B) base polymer, and more ideally 1 to 30 parts by mass. If within the aforementioned range, there is less risk of pattern interconnection and decreased resolution. (C) Crosslinking agent can be used alone or in combination of two or more types.

[0871] [(D) Polymers containing fluorine atoms]

[0872] The chemically amplified negative resist composition of the present invention, in order to achieve high contrast, suppress chemical flashes of acid during high-energy ray irradiation, and shield the mixing of acid from the antistatic film and suppress undesirable pattern degradation during the coating of the antistatic film material onto the resist film, may also contain a polymer containing fluorine atoms as component (D). This polymer containing fluorine atoms contains 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 may also further contain 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.). The aforementioned polymers containing fluorine atoms also act as surfactants, thus preventing the re-adhesion of insoluble substances that may be generated during the development process to the substrate, and therefore also effective against development defects.

[0873] [Chemistry 282]

[0874]

[0875] 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 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 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-labile group, 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 may also be inserted between the carbon-carbon bonds. 109 A linear or branched hydrocarbon group with 1 to 5 carbon atoms, which may also have heteroatom-containing groups inserted between hydrogen atoms or carbon-carbon bonds. R 110 It is a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms, into which heteroatoms may be inserted between carbon-carbon bonds. R 111A saturated hydrocarbon group with 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, wherein a portion of the -CH2- group 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.

[0876] 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.

[0877] 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, but alkyl groups with 1 to 15 carbon atoms are preferred. In addition to the aforementioned alkyl groups, further 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-pentadecayl. Furthermore, fluorinated hydrocarbon groups can be groups in which some or all of the hydrogen atoms bonded to the carbon atoms of the aforementioned hydrocarbon groups are replaced by fluorine atoms.

[0878] In equation (D4), X 1Examples of (k+1) valence hydrocarbon groups representing carbon numbers from 1 to 20 include alkyl groups with 1 to 20 carbon atoms or cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms that have further removed k hydrogen atoms. Also, X 1 Examples of (k+1) valent fluorinated hydrocarbon groups with carbon numbers from 1 to 20 include groups in which at least one hydrogen atom of the aforementioned (k+1) valent hydrocarbon group is replaced by a fluorine atom.

[0879] Specific examples of repeated units D1 to D4 can be listed below, but are not limited to these. Also, in the following formula, R... B As mentioned above.

[0880] [Chemistry 283]

[0881]

[0882] [Chemistry 284]

[0883]

[0884] [Chemistry 285]

[0885]

[0886] In equation (D5), R 109 and R 110 Examples of hydrocarbon groups with 1 to 5 carbon atoms include alkyl, alkenyl, and ynyl groups, but alkyl is preferred. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and n-pentyl. Furthermore, groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms may be inserted between the carbon-carbon bonds of the aforementioned hydrocarbon groups.

[0887] In equation (D5), -OR 109 A hydrophilic group is preferred. In this case, R 109 Alkyl groups with 1 to 5 carbon atoms that have an oxygen atom inserted between carbon-carbon bonds are preferred.

[0888] In equation (D5), X 2 *-C(=O)-O- or *-C(=O)-NH- are preferred. Furthermore, R C Methyl is preferred. X 2 The presence of a carbonyl group enhances the ability to capture acids from the antistatic membrane. Furthermore, if R... D If the methyl group is used, it becomes a rigid polymer with a higher glass transition temperature (Tg), thus inhibiting acid diffusion. As a result, the resist film exhibits good stability over time, without deterioration in resolution or pattern shape.

[0889] Repeating unit D5 can be listed below, but is not limited to these. Also, in the following formula, R... C As mentioned above.

[0890] [Chemistry 286]

[0891]

[0892] [Chemistry 287]

[0893]

[0894] 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, and 1,1-dimethylethane-1,2-diyl.

[0895] 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 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.

[0896] Repeating unit D6 can be listed below, but is not limited to these. Also, in the following formula, R... C As mentioned above.

[0897] [Chemistry 288]

[0898]

[0899] [Chemistry 289]

[0900]

[0901] [Chemistry 290]

[0902]

[0903] [Chemistry 291]

[0904]

[0905] The content of repeating units D1 to D4 is preferably 15 to 95 mol% of all repeating units in the aforementioned polymer containing fluorine atoms, and more preferably 20 to 85 mol%. The content of repeating units D5 and / or D6 is preferably 5 to 85 mol% of all repeating units in the aforementioned polymer containing fluorine atoms, and more preferably 15 to 80 mol%. Repeating units D1 to D6 can be used alone or in combination of two or more.

[0906] (D) Polymers containing fluorine atoms may also contain other repeating units besides the aforementioned repeating units. Examples of such repeating units can be found in paragraphs

[0046] to

[0078] of Japanese Patent Application Publication No. 2014-177407. (D) When polymers containing fluorine atoms contain other repeating units, it is preferable that their content is 50 mol% or less of all repeating units in the aforementioned polymers containing fluorine atoms.

[0907] (D) A polymer containing fluorine atoms can be synthesized by copolymerizing monomers, which are to be protected with protecting groups as needed, using known methods, followed by a deprotection reaction as required. The copolymerization reaction is not particularly limited, but free radical polymerization or anionic polymerization is preferred. The above method can be found in Japanese Patent Application Publication No. 2004-115630.

[0908] (D) For polymers containing fluorine atoms, a Mw of 2000–50000 is preferred, and 3000–20000 is even better. If the Mw is less than 2000, it will promote acid diffusion, sometimes resulting in deterioration of resolution and impaired stability over time. If the Mw is too high, the solubility in the solvent will decrease, sometimes causing coating defects. Also, for polymers containing fluorine atoms in (D), an Mw / Mn ratio of 1.0–2.2 is preferred, and 1.0–1.7 is even better.

[0909] 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 base polymer (B) is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass. The polymer containing fluorine atoms (D) can be used alone or in combination of two or more.

[0910] [(E) Quenching Agent]

[0911] 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 used to prevent the acid generated from the photoacid generator in the chemically amplified resist composition from diffusing to the unexposed area and forming the desired pattern.

[0912] The aforementioned quenching agents can be exemplified by known basic compounds. Examples of 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 hydroxyphenyl 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 preferred. Preferred examples include tris[2-(methoxymethoxy)ethyl]amine, tris[2-(methoxymethoxy)ethyl]amine-N-oxide, dibutylaminobenzoic acid, morpholine derivatives, and imidazole derivatives. By adding such basic compounds, for example, the diffusion rate of acid in the resist film can be further inhibited, or the shape can be modified.

[0913] Furthermore, examples of quenchers mentioned above 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 the unstable acid group, releasing the α-unfluorinated carboxylic acid through salt exchange with the α-unfluorinated onium salt. Since the α-unfluorinated carboxylic acid hardly undergoes a deprotection reaction, it functions as a quencher.

[0914] Onium salts of carboxylic acids that are not fluorinated at the α-position, for example, those represented by the formula (E1).

[0915] [Chemistry 292]

[0916] R 201 -CO2 - Mq A + (E1)

[0917] In equation (E1), R 201 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain hydrogen atoms or heteroatoms, but the hydrogen atom bonded to the carbon atom at the α position of the carboxyl group is replaced by a fluorine atom or a fluoroalkyl group.

[0918] R 201The hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 40 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, and tricyclic [5.2.1.0]. 2,6 [Cyclic 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; cyclohexenyl groups with 3 to 40 carbon atoms; 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.]

[0919] Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, 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; and aryloxoalkyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, and 2-(2-naphthyl)-2-oxoethyl.

[0920] 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 ideal. Specific examples of sulfonium cations can be found 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 those represented by formula (Z-3), but are not limited to these. Specific examples of monazine cations can be found in paragraph

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

[0921] The aforementioned ammonium cation is preferably represented by the formula (am-1).

[0922] [Chemistry 293]

[0923]

[0924] In equation (am-1), R q11 ~R q14 Each can be an independent hydrocarbon group with 1 to 40 carbon atoms, and may also contain heteroatoms. Also, R q11 ~R q14 Any two of them can also bond to each other and form a ring together with the nitrogen atom they are bonded to. Specific examples of the aforementioned hydrocarbon groups can be given and explained in the description of formula (A) regarding R. 1 The hydrocarbon group shown is an example of the same.

[0925] Specific examples of ammonium cations represented by formula (am-1) are listed below, but are not limited to these.

[0926] [Chemistry 294]

[0927]

[0928] The anions of onium salts represented by formula (E1) can be listed below, but are not limited to these.

[0929] [Chemistry 295]

[0930]

[0931] [Chemistry 296]

[0932]

[0933] [Chemistry 297]

[0934]

[0935] The aforementioned quenching agent should also be a sulfonium salt of a carboxylic acid containing an iodinated benzene ring, represented by the formula (E2).

[0936] [Chemistry 298]

[0937]

[0938] 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.

[0939] In equation (E2), R 211 The radicals are hydroxyl, fluorine, chlorine, bromine, amino, nitro, cyano, saturated hydrocarbon group with 1 to 6 carbon atoms, saturated hydrocarbon oxygen group with 1 to 6 carbon atoms, saturated hydrocarbon carbonyl oxygen group with 2 to 6 carbon atoms, saturated hydrocarbon sulfonyl oxygen group with 1 to 4 carbon atoms, and -N(R) 211A )-C(=O)-R 211B or -N(R) 211A )-C(=O)-OR 211B The hydrogen atoms of the saturated hydrocarbon group, saturated hydrocarbon oxygen group, saturated hydrocarbon carbonyl oxygen group, or saturated hydrocarbon sulfonyl oxygen group may also 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.

[0940] In formula (E2), L 21 It is a single bond or a (u+1) valence linker with 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.

[0941] In equation (E2), R 212 R 213 and R 214 Each group consists of a halogen atom or may contain heteroatoms and has 1 to 20 carbon atoms. These groups 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 groups can be replaced by hydroxyl, carboxyl, halogen, oxo, cyano, nitro, sulfonyl lactone ring, sulfonyl, or sulfonium salt-containing groups. A portion of the -CH2- group can also be replaced by 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.

[0942] Specific examples of compounds represented by formula (E2) can be found in Japanese Patent Application Publication No. 2017-219836. Compounds represented by formula (E2) exhibit high absorption, high sensitization effect, and high acid diffusion control effect.

[0943] The aforementioned quenching agent may also be a nitrogen-containing carboxylate compound represented by the following formula (E3).

[0944] [Chemistry 299]

[0945]

[0946] In equation (E3), R 221 ~R 224 Each is independently a hydrogen atom, -L 22 -CO2 - Or it may contain a hydrocarbon group with 1 to 20 carbon atoms that is a heteroatom. 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 A hydrocarbon group consisting of 1 to 20 carbon atoms, which may also contain heteroatoms.

[0947] In equation (E3), ring R r The formula refers to a 2-6 carbon ring containing carbon and nitrogen atoms, wherein some or all of the hydrogen atoms bonded to the carbon atoms of the ring may be replaced by a hydrocarbon group with 1-20 carbon atoms, or -L 22 -CO2 - Alternatively, a portion of the -CH2- group of the ring can be replaced by a sulfur atom, an oxygen atom, or a nitrogen atom. The aforementioned ring can be either an alicyclic or aromatic ring; however, 5-membered or 6-membered rings are preferred. Specific examples include pyridine rings, pyrrole rings, pyrrolidine rings, piperidine rings, pyrazole rings, imidazoline rings, pyridazine rings, pyrimidine rings, pyrazine rings, imidazoline rings, oxazole rings, thiazole rings, morpholine rings, thiazine rings, and triazole rings.

[0948] The carboxylic acid onium 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 ring R r At least one of the hydrogen atoms bonded to the carbon atom is -L 22 -CO2 - replace.

[0949] In equation (E3), Mq B + It can be a sulfonium cation, a monazine cation, or an ammonium cation, but a sulfonium cation is preferred. Specific examples of the aforementioned sulfonium cations can be found 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 to these examples.

[0950] The anions of compounds represented by formula (E3) can be listed below, but are not limited to these.

[0951] [Chemical 300]

[0952]

[0953] [Chemical Engineering 301]

[0954]

[0955] [Chemical 302]

[0956]

[0957] [Chemical 303]

[0958]

[0959] [Chemical 304]

[0960]

[0961] [Chemical 305]

[0962]

[0963] Furthermore, the aforementioned quenching agents can also be betaine-type compounds made of weak acids. Specific examples are listed below, but are not limited to these.

[0964] [Chemical 306]

[0965]

[0966] The aforementioned quenching agents can be further exemplified by the polymer-type quenching agent disclosed in Japanese Patent Application Publication No. 2008-239918. This quenching agent improves the rectangularity of the resist pattern by aligning to the surface of the resist film. The polymer-type quenching agent also has the effect of preventing film loss and rounding of the pattern top when using a protective film for immersion exposure.

[0967] When the chemically amplified negative resist composition of the present invention contains the (E) quencher, its content is ideally 0 to 50 parts by mass relative to 80 parts by mass of the (B) base polymer, and more ideally 0.1 to 40 parts by mass. The (E) quencher can be used alone or in combination of two or more.

[0968] When the chemically amplified negative resist composition of the present invention contains a photoacid generator (component A) and a quencher (component E), it is preferable that the photoacid generator to quencher content ratio ((A) / (E)) is less than 6 by mass, more preferably less than 5, and ideally less than 4. If the photoacid generator to quencher content ratio 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.

[0969] [(F) Organic solvents]

[0970] 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 aforementioned organic solvent, as long as it can dissolve each component. Examples of such organic solvents include: 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) and ethylene 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 mixed solvents of the above.

[0971] Among the above-mentioned organic solvents, 1-ethoxy-2-propanol, PGMEA, PGME, cyclohexanone, EL, γ-butyrolactone, and the above-mentioned mixed solvents are preferred.

[0972] When the chemically amplified negative resist composition of the present invention contains (F) organic solvent, its content is ideally 200 to 10,000 parts by mass relative to 80 parts by mass of the (B) base polymer, and more ideally 400 to 6,000 parts by mass. The (F) organic solvent can be used alone or in combination of two or more.

[0973] (G) Other photoacid generating agents

[0974] The chemically amplified negative resist composition of the present invention may also contain a photoacid generator other than the onium salt 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, as long as they are compounds that generate acid upon irradiation by high-energy rays. Ideal photoacid generators include sulfonium salts, sulfonium salts, sulfonyl diazomethanes, N-sulfonyloxyimides, oxime-O-sulfonate type acid generators, etc.

[0975] Other specific examples of 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 partially fluorinated sulfonates described in paragraphs

[0080] to

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

[0976] The aforementioned photoacid generator is preferably a salt compound containing an anion with the structure shown below.

[0977] [Chemical 307]

[0978]

[0979] [Chemical 308]

[0980]

[0981] [Chemical 309]

[0982]

[0983] [Chemical 310]

[0984]

[0985] [Chemistry 311]

[0986]

[0987] [Chemistry 312]

[0988]

[0989] [Chemistry 313]

[0990]

[0991] [Chemical 314]

[0992]

[0993] [Chemical 315]

[0994]

[0995] [Chemistry 316]

[0996]

[0997] [Chemistry 317]

[0998]

[0999] Furthermore, it is also ideal for the aforementioned photoacid generator to be a salt compound containing an anion represented by the following formula (G1).

[1000] [Chemistry 318]

[1001]

[1002] 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.

[1003] In formula (G1), L 31 It can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond.

[1004] In formula (G1), L 32 It can be an ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond.

[1005] In formula (G1), L F 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.

[1006] L FThe 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; cyclopentane-diyl, cyclohexane-diyl, norcamphene-diyl, and adamantane-diyl; unsaturated aliphatic alkyl 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 them. Also, L F 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 obtained by further removing one or two hydrogen atoms from the aforementioned examples of hydrocarbon groups representing 1 to 20 carbon atoms.

[1007] 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.

[1008] 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 is 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.

[1009] R 301 R 301A and R 301BThe 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 a saturated hydrocarbon oxygen group with 1 to 6 carbon atoms can be exemplified by examples similar to the aforementioned saturated hydrocarbon groups, R. 301 The saturated hydrocarbon base of the carbonyl group of the saturated hydrocarbon with carbon numbers of 2 to 6 can be exemplified by the saturated hydrocarbon groups with carbon numbers of 1 to 5 in the specific examples of the aforementioned saturated hydrocarbon groups with carbon numbers of 1 to 6.

[1010] R 301B 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.

[1011] In equation (G1), R 302 It is a saturated hydrocarbon group with 1 to 20 carbon atoms or an arylene group with 6 to 20 carbon atoms. Some or all of the hydrogen atoms of the saturated hydrocarbon group may be replaced by halogen atoms other than fluorine atoms. Some or all of the hydrogen atoms of the arylene group may also 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.

[1012] R 302 The saturated alkylene groups with 1 to 20 carbon atoms can be linear, branched, or cyclic. Specific examples include alkyl alkylene groups with 1 to 20 carbon atoms such as methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl; and cyclic saturated alkylene groups with 3 to 20 carbon atoms such as cyclopentanediyl, cyclohexanediyl, norcamphenediyl, and adamantanediyl.

[1013] R 302Specific examples of arylene groups with 6 to 20 carbon atoms include phenylene, naphthylene, phenanthrenediyl, and anthracenediyl. The saturated hydrocarbon group with 1 to 20 carbon atoms in the substituents of the aforementioned arylene groups and the hydrocarbon group with 1 to 20 carbon atoms can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, decadecyl, heptadecanyl, octadecyl, nonadecanyl, and icosyl; and cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl, which are cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms. Specific examples of the aforementioned arylene substituents having 6 to 14 carbon atoms include phenylene, naphthylene, phenanthrenediyl, anthracenediyl, etc.

[1014] The anion represented by formula (G1) is preferably the anion represented by formula (G2).

[1015] [Chemistry 319]

[1016]

[1017] In equation (G2), p, q, r, L 31 L F and R 301 As mentioned before. s2 is 1, 2, 3, or 4. R 302A It can be a saturated hydrocarbon group with 1 to 14 carbon atoms, a saturated hydroxyl group with 1 to 14 carbon atoms, an aryl group with 6 to 14 carbon atoms, a halogen atom, or a hydroxyl group. Also, when s² is 2, 3, or 4, each R... 302A They can be the same or different.

[1018] Specific examples of anions represented by formula (G1) are listed below, but are not limited to these.

[1019] [Chem.320]

[1020]

[1021] [Chemistry 321]

[1022]

[1023] [Chemistry 322]

[1024]

[1025] [Chemistry 323]

[1026]

[1027] [Chemistry 324]

[1028]

[1029] [Chemistry 325]

[1030]

[1031] [Chemistry 326]

[1032]

[1033] [Chemistry 327]

[1034]

[1035] [Chemistry 328]

[1036]

[1037] [Chemistry 329]

[1038]

[1039] [Chemistry 330]

[1040]

[1041] [Chemistry 331]

[1042]

[1043] [Chemistry 332]

[1044]

[1045] [Chemistry 333]

[1046]

[1047] [Chemistry 334]

[1048]

[1049] [Chemistry 335]

[1050]

[1051] [Chemistry 336]

[1052]

[1053] [Chemistry 337]

[1054]

[1055] [Chemistry 338]

[1056]

[1057] [Chemistry 339]

[1058]

[1059] [Transformation 340]

[1060]

[1061] [Chemistry 341]

[1062]

[1063] [Chemistry 342]

[1064]

[1065] [Chemistry 343]

[1066]

[1067] [Chemistry 344]

[1068]

[1069] [Chemistry 345]

[1070]

[1071] [Chemistry 346]

[1072]

[1073] [Chemistry 347]

[1074]

[1075] (G) Among 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 the same as those shown in formula (Z-1) and formula (Z-3), but are not limited to these. Specific examples of the aforementioned monazine cation may be the same as those shown in formula (Z-2), but are not limited to these.

[1076] For the acids produced by the aforementioned photoacid generators, a pKa of -2.0 or higher is ideal, and -1.0 or higher is even better. Furthermore, an upper limit of 2.0 for the pKa is preferred. The pKa values ​​were calculated using the pKa database in ACD / Chemsketch ver: 9.04, software manufactured by Advanced Chemistry Development, Inc.

[1077] When the chemically amplified negative resist composition of the present invention contains (G) other photoacid generating agents, the content of such agents is preferably 1 to 10 parts by mass relative to 80 parts by mass of the aforementioned base polymer, and more preferably 1 to 5 parts by mass. By containing other photoacid generating agents, the amount of acid generated in the exposed area and the solubility inhibition of the unexposed area can be appropriately adjusted. (G) Other photoacid generating agents can be used alone or in combination of two or more.

[1078] [(H) surfactant]

[1079] To improve the coating properties of the chemically amplified negative resist composition of the present invention, it may also contain a conventional surfactant as the (H) component. Examples of such surfactants include PF-636 (manufactured by OMNOVA SOLUTIONS) and FC-4430 (manufactured by 3M Corporation). Furthermore, several examples are disclosed in Japanese Patent Application Publication No. 2004-115630, and these examples are well known; reference can be made to select the appropriate one. 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.

[1080] [Resist Pattern Formation Method]

[1081] The resist pattern forming method of the present invention includes the following steps: forming a resist film on a substrate using the aforementioned chemically amplified negative resist composition, irradiating the aforementioned resist film with a pattern using high-energy rays (i.e., exposing the aforementioned resist film with high-energy rays), and developing the resist film irradiated with the aforementioned pattern using an alkaline developer.

[1082] The aforementioned substrate can be, for example, a substrate used for integrated circuit manufacturing (Si, SiO, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective film, etc.) or a substrate used for manufacturing transmissive or reflective mask circuits (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, more preferably at 80–140°C for 1–10 minutes, to form a resist film.

[1083] Next, the aforementioned resist film is exposed and the pattern is irradiated using high-energy rays. Examples of such high-energy rays 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 exposure is preferred.

[1084] When using ultraviolet light, far ultraviolet light, excimer lasers, EUV, X-rays, gamma rays, or synchrotron radiation to generate high-energy rays, a mask is used to form the desired pattern, with an exposure dose preferably ranging from 1 to 500 mJ / cm². 2 It is even better to achieve 10-400 mJ / cm 2 Irradiation is performed in this manner. When using EB, to form the desired pattern, the optimal exposure is 1–500 μC / cm. 2 It is better to achieve a temperature range of 10–400 μC / cm. 2 Irradiation in this manner.

[1085] In addition to the usual exposure method, the immersion method, in which the mask and the resist film are immersed together, can also be used, depending on the circumstances. In this case, a protective film that is insoluble in water can also be used.

[1086] Secondly, the product is exposed to heat on a heating plate, preferably at 60–150°C for 1–20 minutes, and more preferably at 80–140°C for 1–10 minutes, followed by post-exposure baking (PEB).

[1087] Then, a developer solution of 0.1-5% by mass, preferably 2-3% by mass, such as TMAH, is used. The development is preferably performed by conventional methods such as dip, puddle, or spray for 0.1-3 minutes, more preferably 0.5-2 minutes, to form the target pattern on the substrate.

[1088] Furthermore, the chemically amplified negative resist composition of the present invention is particularly useful for forming patterns with good resolution and low LER. Moreover, the chemically amplified negative resist composition of the present invention is particularly useful for pattern formation on substrates with surfaces made of materials where it is difficult to achieve good adhesion of the resist pattern, thus easily leading to pattern peeling and collapse. Examples of such substrates include substrates with a chromium film sputtered on the outermost surface, substrates containing a chromium compound selected from one or more light elements selected from oxygen, nitrogen, and carbon, and substrates with a surface layer containing SiO2 or SiO2. x Substrates containing tantalum compounds, molybdenum compounds, cobalt compounds, nickel compounds, tungsten compounds, tin compounds, etc. The chemically amplified negative resist composition of this invention is particularly useful for pattern formation using a blank photomask as the substrate. In this case, the blank photomask can be either transmissive or reflective.

[1089] Regarding transmissive blank photomasks, blank photomasks with a light-shielding film formed of a chromium-based material can be blank photomasks for binary photomasks or blank photomasks for phase-shifting photomasks. When used as a blank photomask for binary photomasks, the light-shielding film can be an anti-reflection layer and a light-shielding layer formed of a chromium-based material. Alternatively, the anti-reflection film on the surface side can be entirely or only on the outermost side of the anti-reflection film on the surface side, 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 photomasks, a blank photomask for phase-shifting photomasks with a chromium-based light-shielding film on the phase-shifting film can be considered.

[1090] The aforementioned blank photomask with a chromium-based material as its outermost layer, as exemplified in Japanese Patent Application Publication No. 2008-26500, Japanese Patent Application Publication No. 2007-302873, or those examples in the prior art, is well known and detailed descriptions are omitted. For example, when a light-shielding film with an anti-reflective layer and a light-shielding layer is constructed from a chromium-based material, the following film composition can be used.

[1091] When a light-shielding film with an anti-reflective layer and a light-shielding layer is formed using chromium-based materials, the anti-reflective layer and the light-shielding layer can be stacked sequentially from the surface side, or they can be stacked sequentially. Furthermore, the anti-reflective layer and the light-shielding layer can each be multiple layers, and the composition can be discontinuously changed between layers with different compositions, or the composition can be continuously varied. The chromium-based materials used can be metallic chromium or materials containing light elements such as oxygen, nitrogen, and carbon. Specifically, metallic chromium, chromium oxide, chromium nitride, chromium carbide, chromium nitride oxide, chromium carbide oxide, chromium carbide nitride, and chromium carbide nitride oxide can be used.

[1092] Furthermore, a reflective blank mask comprises: a substrate, and a multilayer reflective film formed on a main surface (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. A reflective mask (EUV reflective mask) having an absorber pattern (pattern of the absorber film) formed by patterning the absorber film can be manufactured from the reflective blank mask (EUV reflective blank mask). The wavelength of EUV light used in EUV lithography is 13-14 nm, typically light with a wavelength of about 13.5 nm.

[1093] The multilayer reflective film is preferably disposed on a main surface of the substrate. However, without sacrificing the effectiveness of the invention, a base film may also be disposed between the substrate and the multilayer reflective film. The absorber film may also be formed in contact with the multilayer reflective film, but it is preferable that the multilayer reflective film is in contact with the absorber film. More preferably, a protective film (a protective film for the multilayer reflective film) is disposed in contact with both the multilayer reflective film and the absorber film. The protective film is used to protect the multilayer reflective film during cleaning, correction, and other processing. Furthermore, the protective film is preferably one that protects the multilayer reflective film and prevents oxidation of the multilayer reflective film when the absorber film is patterned using etching. Alternatively, a conductive film may be disposed under other main surfaces (the back side) opposite to a main surface of the substrate, preferably in contact with other main surfaces, to electrostatically hold the reflective mask in the exposure apparatus. Furthermore, here, one main surface of the substrate is designated as the front side and upper side, and the other main surfaces are designated as the back side and lower side. However, the front and back sides and the top and bottom sides are determined for simplicity. One main surface and the other main surfaces can be any of the two main surfaces (film forming surfaces) in the substrate, and the front and back sides and the top and bottom sides can be interchanged. More specifically, it can be formed by a method exemplified by Japanese Patent Application Publication No. 2021-139970 or therein as known prior art.

[1094] According to the resist pattern forming method of the present invention, even when using a substrate whose outermost surface is made of a material that easily affects the shape of the resist pattern (e.g., a transmissive or reflective blank mask), a pattern with extremely high resolution, small LER, excellent rectangularity, and excellent pattern fidelity can still be obtained.

[1095] Example

[1096] The following examples, embodiments, and comparative examples illustrate the present invention in detail, but the present invention is not limited to the following embodiments. Furthermore, the apparatus used is shown below.

[1097] •IR: NICOLET 6700, Thermofisher Scientific

[1098] ·1 H-NMR: ECA-500 manufactured by Nippon Electronics Co., Ltd.

[1099] MALDI TOF-MS: S3000 manufactured by Nippon Electronics Co., Ltd.

[1100] [1] Synthesis of onium salts

[1101] [Example 1-1] Synthesis of onium salt PAG-1

[1102] [Chemistry 348]

[1103]

[1104] (1) Synthesis of intermediate In-1

[1105] 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, and maturation was carried out for 2 hours. After maturation, the reaction solution was cooled, 50 g of water was added, and the reaction was stopped. Another 50 g of dichloromethane was added, and the target compound was extracted. A standard aqueous work-up was performed, the solvent was distilled off, hexane was added, and recrystallization was carried out to obtain 13.7 g of white crystalline intermediate In-1 (95% yield).

[1106] (2) Synthesis of onium salt PAG-1

[1107] Under nitrogen atmosphere, the starting material SM-2 (8.7 g) was suspended in a mixed solvent of THF (30 g) and water (30 g) in a reaction vessel. A 25% (w / w) sodium hydroxide aqueous solution (2.5 g) was added dropwise, and the mixture was stirred at room temperature for 5 hours. Then, intermediate In-1 (8.7 g) was added, and the mixture was matured at room temperature for another 3 hours. After maturation, water (50 g) was added to stop the reaction. Dichloromethane (60 g) was added, and the target compound was extracted. A standard aqueous work-up was performed, the solvent was distilled off, diisopropyl ether was added, and recrystallization was carried out to obtain 14.5 g of ononium salt PAG-1 as white crystals (92% yield).

[1108] The IR spectral data and TOF-MS results of PAG-1 are shown below. Also, the nuclear magnetic resonance spectroscopy (NMR spectroscopy) 1 The results of H-NMR / DMSO-d6 are as follows Figure 1 As shown.

[1109] IR(D-ATR): ν=3062,2971,1720,1610,1586,1465,1438,1386,1276,1224,1187,1 105,1082,1036,1019,966,904,886,853,821,772,707,682,643,625,548,487cm -1 .

[1110] MALDI TOF-MS: POSITIVE M + 277 (equivalent to C) 18 H 13 OS + )

[1111] NEGATIVE M - 771 (equivalent to C) 40 H 35 O 12 S2 - )

[1112] [Synthetic Examples 1-2 to 1-8] Synthesis of PAG-2 to PAG-8

[1113] Onium salts PAG-2 to PAG-8, represented by the following formulas, were synthesized using the corresponding raw materials and known organic synthesis reactions.

[1114] [Chemistry 349]

[1115]

[1116] [Chemical 350]

[1117]

[1118] [2] Preparation of chemically amplified negative resist composition

[1119] [Examples 1-1 to 1-54, Comparative Examples 1-1 to 1-10]

[1120] The components were dissolved in an organic solvent according to the compositions shown in Lists 1 to 3. The resulting solutions were filtered through a UPE filter and / or a nylon filter with sizes selected from 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 solvent was a mixture of 790 parts by weight of PGMEA, 1580 parts by weight of EL, and 1580 parts by weight of PGME. Furthermore, a portion of the compositions contained 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.

[1121] [Table 1]

[1122]

[1123]

[1124] [Table 2]

[1125]

[1126]

[1127] [Table 3]

[1128]

[1129] The structures of polymers P-1 to P-30 in Tables 1-3 are shown in Table 4 below. Also, Mw is the converted value of polystyrene obtained using GPC with THF or DMF as solvent.

[1130] [Table 4]

[1131]

[1132]

[1133] The structure of each unit is shown in Table 4.

[1134] [Chemistry 351]

[1135]

[1136] [Chemistry 352]

[1137]

[1138] [Chemistry 353]

[1139]

[1140] [Chemistry 354]

[1141]

[1142] [Chemistry 355]

[1143]

[1144] [Chemistry 356]

[1145]

[1146] Tables 1-3 show the other photoacid generators PAG-A, comparative photoacid generators cPAG-1 to cPAG-4, quenchers Q-1 to Q-4, and polymers containing fluorine atoms FP-1 to FP-5.

[1147] [Chemistry 357]

[1148]

[1149] [Chemistry 358]

[1150]

[1151] [Chemistry 359]

[1152]

[1153] [Hua360]

[1154]

[1155] [3] Evaluation of EB lithography

[1156] [Examples 2-1 to 2-54, Comparative Examples 2-1 to 2-10]

[1157] Various chemically amplified negative resist compositions (R-1 to R-54, CR-1 to CR-10) were spin-coated using ACT-M (manufactured by Tokyo Power Technology Co., Ltd.) onto a 152 mm square blank mask with a silicon oxide film as the outermost surface, which had been pre-coated with hexamethyldisilazane (HMDS) vapor. The mask was then pre-baked at 110°C for 600 seconds on a heated plate to produce a resist film with a thickness of 80 nm. The thickness of the obtained resist film was measured using the optical measurement instrument Nanospec (manufactured by Nanometrics Co., Ltd.). Measurements were taken at 81 points on the blank substrate surface, extending 10 mm from the outer edge of the blank photomask, and the average thickness and thickness range were calculated.

[1158] Exposure was performed using an electron beam exposure apparatus (EBM-5000plus manufactured by Nuflare Technology, accelerating voltage 50kV), with PEB applied at 120°C for 600 seconds, followed by development with 2.38% by mass TMAH aqueous solution to obtain a negative pattern.

[1159] 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 defined as the 1:1 line-to-space ratio (LS) at 200 nm with 1:1 resolution. 2 The resolution (limiting resolution) was defined as the smallest size of a 200nm LS pattern with a 1:1 exposure ratio. For the 200nm LS pattern obtained after optimal exposure, edge detection was performed on 80 points across 32 edges of the 200nm LS pattern using SEM. The deviation (standard deviation, σ) was calculated as three times the value of 3σ, which was taken as the LER (nm). The pattern shape was visually determined to be rectangular. Furthermore, for pattern fidelity evaluation, when a 120nm square dot pattern was configured at a density of 36%, the area loss (%) value at one corner of the dot pattern was calculated. The smaller this value, the better the rectangularity of the dot shape. The results are shown in Tables 5-7.

[1160] [Table 5]

[1161]

[1162] [Table 6]

[1163]

[1164]

[1165] [Table 7]

[1166]

[1167]

[1168] 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 unsatisfactory acid generator design, resulting in unsatisfactory performance in terms of resolution, LER, and pattern rectangularity.

[1169] The resist patterning method using the chemically amplified negative resist composition of the present invention is useful in optical lithography during the manufacture of semiconductor devices, especially in the processing of transmissive or reflective blank photomasks.

Claims

1. A chemically amplified negative resist composition, comprising: (A) a photo-acid generator consisting of 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 (Bl), in the formula, nl is 0 or 1, n2 is 0, 1, 2, 3 or 4, n3 is 1, 2, 3 or 4, n4 is 0 or 1, n5 is 0, 1, 2, 3 or 4, n6 is 0, 1, 2, 3 or 4, but 1 < n2 + n3 < 5 when nl is 0, and 1 < n2 + n3 < 7 when nl is 1, R 1 R1is a hydrocarbon group having a carbon number of 1 to 20, R 2 halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, hydrocarbon group having 1 to 20 carbon atoms which can have a hetero atom, hydrocarbon oxy group having 1 to 20 carbon atoms which can have a hetero atom, hydrocarbon thio group having 1 to 20 carbon atoms which can have a hetero atom, or hydrocarbon oxy carbonyl group having 1 to 20 carbon atoms which can have a hetero atom, each R 2 may be the same or different from each other, and a plurality of R 2 may be bonded to each other and form a ring together with the carbon atom to which they are bonded, and R 3 halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, hydrocarbon group having 1 to 20 carbon atoms which can have a hetero atom, hydrocarbon oxy group having 1 to 20 carbon atoms which can have a hetero atom, hydrocarbon thio group having 1 to 20 carbon atoms which can have a hetero atom, or hydrocarbon oxy carbonyl group having 1 to 20 carbon atoms which can have a hetero atom, each R 3 may be the same or different from each other, and a plurality of R 3 may be bonded to each other and form a ring together with the carbon atom to which they are bonded, R 4 a halogen atom, a nitro group, a cyano group, a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms which can have a hetero atom, a hydrocarbon oxy group having 1 to 20 carbon atoms which can have a hetero atom, or a hydrocarbon thio group having 1 to 20 carbon atoms which can have a hetero atom, and when n6 is 2, 3 or 4, each R 4 which can be the same or different from each other, but a plurality of R 4 do not bond to each other and form a ring together with the carbon atom to which they are bonded, L A , L B and L C are each independently a single bond, an ether linkage, an ester linkage, a sulfonate ester linkage, an amide linkage, a sulfonamide linkage, a carbonate linkage, or a carbamate linkage, X L1 is a single bond, or an alkylene group having a carbon number of 1 to 40 which can also contain heteroatoms, Z + is an onium cation, in the formula, al is 0 or 1, a2 is 0, 1 or 2, a3 is an integer satisfying 0 < a3 < 5 + 2(a2) - a4, and a4 is 1, 2 or 3, R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 11 a halogen atom, a nitro group, a carboxyl group, a saturated hydrocarbon group having 1 to 6 carbon atoms which can be substituted with a halogen atom, a saturated hydrocarbonoxy group having 1 to 6 carbon atoms which can be substituted with a halogen atom, or a saturated hydrocarbonyloxy group having 2 to 8 carbon atoms which can be substituted with a halogen atom, A 1 is a single bond or a saturated hydrocarbylene group having a carbon number of 1 to 10, and a part of -CH2- of the saturated hydrocarbylene group can also be replaced with -O-.

2. The chemically amplified negative tone resist composition of claim 1, wherein, the onium salt is represented by the following formula (Al), wherein n2, n3, n5, n6, R 1 ~R 4 , L A , L B , L C , X L1 and Z + are as previously described.

3. The chemically amplified negative resist composition according to claim 2, wherein, the onium salt is represented by the following formula (A2), wherein n2, n3, n5, n6, R 1 ~R 4 , L A and Z + are as previously described.

4. The chemically amplified negative tone resist composition of claim 1, wherein, Z + sulfonium cation represented by the following formula (Z-1) or a phosphonium cation represented by the following formula (Z-2), wherein R ct1 ~R ct5 each independently is a halogen atom, or a hydrocarbon group having a carbon number of 1 to 30 which can also contain a hetero atom, and R ct1 and R ct2 may also be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

5. The chemically amplified negative tone resist composition of claim 1, wherein, Z + sulfonium cation represented by the following formula (Z-3), in the formula, ml 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, mlO is 0, 1 or 2, ml l is 0 or 1, ml2 is 0, 1, 2, 3 or 4, ml3 is 0, 1 or 2, ml4 is 0, 1 or 2, but 0 < m6 + m9 < 4 when ml is 0, 0 < m6 + m9 < 6 when ml is 1, 0 < m7 + mlO < 4 when m2 is 0, 0 < m7 + mlO < 6 when m2 is 1, 1 < m4 + m5 + m8 + ml4 < 4 when m3 is 0, 1 < m4 + m5 + m8 + ml4 < 6 when m3 is 1, 0 < ml2 + ml3 < 4 when ml l is 0, 0 < ml2 + ml3 < 6 when ml l is 1, and further, m4 + ml2 > 1, R F1 ~R F3 each independently is a fluorine atom, a fluorinated saturated hydrocarbon group having a carbon number of 1 to 6, a fluorinated saturated hydrocarbon oxy group having a carbon number of 1 to 6, or a fluorinated saturated hydrocarbon thio group having a carbon number of 1 to 6, and when m5 is 2 or more, each R F1 each independently is a fluorine atom, a fluorinated saturated hydrocarbon group having a carbon number of 1 to 6, a fluorinated saturated hydrocarbon oxy group having a carbon number of 1 to 6, or a fluorinated saturated hydrocarbon thio group having a carbon number of 1 to 6, and when m5 is 2 or more, each R F2 each independently is a fluorine atom, a fluorinated saturated hydrocarbon group having a carbon number of 1 to 6, a fluorinated saturated hydrocarbon oxy group having a carbon number of 1 to 6, or a fluorinated saturated hydrocarbon thio group having a carbon number of 1 to 6, and when m5 is 2 or more, each R F3 each independently is a fluorine atom, a fluorinated saturated hydrocarbon group having a carbon number of 1 to 6, a fluorinated saturated hydro R ct6 ~R ct9 a halogen atom other than an iodine atom and a fluorine atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbons which can have a hetero atom, a hydrocarbon oxy group having 1 to 20 carbons which can have a hetero atom, or a hydrocarbon thio group having 1 to 20 carbons which can have a hetero atom, when m8 is 2, 2 R ct6 which can be the same or different, 2 R ct6 may be bonded to each other and form a ring together with the carbon atom to which they are bonded, when m9 is 2, 2 R ct7 which can be the same or different, 2 R ct7 may be bonded to each other and form a ring together with the carbon atom to which they are bonded, when m10 is 2, 2 R ct8 which can be the same or different, 2 R ct8 may be bonded to each other and form a ring together with the carbon atom to which they are bonded, when m13 is 2, 2 R ct9 which can be the same or different, 2 R ct9 may be bonded to each other and form a ring together with the carbon atom to which they are bonded, Further, the directly bonded S in the cation of the formyl sulfonium + may also be bonded to each other and to S + to form a ring, L D and L E each independently is a single bond, ether bond, ester bond, amide bond, sulfonate ester bond, sulfonamide bond, carbonate ester bond, or carbamate ester bond, X L2 An alkylene group having a carbon number of 1 to 40 which is a single bond or can also contain a hetero atom.

6. The chemically amplified negative tone resist composition of claim 1, wherein, the polymer further contains at least one selected from a repeating unit represented by the following formula (B2) and a repeating unit represented by the following formula (B3), in the formula, bl 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, and b6 is 1 or 2, R A each independently is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 21 a halogen atom, or a hydrocarbon group having a carbon number of 1 to 20 which can also contain a heteroatom, R 22 and R 23 each independently is a hydrogen atom, a saturated hydrocarbon group having a carbon number of 1 to 15 or an aryl group having a carbon number of 6 to 15, the hydrocarbon group can also be substituted with a hydroxyl group or a saturated hydrocarbonoxy group having a carbon number of 1 to 6, and the aryl group can also have a substituent, but R 22 and R 23 are not simultaneously a hydrogen atom, and R 22 and R 23 may also be bonded to each other and form a ring together with the carbon atom to which they are bonded, and a part of -CH2- of the ring can also be substituted with -O- or -S-, R 31 a halogen atom, or a hydrocarbon group having a carbon number of 1 to 20 which can also contain a heteroatom, R 32 and R 33 each independently is a hydrogen atom, a saturated hydrocarbon group having a carbon number of 1 to 15 or an aryl group having a carbon number of 6 to 15, the hydrocarbon group can also be substituted with a hydroxyl group or a saturated hydrocarbonoxy group having a carbon number of 1 to 6, and the aryl group can also have a substituent, but R 32 and R 33 are not simultaneously a hydrogen atom, and R 32 and R 33 may also be bonded to each other and, together with the carbon atom to which they are bonded, form a ring, a part of -CH2- of the ring can also be substituted with -O- or -S-, A 2 is a single bond or a saturated hydrocarbylene group having a carbon number of 1 to 10, a part of -CH2- of the saturated hydrocarbylene group can also be replaced by -O-, W 1 and W 2 each independently is a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 10, an aliphatic hydrocarbon carbonyl group having a carbon number of 2 to 10, or an aryl group having a carbon number of 6 to 15, which aryl group can also have a substituent.

7. The chemically amplified negative tone resist composition of claim 1, wherein, the polymer further contains at least one selected from a repeating unit represented by the following formula (B4), a repeating unit represented by the following formula (B5) and a repeating unit represented by the following formula (B6), in the formula, c and d are each independently 0, 1, 2, 3 or 4, el is 0 or 1, e2 is 0, 1 or 2, and e3 is 0, 1, 2, 3, 4 or 5, R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 41 and R 42 each independently is a hydroxyl group, a halogen atom, a saturated hydrocarbon group having 1 to 8 carbons which can be substituted with a halogen atom, a saturated hydrocarbon oxy group having 1 to 8 carbons which can be substituted with a halogen atom, or a saturated hydrocarbon carbonyloxy group having 2 to 8 carbons which can be substituted with a halogen atom, R 43 a saturated hydrocarbon group having a carbon number of 1 to 20, a saturated hydrocarbon oxy group having a carbon number of 1 to 20, a saturated hydrocarbon carbonyloxy group having a carbon number of 2 to 20, a saturated hydrocarbon oxyhydrocarbon group having a carbon number of 2 to 20, a saturated hydrocarbon sulfidohydrocarbon group having a carbon number of 2 to 20, a halogen atom, a nitro group, a cyano group, a saturated hydrocarbon sulfinyl group having a carbon number of 1 to 20, or a saturated hydrocarbon sulfonyl group having a carbon number of 1 to 20, A 3 is a single bond or a saturated hydrocarbylene group having a carbon number of 1 to 10, and a part of -CH2- of the saturated hydrocarbylene group can also be replaced with -O-.

8. The chemically amplified negative resist composition according to claim 6, wherein the polymer contains at least one selected from a repeating unit represented by the following formula (B7), a repeating unit represented by the following formula (B8), a repeating unit represented by the following formula (B9), a repeating unit represented by the following formula (BlO) and a repeating unit represented by the following formula (Bl l), in the formula, fl and f2 are each independently 0, 1, 2 or 3, gl is 0 or 1, g2 is 0, 1, 2, 3 or 4, and g3 is 0, 1, 2, 3 or 4, but 0 < g2 + g3 < 4 when gl is 0, and 0 < g2 + g3 < 6 when gl is 1, R A each independently is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Z 1 is a single bond or also a phenylene group which can have substituents, Z 2 is a single bond, **-C(=O)-O-Z 21 -, **-C(=O)-NH-Z 21 or **-O-Z 21 -, Z 21 is a divalent group obtained by replacing hydrogen of a carboxylic acid with a carbon number 1 to 6 aliphatic hydrocarbylene group, phenylene group or a combination thereof, and can also contain a halogen atom, a carbonyl group, an ester bond, an ether bond or a hydroxyl group, Z 3 is a single bond, an ether linkage, an ester linkage, an amide linkage, a sulfonate ester linkage, a sulfonamide linkage, a carbonate linkage, or a carbamate linkage, Z 4 a divalent group obtained by combining one or two of a single bond, an aliphatic hydrocarbylene group having a carbon number of 1 to 6, a phenylene group, or a combination thereof, and can also have a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group, Z 5 each independently is a single bond, a phenylene group which can also have a substituent, a naphthylene group or a *-C(=O)-O-Z 51 -, Z 51 is an aliphatic hydrocarbylene group having a carbon number of 1 to 10, a phenylene group or a naphthylene group, the aliphatic hydrocarbylene group can also have a halogen atom, a hydroxyl group, an ether bond, an ester bond or a lactone ring, Z 6 is a single bond, an ether linkage, an ester linkage, an amide linkage, a sulfonate ester linkage, a sulfonamide linkage, a carbonate linkage, or a carbamate linkage, Z 7 each independently a single bond, ***-Z 71 -C(=O)-O-, ***-C(=O)-NH-Z 71 - or ***-O-Z 71 -, Z 71 is an alkylen group having 1 to 20 carbon atoms which can also contain heteroatoms, Z 8 each independently a single bond, ****-Z 81 -C(=O)-O-, ****-C(=O)-NH-Z 81 - or ****-O-Z 81 -, Z 81 is a hydrocarbylene group having a carbon number of from 1 to 20, which can also contain heteroatoms, Z 9 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, phenylene substituted by trifluoromethyl groups, -C(=O)-O-Z 91 -, -C(=O)-N(H)-Z 91 - or -O-Z 91 -, Z 91 is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, phenylene, fluorinated phenylene or phenylene substituted by trifluoromethyl groups, which can also contain a carbonyl group, an ester bond, an ether bond or a 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, *** represents the bond between Z and 6 atomic bonds, **** represents the bond between Z and 7 atomic bonds, L 1 is a single bond, an ether linkage, an ester linkage, a carbonyl group, a sulfonate ester linkage, a sulfonamide linkage, a carbonate ester linkage, or a carbamate ester linkage, Rf 1 and Rf 2 each independently is a fluorine atom or a fluorinated saturated hydrocarbon group having a carbon number of 1 to 6, Rf 3 and Rf 4 each independently is a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having a carbon number of 1 to 6, Rf 5 and Rf 6 each independently is a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having a carbon number of 1 to 6, but all Rf 5 and Rf 6 are not simultaneously a hydrogen atom, Rf 7 is a fluorine atom, a fluorinated alkyl group having a carbon number of 1 to 6, a fluorinated alkoxy group having a carbon number of 1 to 6, or a fluorinated alkylthio group having a carbon number of 1 to 6, R 51 and R 52 each independently is a hydrocarbon group of 1 to 20 carbon numbers which can also contain hetero atoms, and R 51 and R 52 may also be bonded to each other and form a ring together with the sulfur atom to which they are bonded, R 53 When g3 is 2, 3, or 4, each R 53 They can be the same or different, multiple Rs 53 They can also bond to each other and form rings together with the carbon atoms they are bonded to. M - a non-nucleophilic counterion, A + is an onium cation.

9. The chemically amplified negative resist composition according to claim 8, wherein the polymer contains a repeating unit represented by the following formula (Bl-1), and a repeating unit represented by the following formula (B2-1), (B2-2) or (B3-1), and a repeating unit represented by the following formula (B8-1), wherein a4, b4, b6, R A , R 22 , R 23 , R 32 , R 33 and A + are as described above, R HF is a hydrogen atom or a trifluoromethyl group, Z 10 is a single bond or -Z 101 -C(=O)-O-, Z 101 is an alkylen group having 1 to 20 carbon atoms which can also contain heteroatoms, and ** is the atomic bond to the oxygen atom in the formula.

10. The chemically amplified negative tone resist composition of claim 8, wherein, (B) the base polymer further contains a polymer containing a repeating unit represented by formula (Bl) and a repeating unit represented by formula (B2) or (B3) and not containing a repeating unit represented by formula (B7) to (Bl l).

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

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

13. The chemically amplified negative resist composition according to claim 1, not containing a crosslinking agent.

14. The chemically amplified negative resist composition according to claim 1, further containing (D) a fluorine atom-containing polymer, the (D) fluorine atom-containing polymer containing at least one selected from the group consisting of a repeating unit represented by the following formula (Dl), a repeating unit represented by the following formula (D2), a repeating unit represented by the following formula (D3) and a repeating unit represented by the following formula (D4), and can further contain at least one selected from the group consisting of a repeating unit represented by the following formula (D5) and a repeating unit represented by the following formula (D6), 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, and k is 1, 2 or 3, R B each independently is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R C each independently is a hydrogen atom or a methyl group, R 101 , R 102 , R 104 and R 105 are each independently a hydrogen atom or a saturated hydrocarbon group having a carbon number of 1 to 10, R 103 , R 106 , R 107 and R 108 are each independently a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 15, a fluorinated hydrocarbon group having a carbon number of 1 to 15 or an acid labile group, R 103 , R 106 , R 107 and R 108 are a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group can also be inserted between carbon-carbon bonds, R 109 a linear or branched hydrocarbon group having a carbon number of 1 to 5, in which a hetero atom-containing group can also be inserted between the carbon atoms, R 110 a linear or branched hydrocarbon group having 1 to 5 carbons into which a hetero atom-containing group can also be inserted between carbon-carbon bonds, R 111 a saturated hydrocarbon group having a carbon number of 1 to 20, of which at least one hydrogen atom is replaced with a fluorine atom, and a part of -CH2- of the saturated hydrocarbon group can also be replaced with an ester bond or an ether bond, X 1 (k+1) valent hydrocarbon group having a carbon number of 1 to 20 or a (k+1) valent fluorinated hydrocarbon group having a carbon number of 1 to 20, X 2 is a single bond, *-C(=O)-O- or *-C(=O)-NH-, * is the atomic bond to the carbon atom of the main chain, X 3 is a single bond, -O-, -C(=O)-O-X 31 -X 32 or -C(=O)-NH-X 31 -X 32 -, X 31 is a single bond or a saturated hydrocarbylene group having a carbon number of 1 to 10, X 32 is a single bond, an ester bond, an ether bond or a sulfonamide bond, and * is an atomic bond with a carbon atom of the main chain.

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

16. The chemically amplified negative tone resist composition of claim 15, wherein, The content ratio of (A) the acid generator to (E) the quencher is not 6 in terms of mass ratio.

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

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

19. A resist pattern forming method comprising the steps of: forming a resist film on a substrate using the chemically amplified negative resist composition according to any one of claims 1 to 18, irradiating a pattern to the resist film using a high-energy ray, and developing the resist film to which the pattern has been irradiated using an alkali developer.

20. The resist pattern forming process according to claim 19, wherein, The high-energy ray is an extreme ultraviolet ray having a wavelength of 3 to 15 nm or an electron beam.

21. The resist pattern forming process according to claim 19, wherein, The topmost surface of the substrate is composed of a material containing at least one selected from the group consisting of chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten and tin.

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

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

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