Chemically amplified negative resist composition and resist pattern forming method

Abstract

The invention relates to a chemically amplified negative resist composition and a resist pattern forming method. The present invention addresses the problem of providing: a negative resist composition for chemically amplifying a resist pattern, said negative resist composition being capable of improving the resolution during pattern formation and achieving excellent LER and pattern loyalty; and a method for forming a resist pattern. The chemically amplified negative resist composition contains (A) a photoacid generator comprising an onium salt represented by the following formula (A), and (B) a base polymer comprising a polymer containing a repeating unit represented by the following formula (B1). # imgabs0 #

Description

Technical Field

[0001] The invention relates to a chemically amplified negative resist composition and a resist pattern forming method. Background Art

[0002] In recent years, with the high integration and high speed of LSI, the pattern rules are also rapidly becoming finer. Among them, chemically amplified resist compositions mainly using acid as a catalyst are used for processing patterns below 0.2μm. In addition, high-energy rays such as ultraviolet rays, far ultraviolet rays, and electron beams (EB) are used as exposure sources. EB lithography is particularly used as an ultra-fine processing technology, and is also indispensable as a processing method for blank photomasks when manufacturing photomasks for semiconductor manufacturing.

[0003] A large number of polymers having an aromatic skeleton with an acidic side chain, such as polyhydroxystyrene, are effectively used as materials for KrF lithography resist compositions using KrF excimer lasers, but they exhibit large absorption for light with a wavelength of around 200 nm and cannot be used as materials for ArF lithography resist compositions using ArF excimer lasers. However, they are important materials for materials for EB lithography resist compositions and extreme ultraviolet (EUV) lithography resist compositions, which are powerful technologies for forming patterns with a processing limit smaller than that prepared by ArF excimer lasers, in terms of obtaining high etching resistance.

[0004] In the processing of blank photomasks, there are chromium compound films represented by chromium oxide formed on the photomask substrate, which have surface materials that easily affect the pattern shape of the chemically amplified resist film. In order to achieve high resolution and maintain the shape after etching, it is also one of the important properties to keep the pattern outline of the resist film rectangular regardless of the type of substrate. In recent years, in order to achieve miniaturization, MBMW (Multi-Beam Mask Writing) drawing processing is sometimes used in the processing of blank masks. At this time, the resist composition uses a low-sensitivity resist composition (high-dose area) that is beneficial to roughness, and the optimization of the resist composition in the high-dose area has also attracted attention.

[0005] The resist compositions used in optical lithography include positive type, which dissolves the exposed part to form a pattern, and negative type, which leaves the exposed part to form a pattern. They are selected to facilitate the user according to the form of the required resist pattern. Chemically amplified negative resist compositions usually contain a polymer that dissolves in an aqueous alkaline developer, an acid generator that decomposes and generates an acid due to exposure light, and a crosslinker that uses the acid as a catalyst and forms crosslinks between polymers to make the polymer insoluble in the aforementioned developer (the polymer and the crosslinker may be integrated in some cases). In addition, a quencher is usually added to control the diffusion of the acid generated by exposure.

[0006] The alkali-soluble units constituting the aforementioned polymer that dissolves in an aqueous alkali developer include units derived from phenols. In the past, such negative resist compositions have been developed in large quantities for exposure, especially for KrF excimer lasers. However, when the exposure light has a wavelength of 150 to 220 nm, the units derived from phenols do not have light transmittance, so they cannot be used as ArF excimer lasers. However, in recent years, negative resist compositions for exposure methods that have obtained finer patterns, i.e., short-wavelength exposure light such as EB and EUV, have again attracted attention, and for example, Patent Documents 1, 2, and 3 have been reported.

[0007] Furthermore, as one of the acid generators, there is a sulfonium salt that generates a sulfonic acid having an aromatic group containing an iodine atom, as described in Patent Document 4. However, this is for the sensitivity enhancement effect in EUV lithography, and its function is mainly to operate as a quencher for fluorinated alkanesulfonic acid. No research has been conducted on acid generators, especially on acid generators used in negative resist compositions using polyhydroxystyrene as a base polymer used in the EB drawing process in blank mask processing.

[0008] In addition, in optical lithography, various improvements have been made by changing the selection and combination of materials used in resist compositions, processing conditions, etc., in order to control sensitivity and pattern profile. One of the focuses of the improvements is the problem of acid diffusion, which has a significant impact on the resolution of chemically amplified resist compositions.

[0009] The quencher is a substance that inhibits acid diffusion, and is a necessary component in order to improve the performance of the resist composition, especially the resolution. Various studies have been conducted on the quencher so far, and generally, amines and weak acid onium salts are used. As an example of weak acid onium salts, Patent Document 5 records that by adding triphenylsulfonium acetate, a good resist pattern without T-top formation, line width difference between isolated patterns and dense patterns, and standing waves can be formed. Patent Document 6 records that by adding ammonium sulfonate or ammonium carboxylate, sensitivity, resolution and exposure latitude can be improved. In addition, Patent Document 7 records a resist composition for KrF lithography and EB lithography containing a combination of photoacid generators that can generate carboxylic acids containing fluorine atoms, which has excellent resolution and improves process tolerance such as exposure latitude and depth of focus. In addition, Patent Document 8 also records a resist composition for F2 lithography using F2 lasers containing a photoacid generator that can generate carboxylic acids containing fluorine atoms, which has excellent line edge roughness (LER) and improves the problem of tailing. They are used in KrF lithography, EB lithography or F2 lithography.

[0010] Patent Document 9 describes a positive photosensitive composition for ArF lithography containing a carboxylic acid onium salt. These are formed by exchanging a strong acid (sulfonic acid) and a weak acid onium salt generated from a photoacid generator by exposure to form a weak acid and a strong acid onium salt, and replacing a strong acid (sulfonic acid) with a weak acid (carboxylic acid) to suppress the acid decomposition reaction of an acid-labile group and shorten (control) the acid diffusion distance, and apparently function as a quencher.

[0011] However, in recent years, not only further improvement of roughness is sought, but also a resist composition with excellent line and space (LS), isoline (IL), isospace (IS) and dot pattern shape is required. The photoacid generator described in Patent Document 10 generates a large volume of acid and suppresses the diffusion of the acid. Although it can obtain a pattern with good resolution and roughness, it has the disadvantage of rounded corners in the dot pattern.

[0012] Prior art literature

[0013] Patent Literature

[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 Laid-Open 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 Summary of the invention

[0024] [Problems to be solved by the invention]

[0025] The present invention is made in view of the above situation, and its object is to provide a chemically amplified negative resist composition and a resist pattern forming method that can improve the resolution during pattern formation and obtain a resist pattern with good LER and pattern fidelity.

[0026] [Methods to solve the problem]

[0027] The inventors of the present application have repeatedly conducted in-depth studies in order to achieve the aforementioned objectives, and have obtained the following insights, leading to the completion of the present invention: when an onium salt containing an aromatic sulfonic acid anion having an aromatic ring structure with a bulky substituent and a fluorine-containing substituent is used as an acid generator and introduced into a resist composition, the generated acid has an appropriate acidity, and the excessive diffusion of the acid is suppressed due to the bulky anion structure, thereby obtaining a pattern with a small LER. In addition, in the dot pattern, a pattern with good rectangularity can be obtained by appropriate dissolution inhibition.

[0028] That is, the present invention provides the following chemically amplified negative resist composition and resist pattern forming method.

[0029] 1. A chemically amplified negative resist composition comprising:

[0030] (A) a photoacid generator composed of an onium salt represented by the following formula (A), and

[0031] (B) A base polymer comprising a polymer containing a repeating unit represented by the following formula (B1).

[0032] [Chemistry 1]

[0033]

[0034] In the formula, n1 and n2 are each independently an integer of 0 to 2. n3 is an integer of 1 to 4 when n2=0, an integer of 1 to 6 when n2=1, and an integer of 1 to 8 when n2=2. n4 is an integer of 0 to 3 when n2=0, an integer of 0 to 5 when n2=1, and an integer of 0 to 7 when n2=2. However, n3+n4 is 1 to 4 when n2=0, 1 to 6 when n2=1, and 1 to 8 when n2=2. n5 is an integer of 1 to 5 when n1=0, an integer of 1 to 7 when n1=1, and an integer of 1 to 9 when n1=2.

[0035] R 1 is an iodine atom or a branched or cyclic hydrocarbon group having 3 to 20 carbon atoms which may contain a hetero atom, and at least one R 1 Bonded to L A When n5 is 2 or more, multiple R 1 They may also bond to each other and to the carbon atoms to which they are bonded to form a ring.

[0036] R 2 is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, and when n4 is 2 or more, a plurality of R 2 They may also bond to each other and to the carbon atoms to which they are bonded to form a ring.

[0037] R F1 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 thioalkoxy group having 1 to 6 carbon atoms.

[0038] L A and L B Each is independently a single bond, an ether bond, an ester bond, an amide bond, a sulfonate bond, a carbonate bond or a urethane bond.

[0039] X L It is a single bond or an alkylene group having 1 to 40 carbon atoms which may contain a hetero atom.

[0040] Z + It is an onium cation.

[0041] [Chemistry 2]

[0042]

[0043] 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. a4 is 1, 2 or 3.

[0044] R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0045] R 11 It is a halogen atom, a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon oxy group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom.

[0046] A 1 It is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of the -CH2- of the saturated alkylene group may be substituted by -O-.

[0047] 2. The chemically amplified negative resist composition according to 1., wherein the onium salt is represented by the following formula (A1).

[0048] [Chemistry 3]

[0049]

[0050] In the formula, n3~n5, R 1 , R 2 , R F1 , L A, L B , X L and Z + Same as above.

[0051] 3. The chemically amplified negative resist composition according to 2., wherein the onium salt is represented by the following formula (A2).

[0052] [Chemistry 4]

[0053]

[0054] In the formula, n5, R 1 , L A , L B , X L and Z + Same as above.

[0055] 4. The chemically amplified negative resist composition according to any one of 1. to 3., wherein Z + It is a sulfonium cation represented by the following formula (cation-1) or an iodonium cation represented by the following formula (cation-2).

[0056] [Chemistry 5]

[0057]

[0058] In the formula, R ct1 ~R ct5 are each independently a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom. ct1 and R ct2 They may also bond to each other and to the sulfur atom to which they are bonded to form a ring.

[0059] 5. The chemically amplified negative resist composition according to any one of 1. to 4., wherein the polymer further contains at least one selected from the group consisting of a repeating unit represented by the following formula (B2) and a repeating unit represented by the following formula (B3).

[0060] [Chemistry 6]

[0061]

[0062] Wherein, b1 is 0 or 1. b2 is 0, 1 or 2. b3 is an integer satisfying 0≤b3≤5+2(b2)-b4. b4 is 1, 2 or 3. b5 is 0, 1 or 2. b6 is 1 or 2.

[0063] R A are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0064] R 12It is a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom or a hetero atom.

[0065] R 13 and R 14 Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may be substituted with a hydroxyl group or a saturated hydrocarbon oxy group having 1 to 6 carbon atoms, and the aryl group may have a substituent. 13 and R 14 cannot be a hydrogen atom at the same time. 13 and R 14 They may also be bonded to each other and to the carbon atom to which they are bonded to form a ring, and a portion of the -CH2- in the ring may be substituted by -O- or -S-.

[0066] R 15 It is a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom or a hetero atom.

[0067] R 16 and R 17 Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may be substituted with a hydroxyl group or a saturated hydrocarbon oxy group having 1 to 6 carbon atoms, and the aryl group may have a substituent. 16 and R 17 cannot be a hydrogen atom at the same time. 16 and R 17 They may also be bonded to each other and to the carbon atom to which they are bonded to form a ring, and a portion of the -CH2- in the ring may be substituted by -O- or -S-.

[0068] A 2 It is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of the -CH2- of the saturated alkylene group may be substituted by -O-.

[0069] W 1 and W 2 Each of them 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, and the aryl group may have a substituent.

[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 of 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).

[0071] [Chemistry 7]

[0072]

[0073] In the formula, c and d are each independently an integer of 0 to 4. e1 is 0 or 1. e2 is 0, 1 or 2. e3 is an integer of 0 to 5.

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

[0075] R 21 and R 22 Each of them is independently a hydroxyl group, a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon oxy group having 1 to 8 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom.

[0076] R 23 It is a saturated hydrocarbon group having 1 to 20 carbon atoms, a saturated hydrocarbon oxy group having 1 to 20 carbon atoms, a saturated hydrocarbon carbonyloxy group having 2 to 20 carbon atoms, a saturated hydrocarbon oxyhydrocarbyl group having 2 to 20 carbon atoms, a saturated hydrocarbon thiohydrocarbyl group having 2 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, a saturated hydrocarbon sulfinyl group having 1 to 20 carbon atoms, or a saturated hydrocarbon sulfonyl group having 1 to 20 carbon atoms.

[0077] A 3 It is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of the -CH2- of the saturated alkylene group may be substituted by -O-.

[0078] 7. A chemically amplified negative resist composition as described in 5., wherein the aforementioned polymer further contains at least one of 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 (B10), a repeating unit represented by the following formula (B11), a repeating unit represented by the following formula (B12), a repeating unit represented by the following formula (B13) and a repeating unit represented by the following formula (B14).

[0079] [Chemistry 8]

[0080]

[0081] In the formula, R B are each independently a hydrogen atom or a methyl group.

[0082] Y 1 Each of them is independently a single bond, an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining them, or *-OY 11 -, *-C(=O)-OY 11 - or *-C(=O)-NH-Y 11 -, and Y 11It is an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these groups, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group.

[0083] Y 2 are independently a single bond or **-Y 21 -C(=O)-O-, and Y 21 It is a hydrocarbylene group having 1 to 20 carbon atoms which may contain a hetero atom.

[0084] Y 3 are independently a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, *-OY 31 -, *-C(=O)-OY 31 - or *-C(=O)-NH-Y 31 -.Y 31 It is an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, or a group having 7 to 20 carbon atoms obtained by combining these groups, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group.

[0085] * is an atomic bond to a carbon atom in the main chain, and ** is an atomic bond to an oxygen atom in the formula.

[0086] Y 4 Each independently represents a single bond or a hydrocarbylene group having 1 to 30 carbon atoms which may contain a hetero atom.

[0087] f1 and f2 are independently 0 or 1, but Y 4 When it is a single bond, f1 and f2 are 0.

[0088] R 31 ~R 48 are each independently a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. 31 and R 32 They may also be bonded to each other and to the sulfur atom to which they are bonded to form a ring, and R 33 and R 34 , R 36 and R 37 , or R 39 and R 40 They may also bond to each other and to the sulfur atom to which they are bonded to form a ring.

[0089] R HF is a hydrogen atom or a trifluoromethyl group.

[0090] XA - It is a non-nucleophilic relative ion.

[0091] 8. A chemically amplified negative resist composition as described in 7., wherein the polymer contains a repeating unit represented by the following formula (B1-1), 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).

[0092] [Chemistry 9]

[0093]

[0094] In the formula, a4, b4, b6, R A , R B , Y 2 , R 13 , R 14 , R 16 , R 17 , R 33 , R 34 , R 35 and R HF Same as above.

[0095] 9. A chemically amplified negative resist composition as described in 7., 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), and does not contain repeating units represented by formulas (B7) to (B14).

[0096] 10. The chemically amplified negative resist composition according to any one of 1. to 9., wherein the content of repeating units having an aromatic ring skeleton in all repeating units of the polymer included in the base polymer is 60 mol% or more.

[0097] 11. The chemically amplified negative resist composition according to any one of 1. to 10., further comprising (C) a cross-linking agent.

[0098] 12. The chemically amplified negative resist composition of 5., which does not contain a cross-linking agent.

[0099] 13. The chemically amplified negative resist composition as described in any one of 1. to 12. further contains (D) a polymer containing fluorine atoms which contains at least one of a repeating unit represented by the following formula (D1), 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 may also contain at least one of a repeating unit represented by the following formula (D5) and a repeating unit represented by the following formula (D6).

[0100] [Chemistry 10]

[0101]

[0102] In the formula, x is an integer of 1 to 3. y is an integer satisfying 0≤y≤5+2z-x. z is 0 or 1. g is an integer of 1 to 3.

[0103] R C are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0104] R D are each independently a hydrogen atom or a methyl group.

[0105] R 101 , R 102 , R 104 and R 105 Each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.

[0106] R 103 , R 106 , R 107 and R 108 are 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, and R 103 , R 106 , R 107 and R 108 In the case of a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group may be inserted between carbon-carbon bonds.

[0107] R 109 It is a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a heteroatom-containing group inserted between carbon-carbon bonds.

[0108] R 110 It is a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a heteroatom-containing group inserted between carbon-carbon bonds.

[0109] R 111 It is a saturated hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom, and a part of the -CH2- group of the saturated hydrocarbon group may be substituted by an ester bond or an ether bond.

[0110] Z 1 It is a (g+1)-valent hydrocarbon group having 1 to 20 carbon atoms or a (g+1)-valent fluorinated hydrocarbon group having 1 to 20 carbon atoms.

[0111] Z 2 It is a single bond, *-C(=O)-O- or *-C(=O)-NH-. * is an atomic bond to a carbon atom of the main chain.

[0112] Z 3 is a single bond, -O-, *-C(=O)-OZ 31 -Z 32 - or *-C(=O)-NH-Z 31-Z 32 -.Z 31 Z is a single bond or a saturated alkylene group having 1 to 10 carbon atoms. 32 It is a single bond, an ester bond, an ether bond or a sulfonamide bond.

[0113] * is the atomic bond to the carbon atom of the main chain.

[0114] 14. The chemically amplified negative resist composition according to any one of 1. to 13., further comprising (E) a quencher.

[0115] 15. The chemically amplified negative resist composition according to 14., wherein the content ratio of the (A) acid generator to the (E) quencher is less than 6 in terms of mass ratio.

[0116] 16. The chemically amplified negative resist composition according to any one of 1. to 15., further comprising (F) an organic solvent.

[0117] 17. A method for forming a resist pattern, comprising the following steps:

[0118] Using the chemically amplified negative resist composition of any one of 1. to 16. to form a resist film on a substrate,

[0119] irradiating the resist film with high energy radiation in a pattern, and

[0120] The resist film irradiated with the above pattern is developed using an alkaline developer.

[0121] 18. The resist pattern forming method according to 17., wherein the high-energy rays are extreme ultraviolet rays or electron beams.

[0122] 19. The resist pattern forming method according to 17. or 18., wherein the outermost 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.

[0123] 20. The resist pattern forming method according to any one of 17. to 19., wherein the substrate is a transmission type or reflection type blank mask.

[0124] 21. A transmission or reflection blank mask, which is formed by coating the chemically amplified negative resist composition as described in any one of 1. to 16.

[0125] [Effects of the Invention]

[0126] The chemically amplified negative resist composition of the present invention utilizes the effect of the onium salt represented by formula (A) to effectively control the acid diffusion caused by exposure during pattern formation. When the resist film is formed and the pattern is formed, a pattern with extremely high resolution, high pattern fidelity, and reduced LER can be obtained. In addition, the effect of the repeating unit represented by formula (B1) can improve the adhesion of the resist film to the substrate when the resist film is formed, and the solubility in the alkaline developer can be controlled. DETAILED DESCRIPTION

[0127] Hereinafter, the present invention will be described in detail. In addition, in the following description, since the structure represented by the chemical formula has an asymmetric carbon, it is possible that there are mirror image isomers and non-mirror image isomers, and in this case, these isomers are represented by one general formula. These isomers can be used alone or as a mixture of two or more.

[0128] [Chemically amplified negative resist composition]

[0129] The chemically amplified negative resist composition of the present invention is characterized by comprising:

[0130] (A) a photoacid generator comprising an onium salt containing an aromatic sulfonic acid anion having an aromatic ring structure containing a bulky substituent and a fluorine-containing substituent, and

[0131] (B) A base polymer comprising a predetermined polymer.

[0132] [(A) Photoacid generator]

[0133] The onium salt of the photoacid generator as the component (A) is represented by the following formula (A).

[0134] [Chemistry 11]

[0135]

[0136] In formula (A), n1 and n2 are each independently an integer of 0 to 2. n3 is an integer of 1 to 4 when n2=0, an integer of 1 to 6 when n2=1, and an integer of 1 to 8 when n2=2.

[0137] In formula (A), n4 is an integer of 0 to 3 when n2 = 0, an integer of 0 to 5 when n2 = 1, and an integer of 0 to 7 when n2 = 2. However, n3 + n4 is 1 to 4 when n2 = 0, 1 to 6 when n2 = 1, and 1 to 8 when n2 = 2.

[0138] In formula (A), n5 is an integer of 1 to 5 when n1=0, an integer of 1 to 7 when n1=1, and an integer of 1 to 9 when n1=2.

[0139] In formula (A), R 1is an iodine atom or a branched or cyclic hydrocarbon group having 3 to 20 carbon atoms which may contain a hetero atom, and at least one R 1 Bonded to and described later L A Specific examples of the aforementioned hydrocarbon group include: branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, tert-pentyl, and 2-ethylhexyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl, tricyclo[5.2.1.0 2,6 ] aliphatic cyclic hydrocarbon groups having 3 to 20 carbon atoms such as decyl and adamantyl; aryl groups such as phenyl, naphthyl, anthracenyl; groups obtained by combining them, etc., but not limited thereto. In addition, part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and part of the -CH2- of the aforementioned hydrocarbon group may be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, etc., and as a result, it may also contain hydroxyl groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sultone rings, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl groups, etc. The aforementioned halogen atoms include; fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., preferably fluorine atoms or iodine atoms. When n5 is 2 or more, each R 1 They can be the same or different.

[0140] When n5 is 2 or more, multiple R 1 They may also be bonded to each other and to form a ring together with the carbon atom to which they are bonded. The aforementioned ring is preferably a 5- to 8-membered ring.

[0141] R in formula (A) 1 The structure formed by bonding with an aromatic ring can be exemplified by the following, but is not limited thereto. A of atomic bonds.

[0142] [Chemistry 12]

[0143]

[0144] [Chemistry 13]

[0145]

[0146] [Chemistry 14]

[0147]

[0148] [Chemistry 15]

[0149]

[0150] [Chemistry 16]

[0151]

[0152] [Chemistry 17]

[0153]

[0154] [Chemistry 18]

[0155]

[0156] In formula (A), R 2 It is a hydrocarbon group having 1 to 20 carbon atoms which may also contain heteroatoms. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be any of linear, branched, and cyclic. Specific examples thereof include: alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.0 2,6 ] cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as decyl, adamantyl, adamantylmethyl; aryl groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, etc. In addition, part or all of the hydrogen atoms of the aforementioned hydrocarbon groups may be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, and part of the -CH2- of the aforementioned hydrocarbon groups may be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, etc., and as a result, they may contain hydroxyl groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sultone rings, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl groups, etc. The aforementioned halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., preferably fluorine atoms or iodine atoms. When n4 is 2 or more, each R 2 They can be the same or different.

[0157] When n4 is 2 or more, multiple R 2 They may also be bonded to each other and to form a ring together with the carbon atom to which they are bonded. The aforementioned ring is preferably a 5- to 8-membered ring.

[0158] In formula (A), R F1 R 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 thioalkoxy group having 1 to 6 carbon atoms. F1 It is preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group or a difluoromethylthio group, and is more preferably a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group. By containing a fluorine atom, the acid strength of the generated acid is improved, so the deprotection reaction proceeds smoothly. When n3 is 2 or more, each R F1They can be the same or different.

[0159] In formula (A), L A and L B Each of them is independently a single bond, an ether bond, an ester bond, an amide bond, a sulfonate bond, a carbonate bond or a carbamate bond. Among them, an ether bond, an ester bond or a sulfonate bond is preferred, and an ether bond or a sulfonate bond is more preferred.

[0160] In formula (A), X L It is a single bond or a alkylene group having 1 to 40 carbon atoms which may contain a hetero atom. The alkylene group may be linear, branched or cyclic, and specific examples thereof include alkanediyl and cyclic saturated alkylene groups. Specific examples of the hetero atom include oxygen atoms, nitrogen atoms, sulfur atoms, etc.

[0161] X L Specific examples of the alkylene group having 1 to 40 carbon atoms which may contain a hetero atom represented by may be listed below, but are not limited thereto. A and L B of atomic bonds.

[0162] [Chemistry 19]

[0163]

[0164] [Chemistry 20]

[0165]

[0166] [Chemistry 21]

[0167]

[0168] [Chemistry 22]

[0169]

[0170] Among them, X L -0~X L -22 and X L -47~X L -58. The onium salt represented by the formula (A) is preferably represented by the following formula (A1).

[0171] [Chemistry 23]

[0172]

[0173] In the formula, n3~n5, R 1 , R 2 , R F1 , L A , L B , X L and Z+ Same as above.

[0174] The onium salt represented by the formula (A1) is preferably represented by the following formula (A2).

[0175] [Chemistry 24]

[0176]

[0177] In the formula, n5, R 1 , L A , L B , X L and Z + Same as above.

[0178] Specific examples of the anion of the onium salt represented by formula (A) include the following, but are not limited thereto.

[0179] [Chemistry 25]

[0180]

[0181] [Chemistry 26]

[0182]

[0183] [Chemistry 27]

[0184]

[0185] [Chemistry 28]

[0186]

[0187] [Chemistry 29]

[0188]

[0189] [Chemistry 30]

[0190]

[0191] [Chemistry 31]

[0192]

[0193] [Chemistry 32]

[0194]

[0195] [Chemistry 33]

[0196]

[0197] [Chemistry 34]

[0198]

[0199] [Chemistry 35]

[0200]

[0201] [Chemistry 36]

[0202]

[0203] [Chemistry 37]

[0204]

[0205] [Chemistry 38]

[0206]

[0207] [Chemistry 39]

[0208]

[0209] [Chemistry 40]

[0210]

[0211] [Chemistry 41]

[0212]

[0213] [Chemistry 42]

[0214]

[0215] [Chemistry 43]

[0216]

[0217] [Chemistry 44]

[0218]

[0219] [Chemistry 45]

[0220]

[0221] [Chemistry 46]

[0222]

[0223] [Chemistry 47]

[0224]

[0225] [Chemistry 48]

[0226]

[0227] [Chemistry 49]

[0228]

[0229] [Chemistry 50]

[0230]

[0231] [Chemistry 51]

[0232]

[0233] [Chemistry 52]

[0234]

[0235] [Chemistry 53]

[0236]

[0237] [Chemistry 54]

[0238]

[0239] [Chemistry 55]

[0240]

[0241] [Chemistry 56]

[0242]

[0243] In formula (A), Z + The onium cation is preferably a sulfonium cation represented by the following formula (cation-1) or an iodonium cation represented by the following formula (cation-2).

[0244] [Chemistry 57]

[0245]

[0246] In formula (cation-1) and (cation-2), R ct1 ~R ct5 Each is independently a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom.

[0247] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0248] The aforementioned hydrocarbon group may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include: alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups having 3 to 30 carbon atoms, such as cyclohexenyl; aryl groups having 6 to 30 carbon atoms, such as phenyl, naphthyl, and thienyl; aralkyl groups having 7 to 30 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them, preferably aryl groups. Furthermore, part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted by a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of the -CH2- of the aforementioned hydrocarbon group may be substituted by a group containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and 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, sultone rings, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl groups, and the like.

[0249] Again, R ct1 and R ct2 They may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. In this case, the sulfonium cation represented by the formula (cation-1) includes the following.

[0250] [Chemistry 58]

[0251]

[0252] In the formula, the dotted line is and R ct3 of atomic bonds.

[0253] Examples of the sulfonium cation represented by the formula (cation-1) include the following, but are not limited thereto.

[0254] [Chemistry 59]

[0255]

[0256] [Chemistry 60]

[0257]

[0258] [Chemistry 61]

[0259]

[0260] [Chemistry 62]

[0261]

[0262] [Chemistry 63]

[0263]

[0264] [Chemistry 64]

[0265]

[0266] [Chemistry 65]

[0267]

[0268] [Chemistry 66]

[0269]

[0270] [Chemistry 67]

[0271]

[0272] [Chemistry 68]

[0273]

[0274] [Chemistry 69]

[0275]

[0276] [Chemistry 70]

[0277]

[0278] [Chemistry 71]

[0279]

[0280] [Chemistry 72]

[0281]

[0282] [Chemistry 73]

[0283]

[0284] [Chemistry 74]

[0285]

[0286] [Chemistry 75]

[0287]

[0288] [Chemistry 76]

[0289]

[0290] [Chemistry 77]

[0291]

[0292] [Chemistry 78]

[0293]

[0294] [Chemistry 79]

[0295]

[0296] [Chemistry 80]

[0297]

[0298] [Chemistry 81]

[0299]

[0300] [Chemistry 82]

[0301]

[0302] [Chemistry 83]

[0303]

[0304] [Chemistry 84]

[0305]

[0306] Examples of the iodonium cation represented by the formula (cation-2) include the following, but are not limited thereto.

[0307] [Chemistry 85]

[0308]

[0309] [Chemistry 86]

[0310]

[0311] Specific examples of the onium salt represented by formula (A) include any combination of the above-mentioned anions and cations.

[0312] In the chemically amplified negative resist composition of the present invention, the content of the (A) photoacid generator is preferably 0.1 to 40 parts by mass, more preferably 1 to 20 parts by mass, relative to 80 parts by mass of the (B) base polymer described later. When the content of the acid generator is within the above range, an acid sufficient to deprotect the acid-labile group is generated, and storage stability is also good. The (A) photoacid generator may be used alone or in combination of two or more.

[0313] The chemically amplified negative resist composition of the present invention may further contain an acid generator other than the onium salt represented by formula (A) (hereinafter also referred to as other acid generator) for the purpose of pattern shape correction, etc. The other acid generator may be an acid generator known to be used in a resist composition. The content of the other acid generator is preferably 0 to 40 parts by mass, and more preferably 0 to 30 parts by mass, relative to 80 parts by mass of the base polymer (B) described later, in view of sensitivity and acid diffusion inhibition effect. The other acid generator may be used alone or in combination of two or more.

[0314] [(B) Base polymer]

[0315] The base polymer of component (B) is a polymer (hereinafter referred to as polymer B) containing a repeating unit represented by the following formula (B1) (hereinafter referred to as repeating unit B1). Repeating unit B1 is a repeating unit that provides etching resistance, adhesion to the substrate, and solubility in an alkaline developer.

[0316] [Chemistry 87]

[0317]

[0318] In formula (B1), a1 is 0 or 1. a2 is 0, 1 or 2, and when it is 0, it represents a benzene skeleton, when it is 1, it represents a naphthalene skeleton, and when it is 2, it represents an 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 preferably that a3 is an integer of 0 to 3 and a4 is 1, 2 or 3. When a2 is 1 or 2, it is preferably that a3 is an integer of 0 to 4 and a4 is 1, 2 or 3.

[0319] In formula (B1), R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0320] In formula (B1), R 11 It is a halogen atom, a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon oxy group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbon carbonyl oxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom. The saturated hydrocarbon group, the saturated hydrocarbon oxy group, and the saturated hydrocarbon carbonyl oxy group may be straight chain, branched, or cyclic. Specific examples thereof include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, and their structural isomers; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; and groups obtained by combining them. If the number of carbon atoms is below the upper limit, the solubility in the alkaline developer is good. When a3 is 2 or more, each R 11 They can be the same or different.

[0321] In formula (B1), A 1is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of -CH2- in the saturated alkylene group may be substituted by -O-. The saturated alkylene group may be linear, branched or cyclic, and specific examples thereof include: alkylene groups having 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 having 3 to 10 carbon atoms such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; and groups obtained by combining them. When the saturated alkylene group contains an ether bond, when a1 in formula (B1) is 1, it may 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. When a1 is 0, the atom bonded to the main chain becomes an etheric oxygen atom, and the second ether bond may 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 etheric oxygen atom. In addition, if the carbon number of the saturated alkylene group is 10 or less, sufficient solubility in an alkaline developer can be obtained, which is more preferable.

[0322] a1 is 0 and A 1 When it is a single bond, that is, the aromatic ring is directly bonded to the main chain of the polymer (that is, there is no connecting group (-C(=O)-OA 1 -)), the repeating unit B1 preferably includes units derived from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene, 6-hydroxy-2-vinylnaphthalene, etc. In particular, the repeating unit represented by the following formula (B1-1) is preferred.

[0323] [Chemistry 88]

[0324]

[0325] In the formula, R A and a4 are the same as above.

[0326] a1 is 1 (i.e., has -C(=O)-OA 1 - as a linking group), the following are preferred examples of repeating unit B1, but are not limited thereto. A Same as above.

[0327] [Chemistry 89]

[0328]

[0329] The repeating unit B1 may be used alone or in combination of two or more.

[0330] Polymer B may also contain at least one of the repeating units represented by the following formula (B2) (hereinafter also referred to as repeating unit B2) and the repeating units represented by the following formula (B3) (hereinafter also referred to as repeating unit B3) (hereinafter, the polymer B containing at least one of the repeating units B2 and repeating units B3 is also referred to as polymer B').

[0331] [Chemistry 90]

[0332]

[0333] Repeating units B2 and B3 are oxidized by the acid generated by the acid generator when exposed to high-energy radiation. 1 The repeating units B2 and B3 cause a leaving reaction, inducing insolubilization in an alkaline developer and a cross-linking reaction between polymers. The negative-type reaction can be more efficiently carried out by utilizing the effects of the repeating units B2 and B3, thereby improving the resolution.

[0334] In formula (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.

[0335] In formula (B3), b5 is 0, 1 or 2, preferably 0 or 1. b6 is 1 or 2, preferably 1.

[0336] In formula (B2) and (B3), R A Each of them is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. Among them, the one in formula (B3) is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0337] In formula (B2), R 12 is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. 12 Specific examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. 15 The hydrocarbon group having 1 to 20 carbon atoms represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include those exemplified as R in the description of formula (A). 2 The same examples are given for hydrocarbon groups represented by 12 They can be the same or different.

[0338] In formula (B2), R 13 and R 14 Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may be substituted with a hydroxyl group or a saturated hydrocarbon oxy group having 1 to 6 carbon atoms, and the aryl group may have a substituent. 13 and R 14cannot be a hydrogen atom at the same time. 13 and R 14 They may also be bonded to each other and to the carbon atoms to which they are bonded to form a ring, and a portion of the -CH2- in the ring may be substituted by -O- or -S-. 13 and R 14 Preferred examples include alkyl groups such as methyl, ethyl, propyl, butyl, and structural isomers thereof, and groups in which a part of hydrogen atoms is substituted with a hydroxyl group or a saturated hydrocarbon oxy group.

[0339] In formula (B3), R 15 is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. 15 Specific examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. 15 The hydrocarbon group having 1 to 20 carbon atoms represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include those exemplified as R in the description of formula (A). 2 The same example applies to the hydrocarbon group represented by 15 They can be the same or different.

[0340] In formula (B3), R 16 and R 17 Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may be substituted with a hydroxyl group or a saturated hydrocarbon oxy group having 1 to 6 carbon atoms, and the aryl group may have a substituent.

[0341] R 16 and R 17 The saturated hydrocarbon group having 1 to 15 carbon atoms represented by may be linear, branched, or cyclic. 13 and R 14 The same examples are given for the saturated hydrocarbon groups represented by .

[0342] R 16 and R 17 Specific examples of the aryl group having 6 to 15 carbon atoms represented by phenyl, naphthyl, anthracenyl, etc., among which phenyl is preferred. In addition, the aryl group may have a substituent, and specific examples of the substituent include a halogen atom, a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom, and a saturated hydrocarbon oxy group having 1 to 6 carbon atoms which may be substituted by a halogen atom.

[0343] Again, R 16 and R 17 cannot be a hydrogen atom at the same time. 16 and R 17 When any one of them is an aryl group which may have a substituent, the other substituent is preferably a hydrogen atom.

[0344] R 16 and R 17 They are preferably the same group, more preferably methyl.

[0345] Again, R 16 and R 17 They may also be bonded to each other and to the carbon atoms to which they are bonded to form a ring, and a portion of the -CH2- in the ring may be substituted by -O- or -S-. Examples of the aforementioned ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, norbornane ring, adamantane ring, tricyclic [5.2.1.0 2,6 ]Decane ring, tetracyclic [6.2.1.1 3,6 .0 2,7 ] dodecane ring, oxa-norbornane ring, thia-norbornane ring, etc., but are not limited thereto.

[0346] In formula (B2), A 2 It is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of -CH2- of the saturated alkylene group may be substituted by -O-. The saturated alkylene group may be straight chain, branched or cyclic, and specific examples thereof include: methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and their structural isomers; cyclic saturated alkylene groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; and groups obtained by combining them. When the saturated alkylene group contains an ether bond, when b1 in formula (B2) is 1, it may 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. When b1 is 0, the atom bonded to the main chain becomes an etheric oxygen atom, and the second etheric bond may 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 etheric oxygen atom.

[0347] In formula (B2) and (B3), W 1 and W 2 Each of them 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, and the aryl group may have a substituent.

[0348] W 1 and W 2The aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by W may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include: alkyl groups having 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 having 3 to 10 carbon atoms, such as cyclopentyl and cyclohexyl; alkenyl groups having 2 to 10 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups having 3 to 10 carbon atoms, such as cyclohexenyl, etc. W. 1 and W 2 The hydrocarbon radical of the aliphatic hydrocarbon carbonyl having 2 to 10 carbon atoms represented by W may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include those having 1 to 9 carbon atoms among the specific examples of the aliphatic hydrocarbon having 1 to 10 carbon atoms described above. 1 and W 2 Specific examples of the aryl group having 6 to 15 carbon atoms represented by : include phenyl, naphthyl, anthracenyl, etc., among which phenyl is preferred. In addition, the aryl group may have a substituent, and specific examples of the substituent include halogen atoms, saturated hydrocarbon groups having 1 to 6 carbon atoms which may be substituted by halogen atoms, and saturated hydrocarbon oxy groups having 1 to 6 carbon atoms which may be substituted by halogen atoms.

[0349] The repeating unit B2 is preferably represented by the following formula (B2-1) or (B2-2).

[0350] [Chemistry 91]

[0351]

[0352] In the formula, b4, R A , R 13 and R 14 Same as above.

[0353] Preferred examples of repeating unit B2 include those shown below, but are not limited thereto. A As mentioned above, Me is methyl and Ac is acetyl.

[0354] [Chemistry 92]

[0355]

[0356] [Chemistry 93]

[0357]

[0358] [Chemistry 94]

[0359]

[0360] [Chemistry 95]

[0361]

[0362] [Chemistry 96]

[0363]

[0364] [Chemistry 97]

[0365]

[0366] [Chemistry 98]

[0367]

[0368] [Chemistry 99]

[0369]

[0370] [Chemical 100]

[0371]

[0372] [Chemistry 101]

[0373]

[0374] [Chemistry 102]

[0375]

[0376] The repeating unit B2 may be used alone or in combination of two or more. The repeating unit B3 is preferably represented by the following formula (B3-1).

[0377] [Chemistry 103]

[0378]

[0379] In the formula, b6, R A , R 16 and R 17 Same as above.

[0380] Preferred examples of repeating unit B3 include those shown below, but are not limited thereto. A As mentioned above, Me is methyl and Ac is acetyl.

[0381] [Chemistry 104]

[0382]

[0383] [Chemistry 105]

[0384]

[0385] [Chemistry 106]

[0386]

[0387] [Chemistry 107]

[0388]

[0389] [Chemistry 108]

[0390]

[0391] [Chemistry 109]

[0392]

[0393] [Chemistry 110]

[0394]

[0395] [Chemistry 111]

[0396]

[0397] [Chemistry 112]

[0398]

[0399] [Chemistry 113]

[0400]

[0401] [Chemistry 114]

[0402]

[0403] [Chemistry 115]

[0404]

[0405] [Chemistry 116]

[0406]

[0407] [Chemistry 117]

[0408]

[0409] [Chemistry 118]

[0410]

[0411] [Chemistry 119]

[0412]

[0413] [Chemistry 120]

[0414]

[0415] [Chemistry 121]

[0416]

[0417] [Chemistry 122]

[0418]

[0419] [Chemistry 123]

[0420]

[0421] [Chemistry 124]

[0422]

[0423] [Chemistry 125]

[0424]

[0425] [Chemistry 126]

[0426]

[0427] [Chemistry 127]

[0428]

[0429] [Chemistry 128]

[0430]

[0431] [Chemistry 129]

[0432]

[0433] [Chemistry 130]

[0434]

[0435] [Chemistry 131]

[0436]

[0437] [Chemistry 132]

[0438]

[0439] [Chemistry 133]

[0440]

[0441] [Chemistry 134]

[0442]

[0443] [Chemistry 135]

[0444]

[0445] [Chemistry 136]

[0446]

[0447] The repeating unit B3 may be used alone or in combination of two or more.

[0448] In order to improve etching resistance, polymers B and B' may also contain at least one selected from the repeating unit represented by the following formula (B4) (hereinafter also referred to as repeating unit B4), the repeating unit represented by the following formula (B5) (hereinafter also referred to as repeating unit B5) and the repeating unit represented by the following formula (B6) (hereinafter also referred to as repeating unit B6).

[0449] [Chemistry 137]

[0450]

[0451] In formulae (B4) and (B5), c and d are each independently an integer of 0 to 4.

[0452] In formula (B4) and (B5), R 21 and R 22 Each of R is independently a hydroxyl group, a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon oxy group having 1 to 8 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom. The saturated hydrocarbon group, saturated hydrocarbon oxy group, and saturated hydrocarbon carbonyloxy group may be straight-chain, branched, or cyclic. When c is 2 or more, each R 21 They may be the same or different from each other. When d is 2 or more, each R 22 They can be the same or different.

[0453] In formula (B6), e1 is 0 or 1. e2 is 0, 1 or 2, and when it is 0, it represents a benzene skeleton, when it is 1, it represents a naphthalene skeleton, and when it is 2, it represents an anthracene skeleton. e3 is an integer of 0 to 5. When e2 is 0, e3 is preferably an integer of 0 to 3, and when e2 is 1 or 2, e3 is preferably an integer of 0 to 4.

[0454] In formula (B6), R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0455] In formula (B6), R23 is a saturated hydrocarbon group having 1 to 20 carbon atoms, a saturated hydrocarbon oxy group having 1 to 20 carbon atoms, a saturated hydrocarbon carbonyl oxy group having 2 to 20 carbon atoms, a saturated hydrocarbon oxy hydrocarbon group having 2 to 20 carbon atoms, a saturated hydrocarbon thio hydrocarbon group having 2 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, a saturated hydrocarbon sulfinyl group having 1 to 20 carbon atoms, or a saturated hydrocarbon sulfonyl group having 1 to 20 carbon atoms. The saturated hydrocarbon group, saturated hydrocarbon oxy group, saturated hydrocarbon carbonyl oxy group, saturated hydrocarbon oxy hydrocarbon group, saturated hydrocarbon thio hydrocarbon group, saturated hydrocarbon sulfinyl group, and saturated hydrocarbon sulfonyl group may be straight-chain, branched, or cyclic. When e3 is 2 or more, each R 23 They can be the same or different.

[0456] R 23 Preferred are halogen atoms such as chlorine atoms, bromine atoms, and iodine atoms; saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, and structural isomers thereof; and saturated hydrocarbon oxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopentyloxy, cyclohexyloxy, and structural isomers of their hydrocarbon moieties. Among them, methoxy and ethoxy are particularly useful.

[0457] Furthermore, the saturated hydrocarbon carbonyloxy group can be easily introduced by chemical modification even after the polymerization of the polymer, and can be used for fine adjustment of the solubility of the base polymer in the alkaline developer. Examples of the saturated hydrocarbon carbonyloxy group include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, butylcarbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, and structural isomers of their hydrocarbon parts. If the carbon number is 20 or less, the effect of controlling and adjusting the solubility of the base polymer in the alkaline developer (mainly the decreasing effect) can be adjusted to an appropriate range, and the generation of scum (development defects) can be suppressed.

[0458] Among the above-mentioned desirable substituents, particularly those which are easily prepared as monomers and can be used effectively include a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, a methoxy group and the like.

[0459] In formula (B6), A 3It is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of -CH2- of the saturated alkylene group may be substituted by -O-. The saturated alkylene group may be linear, branched or cyclic, and specific examples thereof include: alkylene groups having 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 having 3 to 10 carbon atoms such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; and groups obtained by combining them. When the saturated alkylene group contains an ether bond, when e1 in formula (B6) is 1, it may be inserted at any position except between the carbon atom at the α position and the carbon atom at the β position relative to the ester oxygen atom. When e1 is 0, the atom bonded to the main chain is an etheric oxygen atom, and the second ether bond may be inserted at any position except between the carbon atom at the α position and the carbon atom at the β position relative to the etheric oxygen atom. In addition, if the carbon number of the saturated alkylene group is 10 or less, sufficient solubility in an alkaline developer can be obtained, which is more preferable.

[0460] e1 is 0 and A 3 In the case of a single bond, in other words, the aromatic ring is directly bonded to the main chain of the polymer (i.e., there is no linking group (-C(=O)-OA 3 -)), preferable examples of the repeating unit B6 include units derived from styrene, 4-chlorostyrene, 4-methylstyrene, 4-methoxystyrene, 4-bromostyrene, 4-acetoxystyrene, 2-hydroxypropylstyrene, 2-vinylnaphthalene, 3-vinylnaphthalene and the like.

[0461] When e1 is 1 (i.e., having -C(=O)-OA 3 - as a linking group), the following are examples of desirable repeating units B6, but are not limited thereto. A Same as above.

[0462] [Chemistry 138]

[0463]

[0464] [Chemistry 139]

[0465]

[0466] When at least one of the repeating units B4 to B6 is used as a constituent unit of the polymer, the etching resistance of the aromatic ring is improved, and the etching resistance due to the addition of a ring structure to the main chain and the EB irradiation resistance during pattern inspection are improved.

[0467] The repeating units B4 to B6 may be used alone or in combination of two or more.

[0468] The polymer B' may further contain at least one selected from the repeating unit represented by the following formula (B7) (hereinafter also referred to as repeating unit B7), the repeating unit represented by the following formula (B8) (hereinafter also referred to as repeating unit B8), the repeating unit represented by the following formula (B9) (hereinafter also referred to as repeating unit B9), the repeating unit represented by the following formula (B10) (hereinafter also referred to as repeating unit B10), the repeating unit represented by the following formula (B11) (hereinafter also referred to as repeating unit B11), the repeating unit represented by the following formula (B12) (hereinafter also referred to as repeating unit B12), the repeating unit represented by the following formula (B13) (hereinafter also referred to as repeating unit B13) and the repeating unit represented by the following formula (B14) (hereinafter also referred to as repeating unit B14). In this case, acid diffusion can be effectively suppressed and resolution can be improved, and a pattern with reduced LER can be obtained.

[0469] [Chemistry 140]

[0470]

[0471] In formulas (B7) to (B14), R B are each independently a hydrogen atom or a methyl group. 1 Each of them is independently a single bond, an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining them, or *-OY 11 -, *-C(=O)-OY 11 - or *-C(=O)-NH-Y 11 -, and Y 11 It is an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining them, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 2 are independently a single bond or **-Y 21 -C(=O)-O-, and Y 21 Y is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. 3 are independently a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, *-OY 31 -, *-C(=O)-OY 31 - or *-C(=O)-NH-Y 31 -.Y 31 It is an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, or a group having 7 to 20 carbon atoms obtained by combining them, and may also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. * is an atomic bond to a carbon atom of the main chain, and ** is an atomic bond to an oxygen atom in the formula. Y 4Each of f1 and f2 is independently 0 or 1, but Y 4 When it is a single bond, f1 and f2 are 0.

[0472] In formula (B7) and (B11), Xa - It is a non-nucleophilic counter ion. - Examples of the non-nucleophilic counter ion represented by include those described in JP-A-2010-113209 and JP-A-2007-145797.

[0473] In formula (B8) and (B12), Y 2 Y 21 -C(=O)-O-, Y 21 The hydrocarbylene group which may contain a hetero atom may be exemplified by the following, but is not limited thereto.

[0474] [Chemistry 141]

[0475]

[0476] In the formula, the dotted lines are atomic bonds.

[0477] In formula (B8) and (B12), R HF is a hydrogen atom or a trifluoromethyl group. In repeating units B8 and B12, R HF Specific examples of a hydrogen atom include those described in Japanese Patent Application Laid-Open No. 2010-116550, HF Specific examples of the trifluoromethyl group include those described in Japanese Patent Application Laid-Open No. 2010-77404. Examples of the repeating units B8 and B12 include those described in Japanese Patent Application Laid-Open No. 2012-246265 and Japanese Patent Application Laid-Open No. 2012-246426.

[0478] Preferred examples of the anion of the monomer providing the repeating unit B10 or B14 include those shown below, but are not limited thereto.

[0479] [Chemistry 142]

[0480]

[0481] [Chemistry 143]

[0482]

[0483] In formulas (B7) to (B14), R 31 ~R 48Each is independently a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. The hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples of the halogen atom and hydrocarbon group include those exemplified as R in the description of formula (cation-1) and (cation-2). ct1 ~R ct5 The same examples are given for the halogen atoms and hydrocarbon groups represented by the above. In addition, part or all of the hydrogen atoms of the above hydrocarbon groups may be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of the -CH2- of the above hydrocarbon groups may be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, 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, sultone rings, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl groups, etc. may be contained.

[0484] Again, R 31 and R 32 They may also be bonded to each other and to the sulfur atom to which they are bonded to form a ring, and R 33 and R 34 , R 36 and R 37 , or R 39 and R 40 They may also be bonded to each other and form a ring together with the sulfur atom to which they are bonded. The ring formed in this case can be exemplified as R in the description of formula (cation-1): ct1 and R ct2 The same example is true of the rings that can be formed by bonding to each other and to the sulfur atoms to which they are bonded.

[0485] Specific examples of the sulfonium cations of repeating units B8 to B10 include the same examples as those exemplified as the sulfonium cations represented by formula (cation-1). Specific examples of the iodonium cations of repeating units B12 to B14 include the same examples as those exemplified as the iodonium cations represented by formula (cation-2).

[0486] Repeating units B7 to B14 are units that generate acid due to irradiation with high-energy rays. It is believed that by including these units in the polymer, acid diffusion can be appropriately suppressed, and a pattern with reduced LER can be obtained. In addition, it is believed that by including these units in the polymer, the phenomenon that the acid evaporates from the exposed part and reattaches to the unexposed part during baking in a vacuum can be suppressed, and it is effective in reducing LER and reducing defects caused by suppressing undesirable negative-type reactions in the unexposed part.

[0487] The repeating units B7 to B14 may be used alone or in combination of two or more.

[0488] The polymers B and B' may contain a (meth)acrylate unit having a lactone structure or an adhesive group such as a hydroxyl group other than a phenolic hydroxyl group, or other repeating units in order to finely adjust the properties of the resist film.

[0489] Examples of the (meth)acrylate unit having an adhesion group include a repeating unit represented by the following formula (B15) (hereinafter also referred to as repeating unit B15), a repeating unit represented by the following formula (B16) (hereinafter also referred to as repeating unit B16), and a repeating unit represented by the following formula (B17) (hereinafter also referred to as repeating unit B17). These units do not exhibit acidity and can be used auxiliaryly as units for providing adhesion to a substrate or units for adjusting solubility.

[0490] [Chemistry 144]

[0491]

[0492] In formulas (B15) to (B17), R A R is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. 51 is -O- or methylene. 52 is a hydrogen atom or a hydroxyl group. 53 is a saturated hydrocarbon group having 1 to 4 carbon atoms. g is an integer of 0 to 3.

[0493] In polymer B, the content of repeating unit B1 is preferably 30 to 95 mol%, and more preferably 50 to 85 mol%, in order to produce a high contrast between the negative-type part and the non-irradiated part (the part not negative-typed) by high-energy ray irradiation for the purpose of obtaining high resolution. In addition, the content of repeating unit B2 and repeating unit B3 is preferably 5 to 70 mol%, and more preferably 10 to 60 mol%, in order to obtain the effect of promoting the negative-type reaction. The content of repeating units B4 to B6 is preferably 0 to 30 mol%, and more preferably 3 to 20 mol%, in order to obtain the effect of improving etching resistance. In addition, other repeating units may also be contained at 0 to 30 mol%, and it is preferable to contain 0 to 20 mol%.

[0494] When polymer B' does not contain repeating units B7 to B14, the content of repeating unit B1 in polymer B' is preferably 25 to 95 mol%, preferably 40 to 85 mol%. The content of repeating units B4 to B6 is preferably 0 to 30 mol%, preferably 3 to 20 mol%. The content of repeating units B2 and repeating units B3 is preferably 5 to 70 mol%, preferably 10 to 60 mol%. In addition, other repeating units may be contained in 0 to 30 mol%, preferably 0 to 20 mol%.

[0495] When polymer B' contains repeating units B7 to B14, the content of repeating unit B1 in polymer B' is preferably 25 to 94.5 mol%, preferably 36 to 85 mol%. The content of repeating units B4 to B6 is preferably 0 to 30 mol%, preferably 3 to 20 mol%. The content of repeating units B2 and B3 is preferably 5 to 70 mol%, preferably 10 to 60 mol%. In addition, the total content of repeating units B1 to B6 is preferably 60 to 99.5 mol%. The content of repeating units B7 to B14 is preferably 0.5 to 20 mol%, preferably 1 to 10 mol%. In addition, it may also contain other repeating units 0 to 30 mol%, preferably 0 to 20 mol%.

[0496] In addition, of 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, thereby reliably obtaining the necessary characteristics of the chemically amplified negative resist composition of the present invention.

[0497] In this case, the polymer B' preferably contains a repeating unit represented by the following formula (B1-1), 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).

[0498] [Chemistry 145]

[0499]

[0500] In the formula, a4, b4, b6, R A , R B , Y 2 , R 13 , R 14 , R 16 , R 17 , R 33 , R 34 , R 35 and R HF Same as above.

[0501] (B) Base polymer When polymer B' is used, a polymer not containing repeating units B7 to B14 and a polymer containing repeating units B7 to B14 may be used in combination. In this case, the content of the polymer not containing repeating units B7 to B14 in the chemically amplified negative resist composition of the present invention is preferably 2 to 5000 parts by mass, more preferably 10 to 1000 parts by mass, relative to 100 parts by mass of the polymer containing repeating units B7 to B14.

[0502] When the chemically amplified negative resist composition is used for mask production, the coating film thickness in the most advanced generation is 150 nm or less, preferably 100 nm or less. The dissolution rate of the base polymer constituting the aforementioned chemically amplified negative resist composition in an alkaline developer (e.g., a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution) is generally preferably 80 nm / sec or less, and more preferably 50 nm / sec or less in order to further reduce defects caused by resist residues, which is often a strong development treatment, and to form a fine pattern. In addition, for example, when LSI chips are made from wafers, when the chemically amplified negative resist composition of the present invention is used in EUV exposure processing, it is necessary to pattern fine lines of 50 nm or less, so the coating film thickness is often set to 100 nm or less. Since it is a thin film, it is believed that the pattern will be degraded due to development, so the dissolution rate of the polymer used is preferably 80 nm / sec or less, and more preferably 50 nm / sec or less.

[0503] The aforementioned polymer can be copolymerized by utilizing a known method to make each monomer protected by a protecting group as required, and then synthesized by deprotection reaction as required. The copolymerization reaction is not particularly limited, and is preferably free radical polymerization or anionic polymerization. For these methods, reference can be made to International Publication No. 2006 / 121096, Japanese Patent Publication No. 2008-102383, Japanese Patent Publication No. 2008-304590, and Japanese Patent Publication No. 2004-115630.

[0504] The weight average molecular weight (Mw) of the aforementioned polymer is preferably 1000 to 50000, more preferably 2000 to 20000. If Mw is 1000 or more, there is no concern that the top of the pattern becomes rounded, the resolution decreases, and the LER deteriorates as is known in the past. On the other hand, if Mw is 50000 or less, there is no concern that the LER increases, especially when forming a pattern with a line width of 100 nm or less. In addition, Mw in the present invention is a polystyrene-converted measurement value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or dimethylformamide (DMF) as a solvent.

[0505] The molecular weight distribution (Mw / Mn) of the polymer is preferably 1.0 to 2.0, preferably 1.0 to 1.8. When the distribution is narrow, foreign matter will not be generated on the pattern after development, and the pattern shape will not be deteriorated.

[0506] [(C) Cross-linking agent]

[0507] When the base polymer (B) does not contain the polymer B', the chemically amplified negative resist composition of the present invention preferably contains a crosslinking agent as the component (C). On the other hand, when the base polymer (B) contains the polymer B', it may or may not contain a crosslinking agent.

[0508] Specific examples of crosslinking agents that can be used in the present invention include epoxy compounds substituted with at least one group selected from hydroxymethyl, alkoxymethyl, and acyloxymethyl, melamine compounds, guanamine compounds, glycoluril compounds or urea compounds, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyloxy groups, etc. These can be used as additives or introduced as pendant groups in the side chains of polymers. In addition, hydroxyl-containing compounds can also be used as crosslinking agents.

[0509] Examples of the epoxy compound include tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether.

[0510] Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, or mixtures thereof, and hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or mixtures thereof.

[0511] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which 1 to 4 hydroxymethyl groups are methoxymethylated, such as tetramethylolguanamine, or mixtures thereof, and tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which 1 to 4 hydroxymethyl groups are acyloxymethylated, such as tetramethylolguanamine, or mixtures thereof.

[0512] Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof, and compounds in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are acyloxymethylated, or mixtures thereof.

[0513] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, compounds in which 1 to 4 methylol groups such as tetramethylol urea are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.

[0514] Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

[0515] Examples of the azide compound include 1,1′-biphenyl-4,4′-bisazide, 4,4′-methylenebisazide, and 4,4′-oxybisazide.

[0516] Examples of the alkenyloxy group-containing compound include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

[0517] In the chemically amplified negative resist composition of the present invention, the content of the crosslinking agent (C) is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass, relative to 80 parts by mass of the base polymer (B). If it is within the above range, the patterns will be connected and there is no concern about reduced resolution. The crosslinking agent (C) can be used alone or in combination of two or more.

[0518] [(D) Fluorine-containing polymer]

[0519] The chemically amplified negative resist composition of the present invention may contain a fluorine atom-containing polymer as component (D) in order to achieve high contrast, suppress chemical flare of acid during high-energy ray irradiation, shield acid from mixing from the antistatic film when the antistatic film material is applied to the resist film, and suppress unexpected and unwanted pattern degradation. The fluorine atom-containing polymer contains at least one selected from the group consisting of a repeating unit represented by the following formula (D1) (hereinafter also referred to as repeating unit D1), a repeating unit represented by the following formula (D2) (hereinafter also referred to as repeating unit D2), a repeating unit represented by the following formula (D3) (hereinafter also referred to as repeating unit D3), and a repeating unit represented by the following formula (D4) (hereinafter also referred to as repeating unit D4), and may further contain at least one selected from the group consisting of a repeating unit represented by the following formula (D5) (hereinafter also referred to as repeating unit D5) and a repeating unit represented by the following formula (D6) (hereinafter also referred to as repeating unit D6). The aforementioned fluorine-atom-containing polymer also has a surfactant function, so it can prevent insoluble matter that may be generated during the development process from re-attaching to the substrate, and thus also has an effect on development defects.

[0520] [Chemistry 146]

[0521]

[0522] In formulae (D1) to (D6), x is an integer of 1 to 3. y is an integer satisfying 0≤y≤5+2z-x. z is 0 or 1. g is an integer of 1 to 3. R C R is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. D are each independently a hydrogen atom or a methyl group. 101 , R102 , R 104 and R 105 R is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. 103 , R 106 , R 107 and R 108 are 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, and R 103 , R 106 , R 107 and R 108 When it is a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group may be inserted between the carbon-carbon bonds. 109 R is a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a heteroatom-containing group inserted between carbon-carbon bonds. 110 It is a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a heteroatom-containing group inserted between carbon-carbon bonds. 111 Z is a saturated hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom, and a portion of the -CH2- in the saturated hydrocarbon group may be substituted by an ester bond or an ether bond. 1 Z is a (g+1)-valent hydrocarbon group having 1 to 20 carbon atoms or a (g+1)-valent fluorinated hydrocarbon group having 1 to 20 carbon atoms. 2 is a single bond, *-C(=O)-O- or *-C(=O)-NH-. * is an atomic bond to a carbon atom of the main chain. Z 3 is a single bond, -O-, *-C(=O)-OZ 31 -Z 32 - or *-C(=O)-NH-Z 31 -Z 32 -.Z 31 Z is a single bond or a saturated alkylene group having 1 to 10 carbon atoms. 32 is a single bond, ester bond, ether bond or sulfonamide bond. * is an atomic bond to a carbon atom of the main chain.

[0523] In formula (D1) and (D2), R 101 , R 102 , R 104 and R 105 The saturated hydrocarbon group having 1 to 10 carbon atoms represented by may be any of straight chain, branched, or cyclic, and specific examples thereof include: alkyl groups having 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 having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornyl. Among them, saturated hydrocarbon groups having 1 to 6 carbon atoms are preferred.

[0524] In formulas (D1) to (D4), R 103 , R 106 , R 107 and R 108 The hydrocarbon group having 1 to 15 carbon atoms represented by the above may be any of straight chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 15 carbon atoms, alkenyl groups having 2 to 15 carbon atoms, alkynyl groups having 2 to 15 carbon atoms, and preferably alkyl groups having 1 to 15 carbon atoms. The above-mentioned alkyl groups include, in addition to the above-mentioned ones, 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, n-pentadecyl, and the like. In addition, the fluorinated hydrocarbon group includes groups in which a part or all of the hydrogen atoms bonded to the carbon atoms of the above-mentioned hydrocarbon groups are substituted with fluorine atoms.

[0525] In formula (D4), Z 1 The (g+1)-valent hydrocarbon group having 1 to 20 carbon atoms represented by may be a group obtained by removing g hydrogen atoms from an alkyl group having 1 to 20 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. 1 Examples of the (g+1)-valent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by include groups in which at least one hydrogen atom in the aforementioned (g+1)-valent hydrocarbon group is substituted with a fluorine atom.

[0526] Specific examples of repeating units D1 to D4 include the following, but are not limited thereto. C Same as above.

[0527] [Chemistry 147]

[0528]

[0529] [Chemistry 148]

[0530]

[0531] [Chemistry 149]

[0532]

[0533] In formula (D5), R 109 and R 110 Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by alkyl, alkenyl, alkynyl, etc. are listed, and alkyl is preferred. Examples of the aforementioned alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, etc. In addition, a group containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom may be inserted between the carbon-carbon bonds of the aforementioned hydrocarbon group.

[0534] In formula (D5), -OR 109Preferably, it is a hydrophilic group. 109 Preferred are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms in which an oxygen atom is inserted between carbon-carbon bonds, and the like.

[0535] In formula (D5), Z 2 It is preferably *-C(=O)-O- or *-C(=O)-NH-. D Preferably it is methyl. 2 The presence of a carbonyl group in the antistatic film improves the capture ability of the acid from the antistatic film. D If it is a methyl group, it will become a hard polymer with a higher glass transition temperature (Tg), so the diffusion of acid will be suppressed. As a result, the stability of the resist film over time will be good, and the resolution and pattern shape will not deteriorate.

[0536] The repeating unit D5 may be exemplified by the following, but is not limited thereto. D Same as above.

[0537] [Chemistry 150]

[0538]

[0539] [Chemistry 151]

[0540]

[0541] In formula (D6), Z 3 The saturated alkylene group having 1 to 10 carbon atoms represented by the alkylene group may be straight-chain, branched or cyclic, and specific examples thereof include methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, 1,1-dimethylethane-1,2-diyl and the like.

[0542] In formula (D6), R 111 The saturated hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom may be straight-chain, branched or cyclic. Specific examples thereof include an alkyl group having 1 to 20 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom.

[0543] The repeating unit D6 may be exemplified by the following, but is not limited thereto. D Same as above.

[0544] [Chemistry 152]

[0545]

[0546] [Chemistry 153]

[0547]

[0548] [Chemistry 154]

[0549]

[0550] [Chemistry 155]

[0551]

[0552] The content of repeating units D1 to D4 is preferably 15 to 95 mol %, more preferably 20 to 85 mol %, of all repeating units of the aforementioned fluorine-containing polymer. The content of repeating units D5 and / or D6 is preferably 5 to 85 mol %, more preferably 15 to 80 mol % of all repeating units of the aforementioned fluorine-containing polymer. Repeating units D1 to D6 may be used alone or in combination of two or more.

[0553] The aforementioned fluorine-containing polymer may also contain other repeating units other than the aforementioned repeating units. Such repeating units may include those described in paragraphs

[0046] to

[0078] of Japanese Patent Publication No. 2014-177407. When the aforementioned fluorine-containing polymer contains other repeating units, the content thereof is preferably 50 mol% or less in all the repeating units of the aforementioned fluorine-containing polymer.

[0554] The fluorine-containing polymer can be synthesized by copolymerizing monomers protected by protective groups as required by known methods, and then performing deprotection reactions as required. The copolymerization reaction is not particularly limited, and is preferably free radical polymerization or anionic polymerization. For these methods, reference can be made to Japanese Patent Publication No. 2004-115630.

[0555] The Mw of the fluorine-containing polymer is preferably 2000 to 50000, and more preferably 3000 to 20000. If the Mw is less than 2000, the diffusion of the acid may be promoted, the resolution may be degraded, and the stability over time may be impaired. If the Mw is too large, the solubility in the solvent may be reduced, and coating defects may occur. In addition, the Mw / Mn of the fluorine-containing polymer is preferably 1.0 to 2.2, and more preferably 1.0 to 1.7.

[0556] When the chemically amplified negative resist composition of the present invention contains a fluorine-containing polymer (D), its content is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass relative to 80 parts by mass of the base polymer (B). The fluorine-containing polymer (D) may be used alone or in combination of two or more.

[0557] [(E) Quencher]

[0558] The chemically amplified negative resist composition of the present invention preferably contains a quencher as component (E). In the present invention, the quencher refers to a material that traps the acid generated by the photoacid generator in the chemically amplified resist composition to prevent it from diffusing to the unexposed area and is used to form a desired pattern.

[0559] The quencher may be a known basic compound. The known basic compound may be a primary, secondary, or tertiary aliphatic amine, a mixed amine, an aromatic amine, a heterocyclic amine, a nitrogen-containing compound having a carboxyl group, a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide, an imide, a carbamate, etc. In particular, the primary, secondary, or tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Laid-Open No. 2008-111103 are preferred, and the amine compounds having a hydroxyl group, an ether bond, an ester bond, a lactone ring, a cyano group, a sulfonate bond, or the compounds having a carbamate group described in Japanese Patent No. 3790649 are particularly preferred. Desirable examples include tris[2-(methoxymethoxy)ethyl]amine, tris[2-(methoxymethoxy)ethyl]amine-N-oxide, dibutylaminobenzoic acid, morpholine derivatives, imidazole derivatives, etc. By adding such a basic compound, for example, the diffusion rate of the acid in the resist film can be further suppressed or the shape can be corrected.

[0560] In addition, the quencher may be an onium salt such as a sulfonium salt, an iodonium salt, or an ammonium salt of a carboxylic acid whose α-position is not fluorinated as described in Japanese Patent Application Laid-Open No. 2008-158339. A sulfonic acid, an imidic acid, or a methylated acid whose α-position is fluorinated is necessary to deprotect an acid-labile group, and a carboxylic acid whose α-position is not fluorinated is released by salt exchange with an onium salt whose α-position is not fluorinated. A carboxylic acid whose α-position is not fluorinated hardly causes a deprotection reaction, and thus functions as a quencher.

[0561] Examples of the onium salt of carboxylic acid in which the α-position is not fluorinated include those represented by the following formula (E1).

[0562] [Chemistry 156]

[0563] R201-cOMqA 十 (E1)

[0564] In formula (E1), R 201 It is a hydrocarbon group having 1 to 40 carbon atoms which may contain a hydrogen atom or a hetero atom, but excludes those in which the hydrogen atom bonded to the carbon atom at the α-position of the carboxyl group is substituted by a fluorine atom or a fluoroalkyl group.

[0565] R 201The hydrocarbon group represented by may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include: alkyl groups having 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, norbornyl, tricyclo[5.2.1.0 2,6 ] Cyclic saturated hydrocarbon groups having 3 to 40 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; alkenyl groups having 2 to 40 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated aliphatic hydrocarbon groups having 3 to 40 carbon atoms, such as cyclohexenyl; aryl groups having 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.), dialkylnaphthyl (dimethylnaphthyl, diethylnaphthyl, etc.); aralkyl groups having 7 to 40 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl, etc.

[0566] Furthermore, part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted by a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of the -CH2- of the aforementioned hydrocarbon group may be substituted by a group containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, it may contain hydroxyl groups, cyano groups, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sultone rings, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl groups, and the like. Examples of the heteroatom-containing hydrocarbon group include heteroaryl groups such as thienyl; 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; aryl pendant oxyalkyl groups such as 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, and 2-(2-naphthyl)-2-oxoethyl; and the like.

[0567] In formula (E1), Mq A +It is an onium cation. The onium cation is preferably a sulfonium cation, an iodonium cation or an ammonium cation, and is more preferably a sulfonium cation or an iodonium cation. Specific examples of the sulfonium cation include the same examples as those exemplified as the sulfonium cation represented by formula (cation-1). Specific examples of the iodonium cation include the same examples as those exemplified as the iodonium cation represented by formula (cation-2).

[0568] Examples of the anion of the onium salt represented by the formula (E1) include the following, but are not limited thereto.

[0569] [Chemistry 157]

[0570]

[0571] [Chemistry 158]

[0572]

[0573] [Chemistry 159]

[0574]

[0575] As the quencher, a sulfonium salt of a carboxylic acid containing an iodinated benzene ring represented by the following formula (E2) can also be preferably used.

[0576] [Chemistry 160]

[0577]

[0578] In formula (E2), s is an integer of 1 to 5. t is an integer of 0 to 3. However, 1≤s+t≤5. u is an integer of 1 to 3.

[0579] In formula (E2), R 211 is a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an amino group, a nitro group, a cyano group, a saturated hydrocarbon group having 1 to 6 carbon atoms, a saturated hydrocarbon oxy group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyloxy group having 2 to 6 carbon atoms, a saturated hydrocarbon sulfonyloxy group having 1 to 4 carbon atoms, -N(R 211A )-C(=O)-R 211B or -N(R 211A )-C(=O)-OR 211B , and part or all of the hydrogen atoms of the saturated hydrocarbon group, saturated hydrocarbon oxy group, saturated hydrocarbon carbonyl oxy group or saturated hydrocarbon sulfonyl oxy group may be substituted by halogen atoms. 211A is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. 211B is a saturated hydrocarbon group having 1 to 6 carbon atoms or an unsaturated aliphatic hydrocarbon group having 2 to 8 carbon atoms. When t and / or u is 2 or more, each R 211 They can be the same or different.

[0580] In formula (E2), L1 It is a single bond or a (u+1)-valent linking group having 1 to 20 carbon atoms, and may contain at least one selected from an ether bond, a carbonyl group, an ester bond, an amide bond, a sultone ring, a lactam ring, a carbonate bond, a halogen atom, a hydroxyl group, and a carboxyl group. The saturated hydrocarbon group, saturated hydrocarbon oxy group, saturated hydrocarbon carbonyl oxy group, and saturated hydrocarbon sulfonyl oxy group may be straight-chain, branched, or cyclic.

[0581] In formula (E2), R 212 , R 213 and R 214 Each independently represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be any of linear, branched, and cyclic. Specific examples thereof include: alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and the like. Furthermore, a part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted by a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, a nitro group, a sultone ring, a sulfonium group, or a group containing a sulfonium salt, and a part of the -CH2- of the aforementioned hydrocarbon group may be substituted by an ether bond, an ester bond, a carbonyl group, an amide bond, a carbonate bond, or a sulfonate bond. Furthermore, R 212 and R 213 They may also bond to each other and to the sulfur atom to which they are bonded to form a ring.

[0582] Specific examples of the compound represented by formula (E2) include those described in Japanese Patent Application Laid-Open No. 2017-219836. The compound represented by formula (E2) has a high sensitization effect due to high absorption and also has a high acid diffusion control effect.

[0583] As the quencher, a nitrogen atom-containing carboxylate type compound represented by the following formula (E3) can also be used.

[0584] [Chemistry 161]

[0585]

[0586] In formula (E3), R 221 ~R 224 are independently a hydrogen atom, -L 2 -CO2 - , or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. 221 With R 222 , R 222 With R 223 , or R 223 With R 224 They may also bond to each other and to the carbon atoms to which they are bonded to form a ring. 2 R is a single bond or a alkylene group having 1 to 20 carbon atoms which may contain a hetero atom. 225It is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom or a hetero atom.

[0587] In formula (E3), ring R r is a ring having 2 to 6 carbon atoms including the carbon atoms and nitrogen atoms in the formula, and part or all of the hydrogen atoms bonded to the carbon atoms in the ring may be replaced by a hydrocarbon group having 1 to 20 carbon atoms, or -L 2 -CO2 - The ring may be substituted with a -CH2- radical, and a part of the -CH2- radical of the ring may be substituted with a sulfur atom, an oxygen atom or a nitrogen atom. The aforementioned ring may be an alicyclic ring or an aromatic ring, and preferably a 5-membered ring or a 6-membered ring. Specific examples thereof include: a pyridine ring, a pyrrole ring, a pyrrolidine ring, a piperidine ring, a pyrazole ring, an imidazoline ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, an imidazoline ring, an oxazole ring, a thiazole ring, a morpholine ring, a thiazine ring, a triazole ring, and the like.

[0588] The carboxylic acid onium salt represented by formula (E3) has at least one -L 2 -CO2 - That is, R 221 ~R 224 At least one of them is -L 2 -CO2 - , and / or ring R r At least one of the hydrogen atoms of a carbon atom is replaced by -L 2 -CO2 - Replacer.

[0589] In formula (E3), Mq B + It is a sulfonium cation, an iodonium cation or an ammonium cation, preferably a sulfonium cation. Specific examples of the sulfonium cation include the same examples as those exemplified as the sulfonium cation represented by the formula (cation-1).

[0590] Examples of the anion of the compound represented by formula (E3) include the following, but are not limited thereto.

[0591] [Chemistry 162]

[0592]

[0593] [Chemistry 163]

[0594]

[0595] [Chemistry 164]

[0596]

[0597] [Chemistry 165]

[0598]

[0599] [Chemistry 166]

[0600]

[0601] [Chemistry 167]

[0602]

[0603] Furthermore, a weakly acidic betaine-type compound may be used as the quencher. Specific examples thereof include those shown below, but are not limited thereto.

[0604] [Chemistry 168]

[0605]

[0606] The aforementioned quencher may further include a polymer quencher described in Japanese Patent Application Publication No. 2008-239918. The quencher improves the rectangularity of the resist pattern by being oriented on the surface of the resist film. The polymer quencher also has the effect of preventing film loss and doming of the pattern when a protective film for immersion exposure is used.

[0607] When the chemically amplified negative resist composition of the present invention contains (E) a quencher, its content is preferably 0 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, relative to 80 parts by mass of the base polymer (B). The (E) quencher may be used alone or in combination of two or more.

[0608] When the chemically amplified negative resist composition of the present invention contains a photoacid generator as component (A) and a quencher as component (E), the content ratio of the photoacid generator to the quencher ((A) / (E)) is preferably less than 6, more preferably less than 5, and even more preferably less than 4 in terms of mass ratio. When the content ratio of the photoacid generator to the quencher contained in the chemically amplified negative resist composition is within the above range, acid diffusion can be sufficiently suppressed, and excellent resolution and dimensional uniformity can be obtained.

[0609] [(F) Organic solvent]

[0610] The chemically amplified negative resist composition of the present invention may also contain an organic solvent as the (F) component. The aforementioned organic solvent is not particularly limited as long as it can dissolve each component. Such organic solvents include, for example, ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone described in paragraphs

[0144] to

[0145] of Japanese Patent Gazette No. 2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether (PGME), and ethylene glycol monomethyl ether (PGME). 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; mixed solvents thereof, etc.

[0611] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, PGME, cyclohexanone, EL, γ-butyrolactone, and a mixed solvent thereof are preferred.

[0612] When the chemically amplified negative resist composition of the present invention contains (F) an organic solvent, its content is preferably 200 to 10,000 parts by mass, more preferably 400 to 6,000 parts by mass, relative to 80 parts by mass of the base polymer (B). The organic solvent (F) may be used alone or in combination of two or more.

[0613] [(G) Surfactant]

[0614] The chemically amplified negative resist composition of the present invention may also contain a conventional surfactant in order to improve the coating properties on the substrate. Examples of the aforementioned surfactant include PF-636 (manufactured by OMNOVA SOLUTIONS), FC-4430 (manufactured by 3M Company), and many examples are also recorded in Japanese Patent Gazette No. 2004-115630. There are many known surfactants, which can be selected as references. When the chemically amplified negative resist composition of the present invention contains a (G) surfactant, its content is preferably 0 to 5 parts by mass relative to 80 parts by mass of the (B) base polymer. The (G) surfactant may be used alone or in combination of two or more.

[0615] [Resist pattern forming method]

[0616] The resist pattern forming method of the present invention comprises 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 that has been irradiated with the aforementioned pattern using an alkaline developer.

[0617] The aforementioned substrate may be, for example, a substrate for integrated circuit manufacturing (Si, SiO, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflection film, etc.), or a substrate for transmissive or reflective mask circuit manufacturing (Cr, CrO, CrON, MoSi2, Si, SiO, SiO2, SiON, SiONC, CoTa, NiTa, TaBN, SnO2, etc.). On the aforementioned substrate, the aforementioned chemically amplified negative resist composition is applied by a spin coating method to a film thickness of 0.03 to 2 μm, and the composition is pre-baked on a hot plate preferably at 60 to 150° C. for 1 to 20 minutes, and more preferably at 80 to 140° C. for 1 to 10 minutes, to form a resist film.

[0618] Then, the resist film is exposed to a pattern using high-energy radiation. Examples of the high-energy radiation include ultraviolet radiation, extreme ultraviolet radiation, excimer laser (KrF, ArF, etc.), EUV, X-rays, gamma rays, synchrotron radiation, EB, etc. In the present invention, EUV or EB is preferably used for exposure.

[0619] When ultraviolet rays, extreme ultraviolet rays, excimer lasers, EUV, X-rays, gamma rays or synchrotron radiation are used as the high energy rays, a mask for forming a target pattern is used and the exposure dose is preferably 1 to 500 mJ / cm 2 More preferably, it is 10 to 400 mJ / cm 2 When EB is used, the exposure dose is preferably 1 to 500 μC / cm 2 More preferably, it is 10 to 400 μC / cm 2 way of irradiation.

[0620] Exposure can be performed by a normal exposure method or, depending on the situation, by a wetting method in which the mask and the resist film are wetted. In this case, a water-insoluble protective film can also be used.

[0621] Then, a post-exposure bake (PEB) is performed on a hot plate at preferably 60-150° C. for 1-20 minutes, and more preferably 80-140° C. for 1-10 minutes.

[0622] Thereafter, by using a developer of an alkaline aqueous solution of TMAH or the like at 0.1 to 5% by mass, preferably 2 to 3% by mass, development is performed by common methods such as dipping, puddle, spraying, etc., preferably for 0.1 to 3 minutes, more preferably 0.5 to 2 minutes, to form a target pattern on the substrate.

[0623] In addition, the chemically amplified negative resist composition of the present invention is particularly useful because it can form patterns with good resolution and low LER. In addition, since it is not easy to obtain the adhesion of the resist pattern, the chemically amplified negative resist composition of the present invention is particularly useful for pattern formation on substrates having materials on the surface that easily cause pattern peeling and pattern collapse. Such substrates include: substrates having a sputtered film of metallic chromium or a chromium compound containing one or more light elements selected from oxygen, nitrogen and carbon on the outermost surface; substrates containing SiO, SiOx, tantalum compounds, molybdenum compounds, cobalt compounds, nickel compounds, tungsten compounds, tin compounds, etc. on the outermost layer. The chemically amplified negative resist composition of the present invention is particularly useful for pattern formation using a blank photomask as a substrate. At this time, the blank photomask can be a transmissive type or a reflective type.

[0624] In the case of a transmission type blank mask, a blank mask having a light shielding film made of a chromium-based material may be a blank mask for a binary mask or a blank mask for a phase shift mask. In the case of a blank mask for a binary mask, the blank mask may have an anti-reflection layer and a light shielding layer made of a chromium-based material as the light shielding film, or the anti-reflection film on the surface side may be entirely made of a chromium-based material, or only the surface side of the anti-reflection film on the surface side may be made of a chromium-based material, and the remaining portion may be made of, for example, a silicon-based compound material that may also contain a transition metal. In the case of a blank mask for a phase shift mask, a blank mask for a phase shift mask having a chromium-based light shielding film on the phase shift film may be used as an object.

[0625] The aforementioned blank photomask having a chromium-based material as the outermost layer is already well known as the current technology as exemplified in Japanese Patent Publication No. 2008-26500, Japanese Patent Publication No. 2007-302873 or therein, and a detailed description thereof is omitted. For example, when a shading film having an anti-reflection layer and a shading layer is formed using a chromium-based material, a film structure as described below can be used.

[0626] When a light-shielding film having an anti-reflection layer and a light-shielding layer is formed using a chromium-based material, the layer structure may be a layer structure in which an anti-reflection layer and a light-shielding layer are stacked in order from the surface layer side, or an anti-reflection layer, a light-shielding layer, and an anti-reflection layer are stacked in order. In addition, the anti-reflection layer and the light-shielding layer may be a plurality of layers, and the layers with different compositions may have a discontinuous change in composition or a continuous change in composition. The chromium-based material used may be metal chromium and a material containing light elements such as oxygen, nitrogen, and carbon in metal chromium. Specifically, metal chromium, chromium oxide, chromium nitride, chromium carbide, chromium nitride oxide, chromium carbide oxide, chromium carbide nitride, chromium carbide oxide, chromium carbide nitride, chromium carbide oxide, and chromium carbide nitride.

[0627] Furthermore, the reflective blank mask includes: a substrate, and a multilayer reflective film formed on one main surface (surface on the outer surface side) of the substrate, specifically, a multilayer reflective film that reflects exposure light such as EUV light, and an absorber film formed on the multilayer reflective film, specifically, an absorber film that absorbs exposure light such as EUV light and reduces reflectivity. A reflective mask (reflective mask for EUV) having an absorber pattern (absorber film pattern) formed by patterning the absorber film is manufactured from the reflective blank mask (reflective blank mask for EUV). The wavelength of EUV light used for EUV lithography is 13 to 14 nm, usually light with a wavelength of about 13.5 nm.

[0628] The multilayer reflective film is usually preferably provided in contact with one of the main surfaces of the substrate, but a base film may be provided between the substrate and the multilayer reflective film as long as the effect of the present invention is not impaired. The absorber film may be formed in contact with the multilayer reflective film, or a protective film (a protective film of the multilayer reflective film) may be provided between the multilayer reflective film and the absorber film and preferably in contact with the multilayer reflective film, and more preferably a protective film (a protective film of the multilayer reflective film) is provided in contact with the multilayer reflective film and the absorber film. The protective film can be used to protect the multilayer reflective film during processing such as cleaning and correction. In addition, the protective film preferably has the function of protecting the multilayer reflective film and preventing oxidation of the multilayer reflective film when the absorber film is patterned by etching. On the other hand, a conductive film used for electrostatically clamping the reflective mask in the exposure device may also be provided under the other main surface (the surface on the inner surface side) which is the opposite side of one of the main surfaces of the substrate and preferably in contact with the other main surface. In addition, here, one of the main surfaces of the substrate is defined as the surface on the outer surface side and the upper side, and the other main surface is defined as the surface on the inner surface side and the lower side, but the outer surface and the inner surface and the upper and lower sides of the two are defined for the convenience of explanation, and the one main surface and the other main surface can be any of the two main surfaces (film forming surfaces) in the substrate, and the outer surface and the inner surface and the upper and lower sides can be replaced with each other. More specifically, it can be formed using Japanese Patent Publication No. 2021-139970 or a method as exemplified in the current technology.

[0629] According to the resist pattern forming method of the present invention, even when using a substrate (such as a transmission or reflection type blank mask) whose outermost surface is made of a material that is easily affected by the shape of the resist pattern, such as a material containing chromium, silicon or tantalum, a pattern with extremely high resolution, small LER, excellent rectangularity and excellent pattern fidelity can still be obtained.

[0630] [Example]

[0631] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0632] The structures of polymers P-1 to P-30 used in the resist composition are shown in the following Table 1. Mw is a polystyrene-equivalent measurement value measured by GPC using THF or DMF as a solvent.

[0633] [Table 1]

[0634]

[0635]

[0636] In Table 1, the structure of each unit is as follows.

[0637] [Chemistry 169]

[0638]

[0639] [Chemistry 170]

[0640]

[0641] [Chemistry 171]

[0642]

[0643] [Chemistry 172]

[0644]

[0645] [Chemistry 173]

[0646]

[0647] [1] Preparation of chemically amplified negative resist composition

[0648] [Examples 1-1 to 1-54, Comparative Examples 1-1 to 1-10]

[0649] The components are dissolved in an organic solvent with the composition shown in Tables 2 to 4 below, and the obtained solutions are filtered through a UPE filter and / or a nylon filter selected from 10 nm, 5 nm, 3 nm and 1 nm in size, thereby obtaining a chemically amplified negative resist composition (R-1 to R-54, CR-1 to CR-10). In addition, the aforementioned organic solvent is a mixed solvent of 790 parts by mass of PGMEA, 1580 parts by mass of EL and 1580 parts by mass of PGME. In addition, in a part of the composition, a fluorine-containing polymer (polymer FP-1 to FP-5) as an additive, tetramethoxymethyl glycoluril (TMGU) as a cross-linking agent, and PF-636 (manufactured by OMNOVA SOLUTIONS) as a surfactant are added.

[0650] [Table 2]

[0651]

[0652]

[0653] [Table 3]

[0654]

[0655]

[0656] [Table 4]

[0657]

[0658] In Tables 2 to 4, the photoacid generators PAG-1 to PAG-9, the comparative photoacid generators cPAG-1 to cPAG-4, the quenchers Q-1 to Q-4, and the fluorine-containing polymers FP-1 to FP-5 are as follows.

[0659] [Chemistry 174]

[0660]

[0661] [Chemistry 175]

[0662]

[0663] [Chemistry 176]

[0664]

[0665] [Chemistry 177]

[0666]

[0667] [Chemistry 178]

[0668]

[0669] [2]EB Lithography Evaluation

[0670] [Examples 2-1 to 2-54, Comparative Examples 2-1 to 2-10]

[0671] Each chemically amplified negative resist composition (R-1 to R-54, CR-1 to CR-10) was spin-coated on a 152 mm square blank mask with a silicon oxide film on the outermost surface after hexamethyldisilazane (HMDS) vapor prime treatment using ACT-M (Tokyo Electron Co., Ltd.), and pre-baked on a hot plate at 110°C for 600 seconds to obtain a resist film with a thickness of 80 nm. The film thickness of the obtained resist film was measured using an optical measuring instrument NANOSPEC (Nanometrics). The measurement was performed at 81 locations within the surface of the blank substrate excluding the outer edge portion from the periphery of the blank substrate to the inner 10 mm, and the average film thickness and the film thickness range were calculated.

[0672] Exposure was performed using an electron beam exposure apparatus (EBM-5000plus manufactured by NuFlare Technology Co., Ltd., accelerating voltage 50 kV), PEB was applied at 120° C. for 600 seconds, and development was performed with a 2.38 mass % TMAH aqueous solution to obtain a negative pattern.

[0673] The obtained resist pattern was evaluated as follows. The obtained blank mask with pattern was observed using an overhead SEM (scanning electron microscope), and the exposure amount at which a 1:1 line and space (LS) of 200 nm was resolved at 1:1 was defined as the optimum exposure amount (μC / cm 2 ), and the minimum size in the exposure amount at which 200nm LS can be resolved at 1:1 is defined as the resolution (limiting resolution). For the 200nm LS pattern obtained by irradiation with the optimal exposure amount, 80-point edge detection is performed on the 32 edges of the 200nm LS pattern using SEM, and the 3 times value (3σ) of its deviation (standard deviation, σ) is calculated and defined as LER (nm). The pattern shape is visually determined to be rectangular. In addition, for the evaluation of pattern fidelity (Fidelity), the area loss (Area loss) value (%) of one corner of the dot pattern is calculated when a square dot pattern with a density of 36% and a size of 120nm is configured. The smaller the value, the better the rectangularity of the dot shape. The results are shown in Tables 5 to 7.

[0674] [Table 5]

[0675]

[0676]

[0677] [Table 6]

[0678]

[0679] [Table 7]

[0680]

[0681] 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 comparative resist compositions (CR-1 to CR-10) have insufficiently designed acid generators and have insufficient performance in terms of resolution, LER and pattern rectangularity.

[0682] The resist pattern forming method using the chemically amplified negative resist composition of the present invention is useful in the manufacture of semiconductor devices, especially in optical lithography in the processing of transmission type or reflection type blank photomasks.

Claims

1. A chemically amplified negative resist composition comprising: (A) a photoacid generator composed 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 (B1); wherein n1 and n2 are independently integers of 0 to 2; n3 is an integer of 1 to 4 when n2=0, an integer of 1 to 6 when n2=1, and an integer of 1 to 8 when n2=2; n4 is an integer of 0 to 3 when n2=0, an integer of 0 to 5 when n2=1, and an integer of 0 to 7 when n2=2; however, n3+n4 is 1 to 4 when n2=0, 1 to 6 when n2=1, and 1 to 8 when n2=2; n5 is an integer of 1 to 5 when n1=0, an integer of 1 to 7 when n1=1, and an integer of 1 to 9 when n1=2; R 1 is an iodine atom or a branched or cyclic hydrocarbon group having 3 to 20 carbon atoms which may contain a hetero atom, and at least one R 1 Bonded to L A The carbon atom adjacent to the carbon atom to which the bond is made; and, when n5 is 2 or more, multiple R 1 They can also bond to each other and to the carbon atoms to which they are bonded to form rings; R 2 is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, and when n4 is 2 or more, a plurality of R 2 They can also bond to each other and to the carbon atoms to which they are bonded to form rings; R F1 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 thioalkoxy group having 1 to 6 carbon atoms; L A and L B are independently a single bond, an ether bond, an ester bond, an amide bond, a sulfonate bond, a carbonate bond or a carbamate bond; X L is a single bond or an alkylene group having 1 to 40 carbon atoms which may contain heteroatoms; Z + is an onium cation; Wherein, a1 is 0 or 1; a2 is 0, 1 or 2; a3 is an integer satisfying 0≤a3≤5+2(a2)-a4; a4 is 1, 2 or 3; R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 11 is a halogen atom, a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon oxy group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom; A 1 It is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of the -CH2- of the saturated alkylene group may be substituted by -O-.

2. The chemically amplified negative resist composition according to claim 1, wherein: The onium salt is represented by the following formula (A1); In the formula, n3~n5, R 1 , R 2 , R F1 , L A , L B , X L and Z + Same as above.

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

4. The chemically amplified negative resist composition according to claim 1, wherein: Z + It is a sulfonium cation represented by the following formula (cation-1) or an iodonium cation represented by the following formula (cation-2); In the formula, R ct1 ~R ct5 are independently a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom; and R ct1 and R ct2 They may also bond to each other and to the sulfur atom to which they are bonded to form a ring.

5. The chemically amplified negative resist composition according to claim 1, wherein: The polymer further contains at least one selected from the group consisting of a repeating unit represented by the following formula (B2) and a repeating unit represented by the following formula (B3); Wherein, b1 is 0 or 1; b2 is 0, 1 or 2; b3 is an integer satisfying 0≤b3≤5+2(b2)-b4; b4 is 1, 2 or 3; b5 is 0, 1 or 2; b6 is 1 or 2; R A are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 12 is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom; R 13 and R 14 are independently a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may be substituted by a hydroxyl group or a saturated hydrocarbon group oxy group having 1 to 6 carbon atoms, and the aryl group may also have a substituent; however, R 13 and R 14 cannot be a hydrogen atom at the same time; and R 13 and R 14 They may also be bonded to each other and to the carbon atoms to which they are bonded to form a ring, and a portion of the -CH2- in the ring may be substituted by -O- or -S-; R 15 is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom; R 16 and R 17 are independently a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the hydrocarbon group may be substituted by a hydroxyl group or a saturated hydrocarbon group oxy group having 1 to 6 carbon atoms, and the aryl group may also have a substituent; however, R 16 and R 17 cannot be a hydrogen atom at the same time; and R 16 and R 17 They may also be bonded to each other and to the carbon atoms to which they are bonded to form a ring, and a portion of the -CH2- in the ring may be substituted by -O- or -S-; A 2 It is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a portion of -CH2- in the saturated alkylene group may be substituted by -O-; W 1 and W 2 Each of them 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, and the aryl group may have a substituent.

6. The chemically amplified negative resist composition according to claim 1, wherein: The polymer further contains at least one selected from the group consisting of 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 an integer of 0 to 4; e1 is 0 or 1; e2 is 0, 1 or 2; e3 is an integer of 0 to 5; R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 21 and R 22 Each of them is independently a hydroxyl group, a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon oxy group having 1 to 8 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom; R 23 is a saturated hydrocarbon group having 1 to 20 carbon atoms, a saturated hydrocarbon oxy group having 1 to 20 carbon atoms, a saturated hydrocarbon carbonyloxy group having 2 to 20 carbon atoms, a saturated hydrocarbon oxyhydrocarbyl group having 2 to 20 carbon atoms, a saturated hydrocarbon thiohydrocarbyl group having 2 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, a saturated hydrocarbon sulfinyl group having 1 to 20 carbon atoms, or a saturated hydrocarbon sulfonyl group having 1 to 20 carbon atoms; A 3 It is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of the -CH2- of the saturated alkylene group may be substituted by -O-.

7. The chemically amplified negative resist composition according to claim 5, wherein: The polymer further contains at least one selected from the group consisting of 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 (B10), a repeating unit represented by the following formula (B11), a repeating unit represented by the following formula (B12), a repeating unit represented by the following formula (B13), and a repeating unit represented by the following formula (B14); In the formula, R B are each independently a hydrogen atom or a methyl group; Y 1 Each of them is independently a single bond, an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining them, or *-OY 11 -, *-C(=O)-OY 11 - or *-C(=O)-NH-Y 11 -, and Y 11 It is an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining them, and may also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group; Y 2 are independently a single bond or **-Y 21 -C(=O)-O-, and Y 21 It is a hydrocarbon group having 1 to 20 carbon atoms which may also contain heteroatoms; Y 3 are independently a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, *-OY 31 -, *-C(=O)-OY 31 - or *-C(=O)-NH-Y 31 -;Y 31 An aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, or a group having 7 to 20 carbon atoms obtained by combining these groups, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group; * is the atomic bond to the carbon atom of the main chain, ** is the atomic bond to the oxygen atom in the formula; Y 4 Each is independently a single bond or an alkylene group having 1 to 30 carbon atoms which may contain a heteroatom; f1 and f2 are independently 0 or 1, but Y 4 When it is a single bond, f1 and f2 are 0; R 31 ~R 48 are independently a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom; and R 31 and R 32 They may also be bonded to each other and to the sulfur atom to which they are bonded to form a ring, and R 33 and R 34 , R 36 and R 37 , or R 39 and R 40 They can also bond to each other and to the sulfur atoms to which they are bonded to form a ring; R HF is a hydrogen atom or a trifluoromethyl group; XA - It is a non-nucleophilic relative ion.

8. The chemically amplified negative resist composition according to claim 7, wherein: The polymer contains a repeating unit represented by the following formula (B1-1), 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); In the formula, a4, b4, b6, R A , R B , Y 2 , R 13 , R 14 , R 16 , R 17 , R 33 , R 34 , R 35 and R HF Same as above.

9. The chemically amplified negative resist composition according to claim 7, wherein: The (B) base polymer further includes a polymer containing a repeating unit represented by the formula (B1) and a repeating unit represented by the formula (B2) or (B3), and not containing a repeating unit represented by the formulas (B7) to (B14).

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

11. The chemically amplified negative resist composition according to claim 1, further comprising (C) a cross-linking agent.

12. The chemically amplified negative resist composition according to claim 5, which does not contain a cross-linking agent.

13. The chemically amplified negative resist composition according to claim 1, further comprising (D) a fluorine-containing polymer comprising at least one selected from the group consisting of a repeating unit represented by the following formula (D1), 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 further comprising 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, x is an integer from 1 to 3; y is an integer satisfying 0≤y≤5+2z-x; z is 0 or 1; g is an integer from 1 to 3; R C are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R D are each 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 are 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, and R 103 , R 106 , R 107 and R 108 When it is a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group may be inserted between the carbon-carbon bonds; R 109 A hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms which may have a heteroatom-containing group inserted between carbon-carbon bonds; R 110 It is a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a heteroatom-containing group inserted between carbon-carbon bonds; R 111 A saturated hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and a portion of -CH2- in the saturated hydrocarbon group may be replaced by an ester bond or an ether bond; Z 1 A (g+1)-valent hydrocarbon group having 1 to 20 carbon atoms or a (g+1)-valent fluorinated hydrocarbon group having 1 to 20 carbon atoms; Z 2 is a single bond, *-C(=O)-O- or *-C(=O)-NH-; * is an atomic bond to a carbon atom of the main chain; Z 3 is a single bond, -O-, *-C(=O)-OZ 31 -Z 32 - or *-C(=O)-NH-Z 31 -Z 32 -;Z 31 is a single bond or a saturated alkylene group having 1 to 10 carbon atoms; Z 32 is a single bond, an ester bond, an ether bond or a sulfonamide bond; * is the atomic bond to the carbon atom of the main chain.

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

15. The chemically amplified negative resist composition according to claim 14, wherein: The content ratio of the (A) acid generator to the (E) quencher is less than 6 in terms of mass ratio.

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

17. A method for forming a resist pattern, comprising the following steps: forming a resist film on a substrate using the chemically amplified negative resist composition according to any one of claims 1 to 16, The resist film is irradiated with a pattern of high energy rays, and The resist film irradiated with the pattern is developed using an alkaline developer.

18. The resist pattern forming method according to claim 17, wherein: The high-energy rays are extreme ultraviolet rays or electron beams.

19. The resist pattern forming method according to claim 17, wherein: The outermost surface of the substrate is made of a material containing at least one selected from the group consisting of chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten and tin.

20. The resist pattern forming method according to claim 17, wherein: The substrate is a transmission type or reflection type blank mask.

21. A transmission or reflection type blank mask, which is formed by coating the chemically amplified negative resist composition according to any one of claims 1 to 16.

Images