Iodonium salt, chemically amplified positive resist composition and resist pattern forming process

Abstract

This invention provides a chemical amplifying positive resist composition for photolithography using high-energy rays, exhibiting good solvent solubility and excellent lithography properties such as resolution, LER, and pattern shape, as well as a method for pattern formation using the chemical amplifying resist composition. A zinc salt represented by the following formula (A).

Description

Technical Field

[0001] This invention relates to zinc salts, chemically amplified positive inhibitor compositions, and methods for forming inhibitor patterns. Prior Technology

[0002] In recent years, with the increasing integration of integrated circuits, there is a demand for forming fine patterns. Pattern processing below 0.2 μm mainly uses chemically amplified resist compositions with acid as a catalyst. The exposure source at this time uses high-energy rays such as ultraviolet light, far-ultraviolet light, and electron beams (EB). EB lithography, in particular, used in ultra-fine processing techniques, has become indispensable for the fabrication of blank photomasks in semiconductor manufacturing. The resist compositions used in such photolithography include positive types that dissolve the exposed area to form a pattern, and negative types that leave the exposed area exposed to form a pattern. These are designed to meet the necessary resist pattern morphology and are easy for users to use.

[0003] Generally, etched patterns using an electro-etching (EB) method do not use a mask. For positive patterns, the area outside the desired resist film is sequentially irradiated with a fine-area EB. For negative patterns, the area where the resist film is to be left is irradiated sequentially. Because it involves scanning the entire area of ​​the finely divided processing surface, it is more time-consuming than batch exposure using a photomask. To avoid reducing production capacity, the resist film must have high sensitivity. Furthermore, due to the long etch time, differences can easily occur between the initial and later etched areas. The stability of the exposed area over time in a vacuum is an important performance requirement. Moreover, especially in the processing of blank photomasks, which are of great use, surface materials such as chromium compounds, primarily chromium oxide, deposited on the photomask substrate, can affect the pattern shape of the chemically amplified resist film. To maintain high resolution and etched shape, maintaining the rectangular pattern outline of the resist film regardless of the substrate type is also an important performance requirement.

[0004] Various improvements have been made to control the sensitivity and pattern profile of the aforementioned resist films by adjusting the selection and combination of materials used in the resist composition and processing conditions. One such improvement addresses the problem of acid diffusion, which significantly affects the resolution of chemically amplified resist films. Photomask processing requires that the shape of the resist pattern obtained be independent of the exposure-per-heat (PEB) time; however, a major reason for this time-dependent change is acid diffusion caused by exposure. This acid diffusion problem is not limited to photomask processing; it also significantly impacts sensitivity and resolution in general resist compositions, and therefore has been extensively explored.

[0005] Patent documents 1 and 2 describe examples of suppressing acid diffusion and reducing roughness by increasing the volume of acid produced by an acid-generating agent. However, such acid-generating agents are still insufficient in suppressing acid diffusion, so it is desirable to develop acid-generating agents with smaller diffusion.

[0006] Furthermore, patent documents 3-6 describe controlling acid diffusion by bonding the sulfonic acid generated during exposure to the resin used in the inhibitor composition. This method of suppressing acid diffusion by introducing repeating units that generate acid during exposure into the base polymer is effective for obtaining patterns with low line edge roughness (LER). However, depending on the structure and introduction rate of these repeating units, there are sometimes cases where the base polymer containing the repeating units that generate acid during exposure exhibits problems with solubility in organic solvents.

[0007] Many polymers with aromatic backbones containing acidic side chains, such as polyhydroxystyrene, have been used as resist compositions for KrF lithography. However, they exhibit significant absorption in light around 200 nm, making them unsuitable as resist compositions for ArF lithography. Nevertheless, resist compositions for EB lithography and extreme ultraviolet (EUV) lithography, which offer advantages in forming patterns with smaller processing limits than ArF lithography, are important materials for achieving high etch resistance.

[0008] As for the base polymers of resist compositions for positive EB lithography and EUV lithography, they mainly use acid generated by a photoacid generator when exposed to high-energy rays as a catalyst. This causes the acidic unstable groups (acid-decomposing protecting groups) that cover the acidic functional groups of the phenol side chains on the base polymer to deprotect, making the material soluble in alkaline developer. The aforementioned acid-unstable groups mainly use tertiary alkyl groups, tert-butoxycarbonyl groups, acetal groups, etc. Here, if a protecting group such as an acetal group is used, which requires a lower activation energy for deprotection, it has the advantage of obtaining a resist film with high sensitivity. However, if the diffusion of the generated acid is not sufficiently suppressed, the unexposed parts of the resist film will also undergo deprotection reaction, which will lead to problems such as LER degradation and a decrease in the dimensional uniformity of pattern linewidth (CDU).

[0009] With the recent advancements in the miniaturization of photoresist patterns, controlling the diffusion of acids generated by photoacid generators has become crucial, leading to the development of various acid diffusion control agents (quenchers). These quenchers include conventional amine compounds as well as onium salt-type quenchers such as strontium and ferrophosphate salts. Patent Document 7 describes onium salts of carboxylic acids containing nitrogen-containing heterocyclic structures such as indole. Furthermore, Patent Documents 8-10 propose quenchers derived from strontium and ferrophosphate cations, as well as betaine-type onium salts with intramolecularly bonded phenylene oxide and carboxylate anions. While these quenchers have demonstrated some degree of performance improvement, satisfactory results have not yet been achieved. To meet future miniaturization requirements, it is desirable to develop photoresist materials with excellent photolithography properties and pattern shapes. [Previous Technical Documents] [Patent Literature]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2009-053518 [Patent Document 2] Japanese Patent Application Publication No. 2010-100604 [Patent Document 3] Japanese Patent No. 4425776 [Patent Document 4] Japanese Patent No. 5201363 [Patent Document 5] Japanese Patent No. 5231357 [Patent Document 6] International Publication No. 2008 / 081832 [Patent Document 7] Japanese Patent No. 6515831 [Patent Document 8] Japanese Patent No. 6848776 [Patent Document 9] Japanese Patent No. 6583136 [Patent Document 10] Japanese Patent No. 6246480 Summary of the Invention

[0011] (The problem the invention aims to solve) In recent years, there has been a demand for resist compositions that not only have excellent line spacing (LS), isolated lines (IL), isolated spacing (IS), but also excellent hole pattern shape, and excellent shape after pattern formation.

[0012] In view of the foregoing, the present invention provides a chemical amplifying positive resist composition that exhibits good solvent solubility and excellent lithography properties such as resolution, LER, and pattern shape, especially in photolithography using high-energy rays such as KrF excimer laser, ArF excimer laser, EB, and EUV, and a pattern forming method using the chemical amplifying resist composition. (Methods for solving problems)

[0013] In order to achieve the aforementioned objective, the inventors of this invention have made efforts to explore and discovered that by using betaine-type ferrous salts, which are alkyl chains with 6 to 18 carbon atoms or fluorinated alkyl chains with 4 to 18 carbon atoms and contain ferrous cations and carboxylate anions within the same molecule, as materials for chemical amplification positive inhibitors, the invention exhibits excellent solvent solubility, resolution, LER, pattern shape, and other imaging properties, especially in EB and EUV lithography.

[0014] That is, the present invention provides the following ferrous salt, chemically amplified positive inhibitor composition and inhibitor patterning method. 1. A zinc salt, represented by the following formula (A), [Chemistry 1] In the formula, n1 is 0 or 1, n2 is 0, 1, 2, 3 or 4, n3 is 0 or 1, and n4 is 0, 1, 2, 3 or 4. LA can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond, or carbamate bond. Ralk is an alkyl group having 6 to 18 carbon atoms or a fluorinated alkyl group having 4 to 18 carbon atoms. When Ralk is an alkyl group having 6 to 18 carbon atoms, the alkyl group has at least one straight-chain structure with 6 or more carbon atoms. When Ralk is a fluorinated alkyl group having 4 to 18 carbon atoms, the fluorinated alkyl group has at least two groups selected from -CF2- and -CF3. Furthermore, the -CH2- portion of the alkyl group and the fluorinated alkyl group may also be replaced by an ether bond or a carbonyl group, and its terminal or carbon-carbon bond may also contain a ring structure selected from cyclopentane ring, cyclohexane ring, adamantane ring, norcamphenic ring, and benzene ring. R1 can be a halogen atom, nitro, cyano, hydroxyl, or it can contain a hydrocarbon group with 1 to 20 carbon atoms, an alkyloxy group with 1 to 20 carbon atoms, or a alkylthio group with 1 to 20 carbon atoms. When n2 is 2, 3, or 4, each R1 can be the same or different from the others. Multiple R1s can also bond to each other and form a ring together with the carbon atoms they are bonded to. R2 can be a halogen atom, nitro, cyano, hydroxyl, or it can contain a hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbon oxygen group with 1 to 20 carbon atoms, or a hydrocarbon thio group with 1 to 20 carbon atoms. When n4 is 2, 3, or 4, each R2 can be the same or different from the others. Multiple R2s can also bond to each other and form a ring together with the carbon atoms they are bonded to. Furthermore, the two aromatic rings bonded by the I+ in the formula can also bond to each other and form a ring together with the iodine atoms they are bonded to. 2. As in 1., the tin salt is represented by the following formula (A1), [Chemistry 2] In the formula, n2, n4, LA, Ralk, R1, and R2 are as described above. 3. A quenching agent composed of a zinc salt such as 1 or 2. 4. A chemical amplification positive inhibitor composition comprising a quencher as described in 3. 5. As in 4, the chemically amplified positive inhibitor composition further includes a base polymer containing a polymer that decomposes due to acid action and has increased solubility in alkaline developing solutions. 6. A chemically amplified positive inhibitor composition as described in 5, wherein the polymer contains a repeating unit represented by the following formula (B1), [Chemistry 3] In the formula, a1 is 0 or 1, a2 is 0, 1 or 2, a3 is an integer satisfying 0 ≤ a3 ≤ 5 + 2(a2) - a4, and a4 is 1, 2 or 3. RA can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R11 can be a halogen atom, a nitro group, a carboxyl group, or a 1-6 carbon saturated hydrocarbon group that can be substituted with a halogen atom, or a 2-8 carbon saturated hydrocarbon carbonyl group that can be substituted with a halogen atom. A1 is a single bond or a saturated alkyl group with 1 to 10 carbon atoms. A portion of the -CH2- group of this saturated alkyl group may also be replaced by -O-. 7. A chemically amplified positive inhibitor composition as described in 5 or 6, wherein the polymer contains a repeating unit represented by the following formula (B2-1). [Chemistry 4] In the formula, RA represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 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, and b5 is 0 or 1. R21 can be a halogen atom, a saturated hydrocarbon group with 1 to 6 carbon atoms that can be substituted with a halogen atom, a saturated hydrocarbon oxygen group with 1 to 6 carbon atoms that can be substituted with a halogen atom, or a saturated hydrocarbon carbonyl group with 2 to 8 carbon atoms that can be substituted with a halogen atom. A2 is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms. A portion of the -CH2- group in this saturated hydrocarbon group may also be replaced by -O-. When X is 1 in b4, it is an acid unstable group; when b4 is 2 or 3, it is a hydrogen atom or an acid unstable group, but at least one of them is an acid unstable group. 8. A chemically amplified positive inhibitor composition as described in any of 5.~7, wherein the polymer contains a repeating unit represented by the following formula (B2-2), [Chemistry 5] In the formula, c1 is 0, 1, or 2; c2 is 0, 1, or 2; c3 is 0, 1, 2, 3, 4, or 5; and c4 is 0, 1, or 2. RA can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R22 and R23 can each be an independent hydrocarbon group with 1 to 10 carbon atoms, and can also bond with each other to form a ring with the carbon atoms they are bonded to. R24 is independently a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorinated alkoxy group having 1 to 5 carbon atoms. R35 can be independently composed of hydrocarbon groups with 1 to 10 carbon atoms and may also contain heteroatoms. A3 is a single bond, phenyl, naphthyl or *-C(=O)-O-A31-, A31 is an aliphatic alkyl group with 1 to 20 carbon atoms, which may also contain hydroxyl, ether bond, ester bond or lactone ring, or phenyl or naphthyl, and * is an atomic bond with the carbon atom of the main chain. 9. A chemically amplified positive inhibitor composition as described in any one of 5. to 8, wherein the polymer contains at least one of the repeating units represented by formula (B3), formula (B4), and formula (B5). [Chemistry 6] In the formula, d is 0, 1, 2, 3, 4, 5, or 6; e is 0, 1, 2, 3, or 4; f1 is 0 or 1; f2 is 0, 1, or 2; and f3 is 0, 1, 2, 3, 4, or 5. RA can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R31 and R32 are each independently a hydroxyl group, a halogen atom, a 1-6 carbon saturated hydrocarbon group that can be substituted with a halogen atom, a 1-6 carbon saturated hydrocarbon oxygen group that can be substituted with a halogen atom, or a 2-8 carbon saturated hydrocarbon carbonyl group that can be substituted with a halogen atom. R33 can be a saturated hydrocarbon group with 1-20 carbon atoms, a saturated hydrocarbon oxygen group with 1-20 carbon atoms, a saturated hydrocarbon carbonyl group with 2-20 carbon atoms, a saturated hydrocarbon oxy group with 2-20 carbon atoms, a saturated hydrocarbon thio group with 2-20 carbon atoms, a halogen atom, a nitro group, or a cyano group. When f2 is 1 or 2, it can also be a hydroxyl group. A4 is a single bond or a saturated alkyl group with 1 to 10 carbon atoms. Part of the -CH2- of this saturated alkyl group can also be replaced by -O-. 10. A chemically amplified positive inhibitor composition as described in any one of formulas 5 to 9, wherein the polymer contains at least one repeating unit selected from the following formulas (B6), (B7), (B8), (B9), and (B10). [Chemistry 7] In the formula, g1 and g2 are each independently 0, 1, 2 or 3, h1 is 0 or 1, h2 is 0, 1, 2, 3 or 4, and h3 is 0, 1, 2, 3 or 4. However, when h1 is 0, 0 ≤ h2 + h3 ≤ 4, and when h1 is 1, 0 ≤ h2 + h3 ≤ 6. Each of RA can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z1 is a single bond or may also have substituents, such as a phenyl group. Z2 can be a single bond, **-C(=O)-O-Z21-, **-C(=O)-NH-Z21-, or **-O-Z21-, where Z21 is a divalent group obtained by aliphatic alkyl group, phenyl group, or combinations thereof with 1 to 6 carbon atoms. It may also contain a halogen atom, carbonyl group, ester bond, ether bond, or hydroxyl group. Z3 can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Z4 is a single bond, or a divalent group obtained by aliphatic alkyl group with 1 to 6 carbon atoms, alkylphenyl group, or combinations thereof. It may also contain a halogen atom, carbonyl group, ester bond, ether bond, or hydroxyl group. Z5 can be a single bond, or it can have substituents such as phenyl, naphthyl, or *-C(=O)-O-Z51-, where Z51 is an aliphatic alkyl group, phenyl, or naphthyl group with 1 to 10 carbon atoms. This aliphatic alkyl group may also contain a halogen atom, hydroxyl group, ether bond, ester bond, or lactone ring. Z6 can be a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Z7 can be a single bond, ***-Z71-C(=O)-O-, ***-C(=O)-NH-Z71-, or ***-O-Z71-. Z71 can also be a alkyl group with 1 to 20 carbon atoms and may contain heteroatoms. Z8 can be a single bond, ****-Z81-C(=O)-O-, ****-C(=O)-NH-Z81-, or ****-O-Z81-. Z81 can also be a alkyl group with 1 to 20 carbon atoms and may contain heteroatoms. Z9 can be a single bond, methylene, ethyl, phenyl, fluorinated phenyl, trifluoromethyl-substituted phenyl, *-C(=O)-O-Z91-, *-C(=O)-N(H)-Z91-, or *-O-Z91-, where Z91 is an aliphatic phenyl group with 1 to 6 carbon atoms, phenyl, fluorinated phenyl, or trifluoromethyl-substituted phenyl. It may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group. * indicates an atomic bond with a carbon atom in the main chain, ** indicates an atomic bond with Z1, *** indicates an atomic bond with Z6, and **** indicates an atomic bond with Z7. L1 can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Rf1 and Rf2 are each independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Rf3 and Rf4 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Rf5 and Rf6 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; however, not all Rf5 and Rf6 are simultaneously hydrogen atoms. Rf7 is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated alkyl thio group having 1 to 6 carbon atoms. R41 and R42 can each be an independent hydrocarbon group with 1 to 20 carbon atoms, and they can also bond to each other and form a ring together with the sulfur atoms they are bonded to. R43 can be a halogen atom other than fluorine, or it can be a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms. When h3 is 2, 3, or 4, the R43 atoms can be the same or different from each other. Multiple R43 atoms can also bond to each other and form a ring together with the carbon atoms they are bonded to. M- is a non-nucleophilic relative ion. A+ is an onium cation. 11. A chemical amplification positive inhibitor composition as described in any one of 5 to 10, wherein the content of repeating units having an aromatic ring skeleton in all repeating units of the base polymer is 60 mol% or more. 12. Any of the chemical amplification positive inhibitor compositions in items 4 to 11 further contain organic solvents. 13. Any chemical amplification positive inhibitor composition as described in any of 4.~12, further includes a photoacid generator. 14. The chemical amplification positive inhibitor composition of any one of 4. to 13, further comprising a polymer containing fluorine atoms, the polymer containing fluorine atoms containing at least one repeating unit selected from the following formula (E1), the following formula (E2), the following formula (E3), and the following formula (E4), and may further contain at least one repeating unit selected from the following formula (E5) and the following formula (E6). [Chemistry 8] In the formula, j1 is 1, 2, or 3; j2 is an integer satisfying 0 ≤ j2 ≤ 5 + 2(j3) - j1; j3 is 0 or 1; and k is 1, 2, or 3. Each of RB is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. RC can be independently represented by a hydrogen atom or a methyl group. R201, R202, R204, and R205 are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. R203, R206, R207, and R208 are each independently a hydrogen atom, a hydrocarbon group with 1 to 15 carbon atoms, a fluorinated hydrocarbon group with 1 to 15 carbon atoms, or an acid-destabilized group. When R203, R206, R207, and R208 are hydrocarbon groups or fluorinated hydrocarbon groups, ether bonds or carbonyl groups may also be inserted between carbon-carbon bonds. R209 can be a hydrogen atom, or a straight-chain or branched hydrocarbon group containing heteroatoms inserted between carbon-carbon bonds, consisting of 1 to 5 carbon atoms. R210 is a linear or branched hydrocarbon group with 1 to 5 carbon atoms, which may also have heteroatoms inserted between carbon-carbon bonds. R211 is a saturated hydrocarbon group with 1 to 20 carbon atoms, in which at least one hydrogen atom is replaced by a fluorine atom. The -CH2- portion of this saturated hydrocarbon group may also be replaced by an ester or ether bond. Z1 is a (k+1) valence hydrocarbon group with 1 to 20 carbon atoms or a (k+1) valence fluorinated hydrocarbon group with 1 to 20 carbon atoms. Z2 represents a single bond, *-C(=O)-O-, or *-C(=O)-NH-, where * represents an atomic bond with a carbon atom in the main chain. Z3 is a single bond, -O-, *-C(=O)-O-Z31-Z32- or *-C(=O)-NH-Z31-Z32-, Z31 is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms, Z32 is a single bond, ester bond, ether bond or sulfonamide bond, and * is an atomic bond with a carbon atom in the main chain. 15. The chemical amplification positive inhibitor composition of any one of claims 4 to 14 further includes a quencher other than the quencher of claim 3. 16. A method for forming a resist pattern, comprising the following steps: A resist film is formed on a substrate using any one of the chemical amplification positive resist compositions described in 4. to 15. The resist film is then irradiated with a pattern using high-energy rays, and the irradiated resist film is developed using an alkaline developer. 17. The resist pattern forming method of 16, wherein the high-energy ray is extreme ultraviolet light or an electron beam with a wavelength of 3 to 15 nm. 18. The resist patterning method of 16 or 17, wherein the outermost surface of the substrate is made of a chromium-containing material. 19. A method for forming a resist pattern as described in any one of 16 to 18, wherein the substrate is a blank photomask. (Effects of the invention)

[0015] The chemically amplified positive resist composition of this invention can provide patterns with extremely high resolution and low LER in microfabrication technologies, especially EB lithography and EUV lithography. Furthermore, the shape of the resist pattern after formation exhibits good rectangularity, making it suitable as a chemically amplified positive photoresist material. Implementation

[0016] The present invention will now be described in detail. Furthermore, in the following description, depending on the structure represented by the chemical formula, there may be asymmetric carbon and possibly mirror-image isomers and non-mirror-image isomers; however, in such cases, one structural formula is used to represent these isomers. These isomers may be used individually or in mixtures of two or more.

[0017] [Fermented Salt] The ferrous salt of this invention is represented by the following formula (A). [Chemistry 9]

[0018] In formula (A), n1 is 0 or 1. When n1 is 0, it is a benzene ring; when n1 is 1, it is a naphthalene ring. From the viewpoint of solvent solubility, a benzene ring with n1 of 0 is preferred. n2 is 0, 1, 2, 3, or 4. From the viewpoint of raw material preparation, n2 of 0, 1, or 2 is preferred. n3 is 0 or 1. When n3 is 0, it is a benzene ring; when n3 is 1, it is a naphthalene ring. From the viewpoint of solvent solubility, a benzene ring with n3 of 0 is preferred. n4 is 0, 1, 2, 3, or 4. From the viewpoint of raw material preparation, n4 of 0, 1, or 2 is preferred.

[0019] In formula (A), LA is a single bond, ether bond, ester bond, sulfonate bond, carbonate bond, or carbamate bond. Among these, single bonds, ether bonds, ester bonds, and sulfonate bonds are preferred, with ether bonds and ester bonds being more preferred.

[0020] In formula (A), Ralk is an alkyl group with 6 to 18 carbon atoms or a fluorinated alkyl group with 4 to 18 carbon atoms.

[0021] When Ralk is an alkyl group having 6 to 18 carbon atoms, the alkyl group has a straight-chain structure with at least one carbon atom having 6 or more carbon atoms. Specific examples of alkyl groups having 6 to 18 carbon atoms represented by Ralk include 1-hexyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetrazyl, 1-tetradecyl, 1-hexadecimal, 1-octadecyl, octane-2-yl, decane-2-yl, decane-4-yl, octadecane-8-yl, 7,7-dimethyloctyl, 7,7-diethylnonyl, 4-butyldodecyl, etc. Furthermore, one of the -CH2- groups of the aforementioned alkyl groups may be replaced by an ether bond or a carbonyl group, and the terminal or carbon-carbon bond may also have a ring structure, such as a cyclopentane ring, a cyclohexane ring, an adamantane ring, a norbornene ring, or a benzene ring. It is preferred that Ralk is a straight-chain alkyl group or a straight-chain ethylene glycol dimethyl ether (glyme) chain.

[0022] When Ralk is a fluorinated alkyl group having 4 to 18 carbon atoms, the fluorinated alkyl group has at least two groups selected from -CF2- and -CF3. Specific examples of fluorinated alkyl groups having 4 to 18 carbon atoms represented by Ralk include 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-hexadecyl, 1-hexadecimal, 1-octadecyl, octane-2-yl, decane-2-yl, decane-4-yl, octadecane-8-yl, 7,7-dimethyloctyl, 7,7-diethylnonyl, 4-butyldodecyl, etc., in which one or all of the hydrogen atoms are replaced by fluorine atoms. Furthermore, one of the -CH2- groups of the aforementioned fluorinated alkyl groups can also be replaced by ether bonds or carbonyl groups, and they can also have cyclic structures at their ends or between carbon-carbon bonds, such as cyclopentane rings, cyclohexane rings, adamantane rings, norcamphenic rings, or benzene rings.

[0023] Ralk is preferred as shown below, but is not limited to these. Also, in the following formulas, dashed lines represent atomic bonds. [Chemistry 10]

[0024] In formula (A), R1 can be a halogen atom, a nitro group, a cyano group, a hydroxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. The aforementioned halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine or iodine atoms being more preferred. Furthermore, the aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, decadecyl, heptadecyl, octadecyl, nonadecanyl, and icosyl; cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl; alkenyl groups with 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclounsaturated cycloalkyl groups with 3 to 20 carbon atoms, such as cyclohexenyl; aryl groups with 6 to 20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them. Among these, aryl is preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- portion of the aforementioned hydrocarbon group can also be replaced by a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, it can also possess hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. Also, when n2 is 2, 3, or 4, each R1 can be the same or different from the others.

[0025] Furthermore, when n2 is 2, 3, or 4, multiple R1 atoms can bond to each other and form a ring together with the carbon atoms they are bonded to. Specific examples of the rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. Also, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, some of the -CH2- groups in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the rings may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), and haloalkyl groups.

[0026] In formula (A), R2 can be a halogen atom, a nitro group, a cyano group, a hydroxyl group, or a hydrocarbon group containing 1 to 20 carbon atoms (heteroatomic), a hydrocarbon oxygen group containing 1 to 20 carbon atoms (heteroatomic), or a hydrocarbon thio group containing 1 to 20 carbon atoms (heteroatomic). It is preferred that the aforementioned halogen atom be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, with fluorine or iodine atoms being more preferred. Furthermore, the aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given that are the same as those exemplified for the hydrocarbon group represented by R1, but are not limited to these. Also, when n4 is 2, 3, or 4, each R2 can be the same or different from the others.

[0027] Furthermore, when n4 is 2, 3, or 4, multiple R2 atoms can also bond to each other and form a ring together with the carbon atoms they are bonded to. Specific examples of the rings formed in this case can be given as examples as those exemplified for rings formed by multiple R1 atoms bonded to each other and the carbon atoms they are bonded to, but are not limited to these examples.

[0028] Furthermore, the two aromatic rings bonded by the I+ in formula (A) can also bond to each other and form a ring together with the iodine atoms they are bonded to. In this case, the structure of the aforementioned ring can be represented by the following formulas, etc. [Chemistry 11]

[0029] The zirconia salt represented by formula (A) is preferably represented by formula (A1). [Chemistry 12] In the formula, n2, n4, LA, Ralk, R1, and R2 are as described above.

[0030] Ideal examples of zirconia salts represented by formula (A) can be listed below, but are not limited to these. [Chemistry 13]

[0031] [Chemistry 14]

[0032] [Chemistry 15]

[0033] [Chemistry 16]

[0034] [Chemistry 17]

[0035] [Chemistry 18]

[0036] [Chemistry 19]

[0037] [Chemistry 20]

[0038] [Chemistry 21]

[0039] [Chemistry 22]

[0040] [Chemistry 23]

[0041] [Chemistry 24]

[0042] [Chemistry 25]

[0043] The monazine salt of this invention can be synthesized using known methods. Specifically, the monazine cation framework can be constructed using the synthesis method disclosed in Japanese Patent No. 5062996, and the target substance can be derived using the subsequent conversion reaction, but it is not limited to these methods.

[0044] The zirconia salt of this invention can be ideally used as a quenching agent.

[0045] The zirconia salt represented by formula (A) is characterized by having a basic carboxylate anion structure on the aromatic ring forming the zirconia cation, and a chain of alkyl groups with 6 to 18 carbon atoms or a chain of fluorinated alkyl groups with 4 to 18 carbon atoms. The aforementioned alkyl and fluorinated alkyl groups increase solvent solubility and have high lipid solubility; therefore, it is believed that the zirconia salt represented by formula (A) will be distributed in the upper layer of the resist film. Especially in EB lithography, when depicting an electron beam, the effect of forward scattering caused by the electron beam in the exposed area cannot be avoided. When using conventional quenchers, there is a concern that the deprotection reaction in the upper part of the pattern may be excessive, resulting in a rounded top shape. By using the quencher of this invention, excessive deprotection reaction in the upper part of the pattern can be effectively suppressed, and the pattern can be corrected to a rectangle. Furthermore, the high basicity of the carboxylate anion within the same molecule can control the diffusion of acid and effectively quench it. Utilizing these synergistic effects, when using the salts of the present invention, it is believed that patterns with good resolution, high contrast, good CDU, and low LER can be obtained, as well as patterns with good rectangularity.

[0046] [Chemical Amplification Positive Inhibitor Composition] [(A) Quenching agent] The chemically amplified positive resist composition of the present invention includes a quencher composed of a zinc salt represented by formula (A) as an essential component. Furthermore, in the present invention, the quencher refers to a compound that captures the acid generated by the acid-generating agent. This suppresses the diffusion rate of the acid generated by the acid-generating agent within the resist film, and even when a substrate with an outermost surface made of a chromium-containing material is used as the substrate, the influence of the acid generated within the resist film on the chromium-containing material can still be suppressed.

[0047] In the chemical amplification positive inhibitor composition of this invention, the content of (A) quencher is ideally 0.1 to 50 parts by mass relative to 80 parts by mass of the base polymer (B) described later, and even more ideally 0.1 to 40 parts by mass. If the quencher content is within the aforementioned range, the generated acid can be effectively captured, resulting in a good pattern shape. Furthermore, storage stability is also good. (A) Quencher can be used alone or in combination of two or more.

[0048] [(B) Basic Polymer] The inhibitor composition of the present invention includes, as component (B), a base polymer containing a polymer that decomposes due to acid action and has increased solubility in alkaline developing solutions.

[0049] The aforementioned polymer is preferably a polymer containing a repeating unit represented by the following formula (B1) (hereinafter also referred to as repeating unit B1). [Chemistry 26]

[0050] In formula (B1), a1 is 0 or 1. a2 is 0, 1, or 2; when a2 is 0, it represents the benzene skeleton; when a2 is 1, it represents the naphthalene skeleton; and when a2 is 2, it represents the anthracene skeleton. a3 is an integer satisfying 0 ≤ a3 ≤ 5 + 2(a2) - a4. a4 is 1, 2, or 3. When a2 is 0, it is preferable that a3 is 0, 1, 2, or 3, and a4 is 1, 2, or 3. When a2 is 1 or 2, it is preferable that a3 is 0, 1, 2, 3, or 4, and a4 is 1, 2, or 3.

[0051] In formula (B1), RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0052] In formula (B1), R11 can be a halogen atom, a nitro group, a carboxyl group, a saturated hydrocarbon group with 1 to 6 carbon atoms that can be substituted with a halogen atom, a saturated hydrocarbon oxygen group with 1 to 6 carbon atoms that can be substituted with a halogen atom, or a saturated hydrocarbon carbonyl oxygen group with 2 to 8 carbon atoms that can be substituted with a halogen atom. The saturated hydrocarbon group, saturated hydrocarbon oxygen group, and saturated hydrocarbon carbonyl oxygen group can be linear, branched, or cyclic. Specific examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, and their structural isomers; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; and groups obtained by combining them. If the number of carbon atoms is below the upper limit, the solubility in alkaline developing solutions is good. When a3 is 2 or more, each R11 can be the same or different from the others.

[0053] In formula (B1), A1 is a single bond or a saturated alkyl group with 1 to 10 carbon atoms. A portion of the -CH2- group may also be replaced by -O-. The aforementioned saturated alkyl group can be linear, branched, or cyclic. Specific examples include methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and their structural isomers, as well as alkyl diyl groups with 1 to 10 carbon atoms; cyclopropane diyl, cyclobutane diyl, cyclopentane diyl, cyclohexane diyl, and other cyclic saturated alkyl groups with 3 to 10 carbon atoms; and groups obtained by combining these. When the aforementioned saturated alkyl group contains an ether bond, when a1 in formula (B1) is 1, it can be inserted anywhere except between the carbon atom at the α-position and the carbon atom at the β-position relative to the ester oxygen atom. Furthermore, when a1 is 0, the atom bonded to the main chain becomes an ether oxygen atom, and a second ether bond can be inserted at any position other than between the carbon atoms at the α and β positions relative to this ether oxygen atom. Also, if the number of carbon atoms in the aforementioned saturated hydrocarbon group is 10 or less, sufficient solubility in alkaline developing solutions can be obtained, which is ideal.

[0054] When a1 is 0 and A1 is a single bond, that is, when the aromatic ring and the polymer backbone are directly bonded (i.e., there is no linking group (-C(=O)-O-A1-)), ideal examples of repeating unit B1 can be found in units from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene, 6-hydroxy-2-vinylnaphthalene, etc. Specifically, examples can be listed below, but are not limited to these. Furthermore, in the following formula, RA is as described above. [Chemistry 27]

[0055] [Chemistry 28]

[0056] [Chemistry 29]

[0057] When a1 is 1 (that is, with -C(=O)-O-A1- as a linking basis), ideal examples of repeating unit B1 can be listed below, but are not limited to these. Also, in the following formula, RA is as described above. [Chemistry 30]

[0058] [Chemistry 31]

[0059] [Chemistry 32]

[0060] [Chemistry 33]

[0061] [Chemistry 34]

[0062] Ideally, the content of repeating unit B1 should be 15-90 mol% of all repeating units constituting the aforementioned polymer, and more preferably 15-80 mol%. However, it is also preferable to include at least one of the repeating units represented by formula (B3) and formula (B4) that provide higher etch resistance to the polymer described later, and this unit has a phenolic hydroxyl group as a substituent, in the aforementioned range. Repeating unit B1 can be used alone or in combination of two or more.

[0063] In the aforementioned polymer, in order to give the exposed portion of the positive resist composition the property of being soluble in alkaline developer, it is preferable to contain repeating units with acidic functional groups protected by acid-destabilized groups, that is, repeating units that are protected by acid-destabilized groups and become alkali-soluble due to acid action (hereinafter also referred to as repeating unit B2).

[0064] The most ideal form of repeating unit B2 can be represented by the following formula (B2-1) (hereinafter also referred to as repeating unit B2-1). [Chemistry 35]

[0065] In formula (B2-1), b1 is 0 or 1. b2 is 0, 1, or 2; when b2 is 0, it is a benzene skeleton; when b2 is 1, it is naphthalene; and when b2 is 2, it is anthracene. b3 is an integer satisfying 0 ≤ b3 ≤ 5 + 2(b2) - b4. b4 is 1, 2, or 3. b5 is 0 or 1. When b2 is 0, it is preferred that b3 is 0, 1, 2, or 3, and b4 is 1, 2, or 3. When b2 is 1 or 2, it is preferred that b3 is 0, 1, 2, 3, or 4, and b4 is 1, 2, or 3.

[0066] In formula (B2-1), RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0067] In formula (B2-1), R21 is a halogen atom, a saturated hydrocarbon group with 1 to 6 carbon atoms that can be substituted with a halogen atom, a saturated hydrocarbon oxygen group with 1 to 6 carbon atoms that can be substituted with a halogen atom, or a saturated hydrocarbon carbonyl oxygen group with 2 to 8 carbon atoms that can be substituted with a halogen atom. The saturated hydrocarbon group, saturated hydrocarbon carbonyl oxygen group, and saturated hydrocarbon oxygen group can be linear, branched, or cyclic. Specific examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, and their structural isomers; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; and groups obtained by combining them. If the number of carbon atoms is below the upper limit, the solubility in alkaline developing solutions is good. When b3 is 2 or more, each R21 can be the same or different from the others.

[0068] In formula (B2-1), A2 is a single bond or a saturated alkyl group with 1 to 10 carbon atoms. A portion of the -CH2- group may also be replaced by -O-. The aforementioned saturated alkyl group can be linear, branched, or cyclic. Specific examples include methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and their structural isomers, as well as alkyl diyl groups with 1 to 10 carbon atoms; cyclopropane diyl, cyclobutane diyl, cyclopentane diyl, cyclohexane diyl, and other cyclic saturated alkyl groups with 3 to 10 carbon atoms; and groups obtained by combining these. When the aforementioned saturated alkyl group contains an ether bond, b1 in formula (B2-1) being 1 can be inserted anywhere except between the carbon atom at the α-position and the carbon atom at the β-position relative to the ester oxygen atom. Furthermore, when b1 is 0, the atom bonded to the main chain becomes an ether oxygen atom, and a second ether bond can be inserted at any position other than between the carbon atoms at the α and β positions relative to this ether oxygen atom. Also, if the number of carbon atoms in the aforementioned saturated hydrocarbon group is 10 or less, sufficient solubility in alkaline developing solutions can be obtained, which is ideal.

[0069] In formula (B2-1), when b4 is 1, X is an acid-destabilized group. When b4 is 2 or 3, X is either a hydrogen atom or an acid-destabilized group independently, but at least one is an acid-destabilized group. That is, the repeating unit B2-1 is either a phenolic hydroxyl group of an aromatic ring bonded to an acidic ring that is protected by an acid-destabilized group, or a carboxyl group of an aromatic ring bonded to an acidic ring that is protected by an acid-destabilized group. The aforementioned acid-destabilized group can be used without particular limitation as long as it is one of the acid-destabilized groups used in most known chemical amplification positive inhibitor compositions that provides an acidic group after acid removal.

[0070] The aforementioned unstable acid groups, such as tertiary saturated hydrocarbon groups. For the aforementioned tertiary saturated hydrocarbon groups, those with 4 to 18 carbon atoms are preferred for obtaining the monomers used in polymerization by distillation.

[0071] The saturated hydrocarbon groups with tertiary carbon atom bonds in the aforementioned tertiary saturated hydrocarbon groups are preferably those with 1 to 15 carbon atoms. These saturated hydrocarbon groups with 1 to 15 carbon atoms can be linear, branched, or cyclic, and may also contain oxygen-containing functional groups such as ether bonds or carbonyl groups between their carbon-carbon bonds. Furthermore, the saturated hydrocarbon groups with tertiary carbon atom bonds can also bond to each other and form rings together with the tertiary carbon atoms they are bonded to.

[0072] Examples of the aforementioned alkyl substituents include methyl, ethyl, propyl, adamantyl, norbornel, tetrahydrofuran-2-yl, 7-oxanorborne-2-yl, cyclopentyl, 2-tetrahydrofuranyl, tricyclo[5.2.1.02,6]decyl, 8-ethyl-8-tricyclo[5.2.1.02,6]decyl, 3-methyl-3-tetracyclo[4.4.0.12,5.17,10]dodecyl, tetracyclo[4.4.0.12,5.17,10]dodecyl, and 3-sideoxy-1-cyclohexyl.

[0073] Examples of the aforementioned tertiary saturated hydrocarbon groups include tert-butyl, tert-pentyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1,2-trimethylpropyl, 1-adamantyl-1-methylethyl, 1-methyl-1-(2-norbornenyl)ethyl, 1-methyl-1-(tetrahydrofuran-2-yl)ethyl, 1-methyl-1-(7-oxanorbornen-2-yl)ethyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-propylcyclopentyl, 1-cyclopentylcyclopentyl, 1-cyclohexylcyclopentyl, 1-(2-tetrahydrofuranyl)cyclopentyl, 1-(7-oxanorbornen-2-yl)cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-cyclopentylcyclohexyl, and 1-cyclohexyl ... Hexyl, 2-methyl-2-norborneol, 2-ethyl-2-norborneol, 8-methyl-8-tricyclo[5.2.1.02,6]decyl, 8-ethyl-8-tricyclo[5.2.1.02,6]decyl, 3-methyl-3-tetracyclo[4.4.0.12,5.17,10]dodecyl, 3-ethyl-3-tetracyclo[4.4.0.12,5.17,10]dodecyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 1-methyl-3-sideoxy-1-cyclohexyl, 1-methyl-1-(tetrahydrofuran-2-yl)ethyl, 5-hydroxy-2-methyl-2-adamantyl, 5-hydroxy-2-ethyl-2-adamantyl, but not limited to these.

[0074] Furthermore, the aforementioned acid-destabilized group can be exemplified by the group represented by formula (B2-1-1). The group represented by formula (B2-1-1) is commonly used as an acid-destabilized group and is a useful option for providing a relatively rectangular pattern at the interface between the pattern and the substrate. When X is the group represented by formula (B2-1-1), an acetal structure is formed. [Chemistry 36] In the formula, the dashed lines represent atomic bonds.

[0075] In formula (B2-1-1), RL1 is a hydrogen atom or a saturated hydrocarbon group with 1 to 10 carbon atoms. The aforementioned saturated hydrocarbon group can be linear, branched, or cyclic.

[0076] RL1 can be appropriately selected based on the design considerations regarding the sensitivity of the decomposable group to acids. For example, if the design prioritizes strong acid decomposition while ensuring relatively high stability, a group with a hydrogen atom or a carbon atom bonded to the acetal carbon atom as a tertiary carbon atom is preferable. Examples of RL1s utilizing tertiary carbon atoms bonded to the acetal carbon atom include tert-butyl, tert-pentyl, and 1-adamantyl, but are not limited to these. If the design prioritizes high reactivity and sensitivity to pH changes, a straight-chain alkyl group is preferable. While the choice also depends on the combination of acid-generating agents and quenchers in the inhibitor composition, when RL2 is designed with a larger terminal alkyl group and a significant change in solubility due to decomposition, a RL1 with a secondary carbon atom bonded to the acetal carbon atom is preferable. Examples of RL1s utilizing secondary carbon atoms bonded to the acetal carbon atom include isopropyl, tert-butyl, cyclopentyl, and cyclohexyl, but are not limited to these.

[0077] In formula (B2-1-1), RL2 is a hydrocarbon group with 1 to 30 carbon atoms. This hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The -CH2- portion of this hydrocarbon group can also be replaced by heteroatoms such as oxygen or sulfur atoms, resulting in ether bonds or thioether bonds. Specific examples of the aforementioned hydrocarbon group include saturated hydrocarbon groups with 1 to 30 carbon atoms and aryl groups with 6 to 30 carbon atoms. Especially in the formation of fine patterns, it is preferable for RL2 to be a hydrocarbon group with 1 to 6 carbon atoms to obtain higher resolution. When RL2 is a hydrocarbon group with 1 to 6 carbon atoms, the alcohol-based deprotection reaction produced is water-soluble. Therefore, when forming positive patterns using an alkaline developer, it will dissolve in the developer, thus suppressing residual defects in the exposed area.

[0078] Ideal examples of the basis represented by equation (B2-1-1) can be listed below, but are not limited to these. Also, in the following equation, RL1 is as described above, and the dashed lines represent atomic bonds. [Chemistry 37]

[0079] [Chemistry 38]

[0080] As other acid-destabilizing groups, acid-destabilizing groups in which the hydrogen atom of the phenolic hydroxyl group is replaced by -CH2COO- (a tertiary saturated hydrocarbon group) can be used. In this case, the aforementioned tertiary saturated hydrocarbon group can be the same as the tertiary saturated hydrocarbon group used for the protection of the aforementioned phenolic hydroxyl group.

[0081] Furthermore, repeating unit B2 can also be represented by the following formula (B2-2) (hereinafter also referred to as repeating unit B2-2). Repeating unit B2-2, because the dissolution rate of the exposure section is increased, is a useful option as a unit containing acid-destabilized groups that provides good performance for linewidth variations in the developing load. [Chemistry 39]

[0082] In equation (B2-2), c1 is 0, 1, or 2. c2 is 0, 1, or 2. c3 is 0, 1, 2, 3, 4, or 5. c4 is 0, 1, or 2.

[0083] In formula (B2-2), RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0084] In formula (B2-2), R22 and R23 are each independently hydrocarbon groups with 1 to 10 carbon atoms, which may also contain heteroatoms. R22 and R23 can also bond to each other and form a ring together with the carbon atoms they are bonded to.

[0085] In formula (B2-2), R24 is independently a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorinated alkoxy group having 1 to 5 carbon atoms.

[0086] In formula (B2-2), R35 can be a hydrocarbon group with 1 to 10 carbon atoms that can also contain heteroatoms.

[0087] In formula (B2-2), A3 is a single bond, an enylphenyl, an enylnaphthyl, or *-C(=O)-O-A31-. A31 may also be an aliphatic enyl group with 1 to 20 carbon atoms, containing a hydroxyl group, an ether bond, an ester bond, or an lactone ring, or an enylphenyl or enylnaphthyl. * indicates an atomic bond between the main chain carbon atom and the main chain carbon atom.

[0088] Ideal examples of repeating unit B2-2 can be listed below, but are not limited to these. Also, in the following formula, RA is as described above. [Chemistry 40]

[0089] [Chemistry 41]

[0090] The content of repeating unit B2 is ideally 5-95 mol% of all repeating units of the aforementioned polymer, and even more ideally 20-80 mol%. Repeating unit B2 can be used alone or in combination of two or more types.

[0091] The aforementioned polymer may also contain at least one of the repeating units represented by formula (B3) (hereinafter also referred to as repeating unit B3.), the repeating units represented by formula (B4) (hereinafter also referred to as repeating unit B4.), and the repeating units represented by formula (B5) (hereinafter also referred to as repeating unit B5.). [Chemistry 42]

[0092] In equations (B3) and (B4), d is 0, 1, 2, 3, 4, 5, or 6. e is 0, 1, 2, 3, or 4.

[0093] In formulas (B3) and (B4), R31 and R32 are each independently a hydroxyl group, a halogen atom, a saturated hydrocarbon group with 1 to 6 carbon atoms that may be substituted with a halogen atom, a saturated hydrocarbon oxygen group with 1 to 6 carbon atoms that may be substituted with a halogen atom, or a saturated hydrocarbon carbonyl oxygen group with 2 to 8 carbon atoms that may be substituted with a halogen atom. The aforementioned saturated hydrocarbon group, saturated hydrocarbon oxygen group, and saturated hydrocarbon carbonyl oxygen group can be linear, branched, or cyclic. When d is 2 or more, each R31 can be the same or different from each other. When e is 2 or more, each R32 can be the same or different from each other.

[0094] In formula (B5), f1 is 0 or 1. f2 is 0, 1 or 2; when f2 is 0, it is a benzene skeleton; when f2 is 1, it is a naphthalene skeleton; and when f2 is 2, it is an anthracene skeleton. f3 is 0, 1, 2, 3, 4 or 5. When f2 is 0, f3 is preferably 0, 1, 2 or 3; when f2 is 1 or 2, f3 is preferably 0, 1, 2, 3 or 4.

[0095] In formula (B5), RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0096] In formula (B5), R33 can be a saturated hydrocarbon group with 1 to 20 carbon atoms, a saturated hydrocarbon oxygen group with 1 to 20 carbon atoms, a saturated hydrocarbon carbonyl group with 2 to 20 carbon atoms, a saturated hydrocarbon oxy group with 2 to 20 carbon atoms, a halogen atom, a nitro group, or a cyano group. When f2 is 1 or 2, it can also be a hydroxyl group. The aforementioned saturated hydrocarbon group, saturated hydrocarbon oxygen group, saturated hydrocarbon carbonyl group, saturated hydrocarbon oxygen group, and saturated hydrocarbon oxy group can be linear, branched, or cyclic. When f3 is 2 or more, each R33 can be the same or different from the others.

[0097] In formula (B5), A4 is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms. Part of the -CH2- of the saturated hydrocarbon group may also be replaced by -O-. The aforementioned saturated hydrocarbon group can be linear, branched, or cyclic. Specific examples can be given in the same way as those illustrated in the description of A1 in formula (B1).

[0098] When at least one of repeating units B3 to B5 is used as a constituent unit of the aforementioned polymer, the etching resistance of the aromatic ring can be obtained, and further, the etching resistance and EB irradiation resistance during pattern inspection can be improved by adding a ring structure to the main chain.

[0099] Regarding the content of repeating units B3 to B5, to achieve the effect of improving etching resistance, it is preferable to have a content of 5 mol% or more among all repeating units constituting the aforementioned polymer. Furthermore, it is preferable that the content of repeating units B3 to B5 is 25 mol% or less among all repeating units constituting the aforementioned polymer, and even more preferable to have 20 mol% or less. When there are no functional groups or the functional groups are other than hydroxyl groups, an introduction amount of 25 mol% or less is ideal as there is no risk of development defects. Repeating units B3 to B5 can be used alone or in combination of two or more.

[0100] If the aforementioned polymer contains at least one of repeating units B1, B2, and B3 to B5, it is preferable from the viewpoint of balancing high etch resistance and resolution. In this case, it is preferable that such repeating units account for 60 mol% or more of all repeating units in the aforementioned polymer, more preferably 70 mol% or more, even more preferably 80 mol% or more, and ideally more than 90 mol% or more.

[0101] The aforementioned polymer may also contain at least one of the repeating units represented by formula (B6) (hereinafter also referred to as repeating unit B6), the repeating units represented by formula (B7) (hereinafter also referred to as repeating unit B7), the repeating units represented by formula (B8) (hereinafter also referred to as repeating unit B8), the repeating units represented by formula (B9) (hereinafter also referred to as repeating unit B9), and the repeating units represented by formula (B10) (hereinafter also referred to as repeating unit B10). [Chemistry 43]

[0102] In formulas (B6) to (B10), RA is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z1 is a single bond or may be a phenyl group with substituents. Z2 is a single bond, **-C(=O)-O-Z21-, **-C(=O)-NH-Z21-, or **-O-Z21-. Z21 is a divalent group obtained by aliphatic alkyl group, phenyl group, or combinations thereof with 1 to 6 carbon atoms, and may also contain a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z3 is a single bond, an ether bond, an ester bond, an amide bond, a sulfonate bond, a sulfonamide bond, a carbonate bond, or a carbamate bond. Z4 is a single bond, or a divalent group obtained by aliphatic alkyl group, phenyl group, or combinations thereof with 1 to 6 carbon atoms, and may also contain a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z5 is independently a single bond, or may contain substituents such as phenyl, naphthyl, or *-C(=O)-O-Z51-. Z51 is an aliphatic alkyl group, phenyl, or naphthyl with 1 to 10 carbon atoms; this aliphatic alkyl group may also contain halogen atoms, hydroxyl groups, ether bonds, ester bonds, or lactone rings. Z6 is a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Z7 is independently a single bond, ***-Z71-C(=O)-O-, ***-C(=O)-NH-Z71-, or ***-O-Z71-. Z71 may also contain heteroatoms and is an alkyl group with 1 to 20 carbon atoms. Z8 is independently a single bond, ****-Z81-C(=O)-O-, ****-C(=O)-NH-Z81-, or ****-O-Z81-. Z81 is an alkyl group with 1 to 20 carbon atoms, which may also contain heteroatoms. Z9 is a single bond, methylene, ethyl, phenyl, fluorinated phenyl, trifluoromethyl-substituted phenyl, *-C(=O)-O-Z91-, *-C(=O)-N(H)-Z91-, or *-O-Z91-. Z91 is an aliphatic alkyl group with 1 to 6 carbon atoms, phenyl, fluorinated phenyl, or trifluoromethyl-substituted phenyl, and may also contain carbonyl, ester, ether, or hydroxyl groups. * indicates an atomic bond with a carbon atom in the main chain. ** indicates an atomic bond with Z1. *** indicates an atomic bond with Z6. **** indicates an atomic bond with Z7.

[0103] The aliphatic alkyl groups represented by Z21, Z51, and Z91 can be straight-chain, branched, or cyclic. Specific examples include alkyl diyl groups such as methane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, 1,1-dimethylethane-1,2-diyl, pentane-1,5-diyl, 2-methylbutane-1,2-diyl, and hexane-1,6-diyl; cyclopropane-diyl, cyclobutane-diyl, cyclopentane-diyl, and cyclohexane-diyl; and groups obtained by combining them.

[0104] Z71 and Z81 can also indicate that the extended hydrocarbon group containing heteroatoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples are listed below, but are not limited to these. [Chemistry 44] In the formula, the dashed lines represent atomic bonds.

[0105] In formula (B6), R41 and R42 are each independently a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, and tributyl; cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclohexenyl and other cyclounsaturated hydrocarbon groups with 3 to 20 carbon atoms; aryl groups with 6 to 20 carbon atoms, such as phenyl, naphthyl, and thiophene; aralkyl groups with 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them, with aryl groups being preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- portion of the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, it may also contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonate ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups.

[0106] Furthermore, R41 and R42 can also bond to each other and form a ring together with the sulfur atoms they are bonded to. Specific examples of the aforementioned rings can be shown in the following formulas. [Chemistry 45] In the formula, the dashed lines represent the atomic bonds between Z and Z4.

[0107] Specific examples of cations in repeating unit B6 can be listed below, but are not limited to these. Also, in the following formula, RA is as described above. [Chemistry 46]

[0108] [Chemistry 47]

[0109] [Chemistry 48]

[0110] [Chemistry 49]

[0111] [Transformation 50]

[0112] [Chemistry 51]

[0113] [Chemistry 52]

[0114] [Chemistry 53]

[0115] [Chemistry 54]

[0116] [Chemistry 55]

[0117] In formula (B6), M- represents a non-nucleophilic relative ion. Preferred non-nucleophilic relative ions are halide ions, sulfonic acid anions, aceimine anions, and methylated acid anions. Specific examples of halide ions include chloride ions and bromide ions. Specific examples of sulfonic acid anions (sulfonate ions) include trifluoromethanesulfonate ions, 1,1,1-trifluoroethanesulfonate ions, nonafluorobutanesulfonate ions, and other fluoroalkyl sulfonate ions; toluenesulfonate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, 1,2,3,4,5-pentafluorobenzenesulfonate ions, and other aryl sulfonate ions; methanesulfonate ions, butanesulfonate ions, and other alkyl sulfonate ions. Specific examples of the aforementioned amide acid anions (amide ions) include bis(trifluoromethylsulfonyl)amide ions, bis(perfluoroethylsulfonyl)amide ions, and bis(perfluorobutylsulfonyl)amide ions. Specific examples of the aforementioned methylated acid anions (methylated ions) include trifluoromethylsulfonyl methylated ions and trifluoroethylsulfonyl methylated ions.

[0118] Other examples of the aforementioned non-nucleophilic relative ions can be exemplified by anions represented by any of the formulas (B6-1) to (B6-4). [Chemistry 56]

[0119] In formula (B6-1), Rfa is a fluorine atom, or it may be a hydrocarbon group with 1 to 40 carbon atoms containing heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given, and the examples are the same as those exemplified by the hydrocarbon group represented by Rfa1 in formula (B6-1-1) described later.

[0120] The anion represented by formula (B6-1) is preferably represented by the following formula (B6-1-1). [Chemistry 57]

[0121] In formula (B6-1-1), Q1 and Q2 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms. However, to improve solvent solubility, at least one of them is preferably trifluoromethyl. m can be 0, 1, 2, 3, or 4, with 1 being particularly preferred. Rfa1 can also be a hydrocarbon group with 1 to 35 carbon atoms containing heteroatoms. Among the aforementioned heteroatoms, oxygen, nitrogen, sulfur, and halogen atoms are preferred, with oxygen atoms being even more ideal. From the viewpoint of obtaining high resolution during the formation of fine patterns, the aforementioned hydrocarbon groups with 6 to 30 carbon atoms are particularly preferred.

[0122] In formula (B6-1-1), Rfa1 represents a hydrocarbon group with 1 to 35 carbon atoms that can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 35 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecanyl, and icosyl; cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norcamphenyl, norcamphenylmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl; unsaturated aliphatic hydrocarbon groups with 2 to 35 carbon atoms, such as 2-propenyl and 3-cyclohexenyl; aryl groups with 6 to 35 carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, and 9-enyl; aralkyl groups with 7 to 35 carbon atoms, such as benzyl and diphenylmethyl; and groups obtained by combining them.

[0123] Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- portion of the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, it may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Specific examples of hydrocarbon groups containing heteroatoms include tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetaminomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-sideoxypropyl, 4-sideoxy-1-adamantyl, 3-sideoxycyclohexyl, etc.

[0124] In formula (B6-1-1), La1 can be a single bond, ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond. From a synthetic point of view, ether bonds or ester bonds are preferred, with ester bonds being more ideal.

[0125] Specific examples of anions represented by formula (B6-1) are listed below, but are not limited to these. Also, in the following formula, Q1 is as described above, and Ac is acetyl. [Chem.58]

[0126] [Chemistry 59]

[0127] [Transformation 60]

[0128] [Chemistry 61]

[0129] [Chemistry 62]

[0130] [Chemistry 63]

[0131] [Chemistry 64]

[0132] [Chemistry 65]

[0133] [Chemistry 66]

[0134] [Chemistry 67]

[0135] In formula (B6-2), Rfb1 and Rfb2 are each independently a fluorine atom, or may contain heteroatoms of 1 to 40 carbon atoms, and are hydrocarbons. The aforementioned hydrocarbons can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given as those exemplified by the hydrocarbon represented by Rfa1 in formula (B6-1-1). Rfb1 and Rfb2 are preferably fluorine atoms or linear fluorinated alkyl groups having 1 to 4 carbon atoms. Furthermore, Rfb1 and Rfb2 can also bond to each other and form a ring together with the group they bond to (-CF2-SO2-N--SO2-CF2-). In this case, the group obtained by the mutual bonding of Rfb1 and Rfb2 is preferably fluorinated ethyl or fluorinated propyl.

[0136] In formula (B6-3), Rfc1, Rfc2, and Rfc3 are each independently a fluorine atom, or may contain heteroatoms and be a hydrocarbon group with 1 to 40 carbon atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given similarly to those exemplified by the hydrocarbon group represented by Rfa1 in formula (B6-1-1). Rfc1, Rfc2, and Rfc3 are preferably fluorine atoms or linear fluorinated alkyl groups with 1 to 4 carbon atoms. Furthermore, Rfc1 and Rfc2 can also be bonded to each other and form a ring together with the group they are bonded to (-CF2-SO2-C--SO2-CF2-). In this case, the group obtained by the mutual bonding of Rfc1 and Rfc2 is preferably a fluorinated ethyl or fluorinated propyl group.

[0137] In formula (B6-4), Rfd can be a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given, and the examples are the same as those exemplified by the hydrocarbon group represented by Rfa1 in formula (B6-1-1).

[0138] Specific examples of anions represented by formula (B6-4) are listed below, but are not limited to these. [Chemistry 68]

[0139] [Chemistry 69]

[0140] The aforementioned examples of non-nucleophilic relative ions can be further illustrated by anions having aromatic rings substituted with iodine or bromine atoms. Specific examples of such anions can be represented by the following formula (B6-5). [Chemistry 70]

[0141] In equation (B6-5), x is 1, 2, or 3. y is 1, 2, 3, 4, or 5. z is 0, 1, 2, or 3. Only 1 ≤ y + z ≤ 5. y being 1, 2, or 3 is more ideal, with 2 or 3 being even better. z being 0, 1, or 2 is preferable.

[0142] In formula (B6-5), XBI is an iodine atom or a bromine atom, and when x and / or y are 2 or more, they can be the same or different.

[0143] In formula (B6-5), L11 is a single bond, ether bond, or ester bond, or may contain a saturated alkyl group with 1 to 6 carbon atoms that is an ether bond or ester bond. The aforementioned saturated alkyl group may be linear, branched, or cyclic.

[0144] In formula (B6-5), L12 is a single bond or a divalent linkage group with 1 to 20 carbon atoms when x is 1, and a (x+1) valent linkage group with 1 to 20 carbon atoms when x is 2 or 3. The linkage group may also contain oxygen atoms, sulfur atoms or nitrogen atoms.

[0145] In formula (B6-5), Rfe is a hydroxyl, carboxyl, fluorine, chlorine, bromine, or amino group, or may contain a 1-20 carbon-1 hydrocarbon group, a 1-20 carbon-1 hydrocarbon oxygen group, a 2-20 carbon-2 hydrocarbon carbonyl group, a 2-20 carbon-2 hydrocarbon oxycarbonyl group, a 2-20 carbon-2 hydrocarbon carbonyl oxygen group, or a 1-20 carbon-1 hydrocarbon sulfonyl oxygen group, or -N(RfeA)(RfeB), -N(RfeC)-C(=O)-RfeD, or -N(RfeC)-C(=O)-O-RfeD. RfeA and RfeB are each independently a hydrogen atom or a 1-6 carbon-1 saturated hydrocarbon group. RfeC is a hydrogen atom or a saturated hydrocarbon group with 1 to 6 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxygen group with 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group with 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl group with 2 to 6 carbon atoms. RfeD is an aliphatic hydrocarbon group with 1 to 16 carbon atoms, an aryl group with 6 to 12 carbon atoms, or an aralkyl group with 7 to 15 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxygen group with 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group with 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl group with 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned hydrocarbon group, hydrocarbon oxygen group, hydrocarbon carbonyl group, hydrocarbon oxygen carbonyl group, hydrocarbon carbonyl group, and hydrocarbon sulfonyl group can be any of the following: linear, branched, or cyclic. When x and / or z are 2 or more, each Rfe can be the same or different from the others.

[0146] Among these, Rfe being hydroxyl, -N(RfeC)-C(=O)-RfeD, -N(RfeC)-C(=O)-O-RfeD, fluorine atom, chlorine atom, bromine atom, methyl, methoxy, etc., is preferred.

[0147] In formula (B6-5), Rf11 to Rf14 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of them is a fluorine atom or a trifluoromethyl group. Furthermore, Rf11 and Rf12 can also combine to form a carbonyl group. It is particularly preferred that both Rf13 and Rf14 are fluorine atoms.

[0148] Specific examples of anions represented by formula (B6-5) are listed below, but are not limited to these. Also, in the following formula, XBI is as described above. [Chemistry 71]

[0149] [Chemistry 72]

[0150] [Chemistry 73]

[0151] [Chemistry 74]

[0152] [Chemistry 75]

[0153] [Chemistry 76]

[0154] [Chemistry 77]

[0155] [Chemistry 78]

[0156] [Chemistry 79]

[0157] [Chemistry 80]

[0158] [Chemistry 81]

[0159] [Chemistry 82]

[0160] [Chemistry 83]

[0161] [Chemistry 84]

[0162] [Chemistry 85]

[0163] [Chemistry 86]

[0164] [Chemistry 87]

[0165] [Chemistry 88]

[0166] [Chemistry 89]

[0167] [Chemistry 90]

[0168] [Chemistry 91]

[0169] [Chemistry 92]

[0170] [Chemistry 93]

[0171] The aforementioned non-nucleophilic relative ions may also include the fluorobenzenesulfonic acid anion with an aromatic group bonded containing an iodine atom as described in Japanese Patent No. 6648726, the anion with an acid decomposition mechanism as described in International Publication No. 2021 / 200056 and Japanese Patent Application Publication No. 2021-70692, the anion with a cyclic ether group as described in Japanese Patent Application Publication No. 2018-180525 and Japanese Patent Application Publication No. 2021-35935, and the anion as described in Japanese Patent Application Publication No. 2018-92159.

[0172] The aforementioned non-nucleophilic relative ions may also be the anions of benzenesulfonic acid derivatives without fluorine atoms as described in Japanese Patent Application Publication No. 2006-276759, Japanese Patent Application Publication No. 2015-117200, Japanese Patent Application Publication No. 2016-65016 and Japanese Patent Application Publication No. 2019-202974, the benzenesulfonic acid anions without fluorine atoms bonded by aromatic groups containing iodine atoms as described in Japanese Patent No. 6645464, and the alkylsulfonic acid anions.

[0173] The aforementioned non-nucleophilic relative ions may also be the anions of disulfonic acid as described in Japanese Patent Application Publication No. 2015-206932, the anions of sulfonamide and sulfenamide as described in International Patent Application Publication No. 2020 / 158366, which are sulfonic acid on one side and different on the other side, or the anions of sulfonamide and carboxylic acid as described in Japanese Patent Application Publication No. 2015-24989.

[0174] In equations (B7) and (B8), g1 and g2 are each independently 0, 1, 2 or 3, with 1 being the preferred value.

[0175] In equation (B9), h1 is 0 or 1. h2 is 0, 1, 2, 3 or 4. h3 is 0, 1, 2, 3 or 4. However, when h1 is 0, 0 ≦ h2 + h3 ≦ 4, and when h1 is 1, 0 ≦ h2 + h3 ≦ 6.

[0176] In formulas (B7), (B8), and (B9), L1 can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Among these, from a synthetic point of view, ether bonds, ester bonds, and carbonyl groups are more ideal, with ester bonds and carbonyl groups being even more ideal.

[0177] In formula (B7), Rf1 and Rf2 are each independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Of these, for Rf1 and Rf2, it is preferable that both are fluorine atoms to improve the acid strength of the produced acid. Rf3 and Rf4 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Of these, it is preferable that at least one of Rf3 and Rf4 is trifluoromethyl to improve solvent solubility.

[0178] In formula (B8), Rf5 and Rf6 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. However, not all of Rf5 and Rf6 are hydrogen atoms simultaneously. Among these, it is preferable that at least one of Rf5 and Rf6 is trifluoromethyl in order to improve solvent solubility.

[0179] In formula (B9), Rf7 is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated alkyl thio group having 1 to 6 carbon atoms. Ideally, Rf7 should be a fluorine atom, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, or difluoromethylthio, with fluorine atom, trifluoromethyl, or trifluoromethoxy being more ideal. When h2 is 2, 3, or 4, each Rf7 can be the same or different.

[0180] In formula (B9), R43 is a halogen atom other than a fluorine atom, or it may be a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given as those exemplified in the description of formula (A) for the hydrocarbon group represented by R1, but are not limited to these. Furthermore, when h3 is 2, 3, or 4, each R43 may be the same or different from the others.

[0181] Furthermore, when h3 is 2, 3, or 4, multiple R43 atoms can bond to each other and form a ring together with the carbon atoms they are bonded to. Specific examples of the rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. Also, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, some of the -CH2- groups in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the rings may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), and haloalkyl groups.

[0182] Specific examples of the anion of repeating unit B7 can be listed below, but are not limited to these. Also, in the following formula, RA is as described above, and Me is a methyl group. [Chemistry 94]

[0183] [Chemistry 95]

[0184] [Chemistry 96]

[0185] [Chemistry 97]

[0186] [Chem. 98]

[0187] [Chemistry 99]

[0188] [Chemistry 100]

[0189] [Chemistry 101]

[0190] [Chemistry 102]

[0191] [Chemistry 103]

[0192] [Chemistry 104]

[0193] [Chemistry 105]

[0194] [Chemistry 106]

[0195] Specific examples of anions in the repeating unit B8 can be listed below, but are not limited to these. Also, in the following formula, RA is as described above. [Chemistry 107]

[0196] [Chemistry 108]

[0197] [Chemistry 109]

[0198] [Chemical 110]

[0199] [Chemistry 111]

[0200] [Chemistry 112]

[0201] [Chemistry 113]

[0202] [Chemistry 114]

[0203] [Chemistry 115]

[0204] [Chemistry 116]

[0205] [Chemistry 117]

[0206] Specific examples of the anions of repeating unit B9 can be listed below, but are not limited to these. Also, in the following formula, RA is as described above. [Chemistry 118]

[0207] [Chemistry 119]

[0208] [Chemistry 120]

[0209] [Chemistry 121]

[0210] [Chemistry 122]

[0211] [Chemistry 123]

[0212] [Chemistry 124]

[0213] [Chemistry 125]

[0214] [Chemistry 126]

[0215] [Chemistry 127]

[0216] [Chemistry 128]

[0217] [Chemistry 129]

[0218] [Chemistry 130]

[0219] [Chemistry 131]

[0220] [Chemistry 132]

[0221] [Chemistry 133]

[0222] [Chemistry 134]

[0223] Specific examples of anions in the repeating unit B10 can be listed below, but are not limited to these. Also, in the following formula, RA is as described above. [Chemistry 135]

[0224] In formulas (B7) to (B10), A+ is an onium cation. Preferably, the onium cation is represented by strontium cation as shown in formula (Z-1) or monium cation as shown in formula (Z-2). [Chemistry 136]

[0225] In formulas (Z-1) and (Z-2), Rct1 to Rct5 are each independently a halogen atom, or may contain a hydrocarbon group with 1 to 30 carbon atoms of heteroatoms.

[0226] Specific examples of halogen atoms represented by Rct1~Rct5 include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0227] Rct1 to Rct5 represent hydrocarbon groups that can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, and tributyl; cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 30 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclohexenyl and other cyclic unsaturated hydrocarbon groups with 3 to 30 carbon atoms; aryl groups with 6 to 30 carbon atoms such as phenyl, naphthyl, and thiophene; aralkyl groups with 7 to 30 carbon atoms such as benzyl, 1-phenylethyl, and 2-phenylethyl; and combinations thereof, with aryl groups being preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- portion of the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, it may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups.

[0228] Furthermore, Rct1 and Rct2 can also bond to each other and form a ring together with the sulfur atoms they are bonded to. Specific examples of the aforementioned ring structures can be shown in the following formulas. [Chemistry 137] In the formula, the dashed lines represent the atomic bonds between Rct3 and Rct3.

[0229] Specific examples of strontium cations represented by formula (Z-1) may be found in paragraphs

[0102] to

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

[0070] to

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

[0230] Specific examples of citric acid represented by formula (Z-2) can be found in paragraph

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

[0231] The Z+ cation represents the onion cation, and the strontium cation represented by formula (Z-3) is also ideal. [Chemistry 138]

[0232] In formula (Z-3), m1 is 0 or 1. When m1 is 0, it is a benzene ring; when m1 is 1, it is a naphthalene ring. From the viewpoint of solvent solubility, a benzene ring with m1 = 0 is preferred. m2 is 0 or 1. When m2 is 0, it is a benzene ring; when m2 is 1, it is a naphthalene ring. From the viewpoint of solvent solubility, a benzene ring with m2 = 0 is preferred. m3 is 0 or 1. When m3 is 0, it is a benzene ring; when m3 is 1, it is a naphthalene ring. From the viewpoint of solvent solubility, a benzene ring with m3 = 0 is preferred.

[0233] In formula (Z-3), m4 is 0, 1, 2, 3, or 4. The more iodine atoms in the cation structure, the higher the absorption, especially for EUV, but the less solvent solubility there will be concerns about precipitation in the inhibitor composition. Therefore, m4 is better if it is 0, 1, 2, or 3, with 0, 1, or 2 being even better.

[0234] In formula (Z-3), m5 can be 0, 1, 2, 3, or 4. From the perspective of raw material scheduling, m5 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being even better. m6 can be 0, 1, 2, 3, 4, 5, or 6. From the perspective of raw material scheduling, m6 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being even better. m7 can be 0, 1, 2, 3, 4, 5, or 6. From the perspective of raw material scheduling, m7 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being even better.

[0235] In formula (Z-3), m8 can be 0, 1, or 2. From the perspective of raw material scheduling, m8 being 0 or 1 is preferred. m9 can be 0, 1, or 2. From the perspective of raw material scheduling, m9 being 0 or 1 is preferred. m10 can be 0, 1, or 2. From the perspective of raw material scheduling, m10 being 0 or 1 is preferred.

[0236] In formula (Z-3), m11 is 0 or 1. When m11 is 0, it is a benzene ring; when m11 is 1, it is a naphthalene ring. From the viewpoint of solvent solubility, the benzene ring with m11 of 0 is preferred.

[0237] In formula (Z-3), m12 is 0, 1, 2, 3, or 4. The more iodine atoms in the cation structure, the higher the absorption, especially for EUV, but the less solvent solubility there is a concern about precipitation in the inhibitor composition. Therefore, m12 is better if it is 0, 1, 2, or 3, with 0, 1, or 2 being even better.

[0238] In equation (Z-3), m13 is 0, 1, or 2. From the perspective of raw material scheduling, m13 being 0 or 1 is preferred. m14 is 0, 1, or 2. Considering the synthesis aspect, m14 being 0 or 1 is preferred.

[0239] When m1 is 0, 0 ≤ m6 + m9 ≤ 4; when m1 is 1, 0 ≤ m6 + m9 ≤ 6. When m2 is 0, 0 ≤ m7 + m10 ≤ 4; when m2 is 1, 0 ≤ m7 + m10 ≤ 6. When m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4; when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6. When m11 is 0, 0 ≤ m12 + m13 ≤ 4; when m11 is 1, 0 ≤ m12 + m13 ≤ 6. Also, m4 + m12 ≥ 1.

[0240] In formula (Z-3), RF1 to RF3 are each independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms. Among these, trifluoromethyl, trifluoromethoxy, and trifluorothiomethoxy are preferred. When m5 is 2 or more, each RF1 may be the same or different from each other; when m6 is 2 or more, each RF2 may be the same or different from each other; when m7 is 2 or more, each RF3 may be the same or different from each other.

[0241] In formula (Z-3), Rct6 to Rct9 can be halogen atoms other than iodine and fluorine atoms, nitro, cyano, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. The hydrocarbon base of the aforementioned hydrocarbon group, hydrocarbon oxy group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given, and the same examples as those exemplified in the description of formula (A) for the hydrocarbon group represented by R1 can be cited. Furthermore, some or all of the hydrogen atoms in the hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon sulfide group mentioned above can be replaced by a group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom, and halogen atom. The -CH2- part of the aforementioned hydrocarbon group can also be replaced by a group containing heteroatoms such as oxygen atom, sulfur atom, and nitrogen atom. As a result, it may also contain hydroxyl group, cyano group, fluorine atom, chlorine atom, bromine atom, iodine atom, carbonyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulfonolactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl group, etc.

[0242] Furthermore, when m8 is 2, the two Rct6 atoms can be the same or different, and they can also bond to each other and form a ring together with the carbon atoms they are bonded to. When m9 is 2, the two Rct7 atoms can be the same or different, and they can also bond to each other and form a ring together with the carbon atoms they are bonded to. When m10 is 2, the two Rct8 atoms can be the same or different, and they can also bond to each other and form a ring together with the carbon atoms they are bonded to. When m13 is 2, the two Rct9 atoms can be the same or different, and they can also bond to each other and form a ring together with the carbon atoms they are bonded to. Specific examples of the rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norcamphene rings, and adamantane rings. Furthermore, some or all of the hydrogen atoms in the aforementioned ring can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. Similarly, some of the -CH2- in the aforementioned ring can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, the ring may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0243] Furthermore, the aromatic rings in the strontium cation represented by formula (Z-3) that are directly bonded to S+ can also bond to each other and form rings together with S+. Specific examples of the aforementioned ring structures can be shown in the following formulas. [Chemistry 139] In the formula, the dashed lines represent atomic bonds.

[0244] In formula (Z-3), LB and LC are each independently a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Of these, LB is preferably a single bond, ether bond, ester bond, or sulfonate bond, with ester bond or sulfonate bond being more preferred. LC is preferably a single bond, ether bond, or ester bond, with single bond being more preferred.

[0245] In formula (Z-3), XL is a single bond, or may contain a heteroatom with 1 to 40 carbon atoms in an extended hydrocarbon group. The aforementioned extended hydrocarbon group can be straight-chain, branched, or cyclic, and specific examples include alkyldiyl, cyclic saturated extended hydrocarbon group, and extended aryl group. Specific examples of the aforementioned heteroatom include oxygen atom, nitrogen atom, sulfur atom, etc.

[0246] XL can also contain heteroatoms with carbon numbers of 1 to 40, and specific examples are listed below, but are not limited to these. Also, in the following formula, * represents the atomic bonds of LB and LC. [Chemistry 140]

[0247] [Chemistry 141]

[0248] [Chemistry 142]

[0249] [Chemistry 143]

[0250] Of these, XL-0~XL-22, XL-29~XL-34, and XL-47~XL-58 are preferred.

[0251] The strontium cation represented by formula (Z-3) is preferably represented by formula (Z-3-1). [Chemistry 144] In the formula, m4~m10, m12~m14, RF1~RF3, Rct6~Rct9, LB, LC and XL are as described above.

[0252] The strontium cation represented by formula (Z-3-1) is preferably represented by formula (Z-3-2). [Chemistry 145] In the formula, m4~m10, RF1~RF3 and Rct6~Rct8 are as described above.

[0253] Specific examples of strontium cations represented by formula (Z-3) are listed below, but are not limited to these. Also, in the following formula, Me is a methyl group. [Chemistry 146]

[0254] [Chemistry 147]

[0255] [Chemistry 148]

[0256] [Chemistry 149]

[0257] [Chemistry 150]

[0258] [Chemistry 151]

[0259] [Chemistry 152]

[0260] [Chemistry 153]

[0261] [Chemistry 154]

[0262] [Chemistry 155]

[0263] [Chemistry 156]

[0264] [Chemistry 157]

[0265] [Chemistry 158]

[0266] [Chemistry 159]

[0267] [Chemistry 160]

[0268] [Chemistry 161]

[0269] [Chemistry 162]

[0270] [Chemistry 163]

[0271] [Chemistry 164]

[0272] [Chemistry 165]

[0273] [Chemistry 166]

[0274] [Chemistry 167]

[0275] [Chemistry 168]

[0276] [Chemistry 169]

[0277] [Chemistry 170]

[0278] [Chemistry 171]

[0279] [Chemistry 172]

[0280] [Chemistry 173]

[0281] The specific structures of repeating units B6 to B10 can be any combination of the aforementioned anions and cations.

[0282] Repeating units B6 to B10 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 moderately suppressed, resulting in a pattern with reduced LER (Left-to-Rate) density. Furthermore, by including these units in the polymer, the phenomenon of acid evaporating from the exposed areas and re-adhering to the unexposed areas during vacuum baking can be suppressed, which is believed to be effective in reducing LER and minimizing shape degradation caused by undesirable film loss in the unexposed areas.

[0283] Among the repeating units B6 to B10, from the perspective of the unit that is most beneficial to blank photomask processing, repeating units B7 to B10 are more ideal in terms of acid strength in terms of acid diffusion suppression and design of acid unstable groups of polymers, and repeating units B8, B9 and B10 are even more ideal.

[0284] The repeating units B6 to B10 are preferably introduced in the range of 0.1 to 30 mol%, and more preferably in the range of 0.5 to 20 mol%, of all repeating units in the aforementioned polymer. Repeating units B6 to B10 can be used alone or in combination of two or more.

[0285] Of all the repeating units in the aforementioned polymer, it is ideal for the content of repeating units with an aromatic ring skeleton to be 65 mol% or more, more preferably 75 mol% or more, and even more preferably 85 mol% or more. When repeating units B6 to B10 are not present, it is preferable for all units to have an aromatic ring skeleton.

[0286] The aforementioned polymers may also contain commonly used (meth)acrylate units protected by acid-indeterminate groups, or (meth)acrylate units with lactone structures or hydroxyl groups other than phenolic hydroxyl groups. These repeating units allow for fine-tuning of the properties of the resist film, but they may also be omitted.

[0287] Examples of (meth)acrylate units with the aforementioned binding groups include repeating units represented by formula (B11) (hereinafter also referred to as repeating unit B11), repeating units represented by formula (B12) (hereinafter also referred to as repeating unit B12), and repeating units represented by formula (B13) (hereinafter also referred to as repeating unit B13). These units are not acidic and can be used as auxiliary units to provide adhesion to the substrate and to adjust solubility. [Chemistry 174]

[0288] In formulas (B11) to (B13), RA is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R51 is -O- or a methylene group. R52 is a hydrogen atom or a hydroxyl group. R53 is a saturated hydrocarbon group with 1 to 4 carbon atoms. i is 0, 1, 2, or 3.

[0289] When the polymer contains repeating units B11 to B13, it is ideal for the content to be 0 to 20 mol% of all repeating units in the aforementioned polymer, and even more ideal to be 0 to 10 mol%. Repeating units B11 to B13 can be used alone or in combination of two or more.

[0290] The aforementioned polymer can be synthesized by copolymerizing monomers protected with protecting groups as needed using known methods, followed by deprotection reactions as required. The copolymerization reaction is not particularly limited, but free radical polymerization or anionic polymerization is preferred. For reference to such methods, see Japanese Patent Application Publication No. 2004-115630.

[0291] For the aforementioned polymer, a weight-average molecular weight (Mw) of 1000-50000 is preferred, and 2000-20000 is even more ideal. If Mw is 1000 or higher, as is known in the past, there is no risk of pattern top rounding leading to reduced resolution and LER degradation. On the other hand, if Mw is 50000 or lower, there is no risk of LER degradation, especially when forming patterns with a linewidth of 100 nm or lower. Furthermore, in this invention, Mw is a polystyrene equivalent value obtained by gel permeation chromatography (GPC) using THF or DMF as a solvent.

[0292] The aforementioned polymer has a narrow dispersion with a molecular weight distribution (Mw / Mn) of 1.0 to 2.0, preferably 1.0 to 1.9, and even more preferably 1.0 to 1.8. With such a narrow dispersion, there will be no foreign matter on the pattern or deterioration of the pattern shape after development.

[0293] Furthermore, regarding the aforementioned basic polymer design, a dissolution rate of 10 nm / min or less for alkaline developer is ideal, 7 nm / min or less is better, and 5 nm / min or less is even more ideal. In advanced generations, when the coating film on the substrate is in the thin film range (below 100 nm), the impact of pattern film loss due to alkaline development increases. When the alkaline dissolution rate of the polymer is greater than 10 nm / min, the pattern collapses, making it impossible to form fine patterns. This is especially noticeable when fabricating photomasks that require defect-free results, as there is a strong tendency for strong development processing. In this invention, the dissolution rate of the basic polymer for alkaline developer is calculated from the film loss during spin-coating of an 8-inch silicon wafer with a polymer solution (polymer concentration: 16.7% by mass, solvent: propylene glycol monomethyl ether acetate (PGMEA)), baking at 100°C for 90 seconds to form a 1000 nm thick film, followed by development with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 23°C for 100 seconds.

[0294] (B) The base polymer of the component may also contain other polymers besides those mentioned above. Other polymers may be those previously known in relation to the base polymer used in the inhibitor composition. There are no particular limitations on the content of other polymers, as long as they do not impair the effects of the present invention.

[0295] [(C) Organic solvent] The inhibitor composition of the present invention may also contain an organic solvent as component (C). There are no particular limitations on the aforementioned organic solvent, as long as it can dissolve each component. Examples of such organic solvents include: ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone as described in paragraphs

[0144] to

[0145] of Japanese Patent Application Publication No. 2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; and propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, etc. Ethers such as monomethyl ether of alcohol, monoethyl ether of propylene glycol, monoethyl ether of ethylene glycol, dimethyl ether of propylene glycol, and dimethyl ether of diethylene glycol; esters such as PGMEA, ethyl ether acetate of propylene glycol, ethyl lactate (EL), ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and tert-butyl ether acetate of propylene glycol; lactones such as γ-butyrolactone; and mixed solvents thereof. When using the unstable group of an acetal-based acid, a high-boiling-point alcohol solvent can be added to accelerate the deprotection reaction of the acetal. Specifically, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, and 1,3-butanediol can be added.

[0296] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, PGME, cyclohexanone, EL, γ-butyrolactone, and mixtures thereof are preferred.

[0297] When the chemical amplification positive inhibitor composition of the present invention contains (C) organic solvent, its content relative to 80 parts by mass of (B) base polymer is ideally 200-10000 parts by mass, and even more ideally 400-5000 parts by mass. (C) Organic solvent can be used alone or in combination of two or more.

[0298] [(D) Photoacid generator] The chemical amplification positive inhibitor composition of the present invention may also contain a photoacid generator as component (D). There are no particular limitations on the aforementioned photoacid generator, as long as it is a compound that produces acid upon irradiation by high-energy rays. Ideal photoacid generators include strontium salts, ferrous salts, sulfonyldiazomethane, N-sulfonoxyimide, and oxime-O-sulfonate type acid generators.

[0299] Specific examples of the aforementioned photoacid generators include nonafluorobutane sulfonate, the partially fluorinated sulfonate described in paragraphs

[0247] to

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

[0261] to

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

[0122] to

[0142] of Japanese Patent Application Publication No. 2008-111103, and the partially fluorinated sulfonate described in paragraphs

[0080] to

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

[0300] Such photoacid generators are preferably salt compounds containing the anions shown below. [Chemistry 175]

[0301] [Chemistry 176]

[0302] [Chemistry 177]

[0303] [Chemistry 178]

[0304] [Chemistry 179]

[0305] [Chemistry 180]

[0306] [Chemistry 181]

[0307] [Chemistry 182]

[0308] [Chemistry 183]

[0309] [Chemistry 184]

[0310] [Chemistry 185]

[0311] [Chemistry 186]

[0312] [Chemistry 187]

[0313] [Chem.188]

[0314] [Chemistry 189]

[0315] [Chemistry 190]

[0316] [Chemistry 191]

[0317] [Chemistry 192]

[0318] [Chemistry 193]

[0319] [Chemistry 194]

[0320] [Chemistry 195]

[0321] [Chemistry 196]

[0322] [Chemistry 197]

[0323] [Chemistry 198]

[0324] [Chemistry 199]

[0325] [Chemistry 200]

[0326] [Chemical Engineering 201]

[0327] [Chemical Engineering 202]

[0328] [Chemical Engineering 203]

[0329] [Chemical 204]

[0330] [Chemical Engineering 205]

[0331] [Chemical Engineering 206]

[0332] [Chemical 207]

[0333] [Chemical Engineering 208]

[0334] [Chemical Engineering 209]

[0335] [Chemical 210]

[0336] [Chemistry 211]

[0337] [Chemistry 212]

[0338] [Chemistry 213]

[0339] [Chemistry 214]

[0340] [Chemical 215]

[0341] [Chemistry 216]

[0342] [Chemistry 217]

[0343] [Chemistry 218]

[0344] [Chemistry 219]

[0345] [Chem.220]

[0346] [Chemistry 221]

[0347] [Chemistry 222]

[0348] [Chemistry 223]

[0349] [Chemistry 224]

[0350] [Chemistry 225]

[0351] [Chemistry 226]

[0352] [Chemistry 227]

[0353] [Chemistry 228]

[0354] [Chemistry 229]

[0355] [Chemistry 230]

[0356] [Chemistry 231]

[0357] [Chemistry 232]

[0358] [Chemistry 233]

[0359] [Chemistry 234]

[0360] [Chemistry 235]

[0361] [Chemistry 236]

[0362] [Chemistry 237]

[0363] [Chemistry 238]

[0364] [Chemistry 239]

[0365] [Chemistry 240]

[0366] [Chemistry 241]

[0367] [Chemistry 242]

[0368] [Chemistry 243]

[0369] [Chemistry 244]

[0370] [Chemistry 245]

[0371] [Chemistry 246]

[0372] [Chemistry 247]

[0373] [Chemistry 248]

[0374] [Chemistry 249]

[0375] [Chemistry 250]

[0376] [Chemistry 251]

[0377] [Chemistry 252]

[0378] [Chemistry 253]

[0379] [Chemistry 254]

[0380] [Chemistry 255]

[0381] [Chemistry 256]

[0382] [Chemistry 257]

[0383] [Chemistry 258]

[0384] [Chemistry 259]

[0385] [Chemistry 260]

[0386] [Chemistry 261]

[0387] [Chemistry 262]

[0388] [Chemistry 263]

[0389] [Chemistry 264]

[0390] [Chemistry 265]

[0391] [Chemistry 266]

[0392] [Chemistry 267]

[0393] [Chemistry 268]

[0394] [Chemistry 269]

[0395] [Chemistry 270]

[0396] [Chemistry 271]

[0397] [Chemistry 272]

[0398] [Chemistry 273]

[0399] [Chemistry 274]

[0400] [Chemistry 275]

[0401] [Chemistry 276]

[0402] [Chemistry 277]

[0403] [Chemistry 278]

[0404] [Chemistry 279]

[0405] [Chemistry 280]

[0406] [Chemistry 281]

[0407] [Chemistry 282]

[0408] [Chemistry 283]

[0409] [Chemistry 284]

[0410] [Chemistry 285]

[0411] [Chemistry 286]

[0412] [Chemistry 287]

[0413] [Chemistry 288]

[0414] [Chemistry 289]

[0415] [Chemistry 290]

[0416] [Chemistry 291]

[0417] [Chemistry 292]

[0418] [Chemistry 293]

[0419] [Chemistry 294]

[0420] [Chemistry 295]

[0421] [Chemistry 296]

[0422] [Chemistry 297]

[0423] [Chemistry 298]

[0424] [Chemistry 299]

[0425] [Chemical 300]

[0426] [Chemical Engineering 301]

[0427] [Chemical 302]

[0428] [Chemical 303]

[0429] [Chemical 304]

[0430] [Chemical 305]

[0431] [Chemical 306]

[0432] [Chemical 307]

[0433] [Chemical 308]

[0434] [Chemical 309]

[0435] [Chemical 310]

[0436] [Chemistry 311]

[0437] [Chemistry 312]

[0438] [Chemistry 313]

[0439] [Chemical 314]

[0440] [Chemical 315]

[0441] [Chemistry 316]

[0442] [Chemistry 317]

[0443] [Chemistry 318]

[0444] [Chemistry 319]

[0445] [Chem.320]

[0446] [Chemistry 321]

[0447] [Chemistry 322]

[0448] [Chemistry 323]

[0449] [Chemistry 324]

[0450] [Chemistry 325]

[0451] [Chemistry 326]

[0452] [Chemistry 327]

[0453] [Chemistry 328]

[0454] [Chemistry 329]

[0455] [Chemistry 330]

[0456] [Chemistry 331]

[0457] [Chemistry 332]

[0458] [Chemistry 333]

[0459] [Chemistry 334]

[0460] [Chemistry 335]

[0461] [Chemistry 336]

[0462] [Chemistry 337]

[0463] [Chemistry 338]

[0464] [Chemistry 339]

[0465] [Transformation 340]

[0466] [Chemistry 341]

[0467] [Chemistry 342]

[0468] [Chemistry 343]

[0469] [Chemistry 344]

[0470] [Chemistry 345]

[0471] [Chemistry 346]

[0472] [Chemistry 347]

[0473] [Chemistry 348]

[0474] [Chemistry 349]

[0475] [Chemical 350]

[0476] [Chemistry 351]

[0477] [Chemistry 352]

[0478] [Chemistry 353]

[0479] [Chemistry 354]

[0480] [Chemistry 355]

[0481] [Chemistry 356]

[0482] [Chemistry 357]

[0483] [Chemistry 358]

[0484] [Chemistry 359]

[0485] [Chemical formula 360]

[0486] [Chemical formula 361]

[0487] [Chemical formula 362]

[0488] [Chemical formula 363]

[0489] [Chemical formula 364]

[0490] [Chemical formula 365]

[0491] [Chemical formula 366]

[0492] [Chemical formula 367]

[0493] [Chemical formula 368]

[0494] [Chemical formula 369] <00023​​​​​​​​​​​​​​​​​​​​​[Chemistry 373]

[0499] [Chemistry 374]

[0500] [Chemistry 375]

[0501] [Chemistry 376]

[0502] [Chemistry 377]

[0503] [Chemistry 378]

[0504] [Chemistry 379]

[0505] [Chemistry 380]

[0506] [Chemistry 381]

[0507] [Chemistry 382]

[0508] [Chemistry 383]

[0509] [Chem. 384]

[0510] [Chem. 385]

[0511] [Chemistry 386]

[0512] [Chemistry 387]

[0513] [Chem.388]

[0514] [Chemistry 389]

[0515] [Chemistry 390]

[0516] [Chemistry 391]

[0517] [Chemistry 392]

[0518] [Chemistry 393]

[0519] [Chem. 394]

[0520] [Chemistry 395]

[0521] [Chemistry 396]

[0522] [Chemistry 397]

[0523] [Chemistry 398]

[0524] [Chemistry 399]

[0525] [Chemical 400]

[0526] [Chemical Engineering 401]

[0527] [Chemical 402]

[0528] [Chemical 403]

[0529] [Chemical 404]

[0530] [Chemical 405]

[0531] [Chemical 406]

[0532] [Chemical 407]

[0533] [Chemical 408]

[0534] [Chemical 409]

[0535] [Chemical 410]

[0536] [Chemistry 411]

[0537] [Chemistry 412]

[0538] [Chemistry 413]

[0539] [Chemistry 414]

[0540] [Chemical 415]

[0541] [Chemistry 416]

[0542] Furthermore, it is also ideal for the aforementioned photoacid generator to be a salt compound containing an anion represented by the following formula (D1). [Chemistry 417]

[0543] In equation (D1), p1 is 1, 2, or 3. p2 is 1, 2, 3, 4, or 5. p3 is 0, 1, 2, or 3. Only 1 ≤ p2 + p3 ≤ 5. q1 is 0 or 1.

[0544] In formula (D1), L21 is a single bond, ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond.

[0545] In formula (D1), L22 is an ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond.

[0546] In formula (D1), LD is a single bond or an extended hydrocarbon group with 1 to 20 carbon atoms when p1 is 1, and a (p1+1) valence hydrocarbon group with 1 to 20 carbon atoms when p1 is 2 or 3. The extended hydrocarbon group and the (p1+1) valence hydrocarbon group may also contain at least one of the following: ether bond, carbonyl group, ester bond, amide bond, sulfonyl lactone ring, amide ring, carbonate bond, halogen atom, hydroxyl group and carboxyl group.

[0547] LD indicates that the hydrocarbon group with 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl diyl groups with 1 to 20 carbon atoms, such as methane-diyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclopentane-diyl, cyclohexane-diyl, norcamphene-diyl, and adamantane-diyl; unsaturated aliphatic hydrocarbon groups with 2 to 20 carbon atoms, such as vinylene and propylene-1,3-diyl; aryl groups with 6 to 20 carbon atoms, such as phenylene and naphthyl; and groups obtained by combining them. Furthermore, LD represents a (p1+1) valence hydrocarbon group with 1 to 20 carbon atoms that can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be obtained by removing one or two hydrogen atoms from the aforementioned hydrocarbon groups with 1 to 20 carbon atoms.

[0548] In formula (D1), Rf21 and Rf22 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom, with at least one being a fluorine atom or a trifluoromethyl atom.

[0549] In formula (D1), R101 is a hydroxyl group, a carboxyl group, a saturated hydrocarbon group with 1 to 6 carbon atoms, a saturated hydrocarbon oxygen group with 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl oxygen group with 2 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, -N(R101A)(R101B), -N(R101C)-C(=O)-R101D, or -N(R101C)-C(=O)-O-R101D. R101A and R101B are each independently a hydrogen atom or a saturated hydrocarbon group with 1 to 6 carbon atoms. R101C is a hydrogen atom or a saturated hydrocarbon group with 1 to 6 carbon atoms. R101D is a saturated hydrocarbon group with 1 to 6 carbon atoms or an unsaturated aliphatic hydrocarbon group with 2 to 8 carbon atoms.

[0550] R101, R101A, R101B, and R101C represent saturated hydrocarbon groups with 1 to 6 carbon atoms, which can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, and n-hexyl; and cyclic saturated hydrocarbon groups with 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Furthermore, the saturated hydrocarbon base of the saturated hydrocarbon oxygen group with 1 to 6 carbon atoms represented by R101 can be the same as the specific examples of the aforementioned saturated hydrocarbon groups. The saturated hydrocarbon base of the saturated hydrocarbon carbonyl oxygen group with 2 to 6 carbon atoms represented by R101 can be those with 1 to 5 carbon atoms among the specific examples of the aforementioned saturated hydrocarbon groups with 1 to 6 carbon atoms.

[0551] R101D represents unsaturated aliphatic hydrocarbon groups with 2 to 8 carbon atoms, which can be linear, branched, or cyclic. Specific examples include alkenyl groups with 2 to 8 carbon atoms such as vinyl, propenyl, butenyl, and hexenyl; alkynyl groups with 2 to 8 carbon atoms such as ethynyl, propynyl, and butynyl; and cyclic unsaturated aliphatic hydrocarbon groups with 3 to 8 carbon atoms such as cyclohexenyl and norcamphenyl.

[0552] In formula (D1), R102 is a saturated hydrocarbon group with 1 to 20 carbon atoms or an aryl group with 6 to 20 carbon atoms. Some or all of the hydrogen atoms of the saturated hydrocarbon group may be replaced by halogen atoms other than fluorine atoms. Some or all of the hydrogen atoms of the aryl group may also be replaced by substituents selected from saturated hydrocarbon groups with 1 to 20 carbon atoms, saturated hydrocarbon oxygen groups with 1 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, halogen atoms and hydroxyl groups.

[0553] R102 indicates that the hydrocarbon group with 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given that are the same as those given for the hydrocarbon group with 1 to 20 carbon atoms represented by LB.

[0554] Specific examples of aryl groups with 6 to 20 carbon atoms represented by R102 include arylphenyl, arylnaphthyl, phenanthrenediyl, and anthracenediyl. The saturated hydrocarbon group with 1 to 20 carbon atoms and the hydrocarbon group with 1 to 20 carbon atoms of the substituents of the aforementioned aryl groups can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, decadecyl, heptadecyl, octadecyl, nonadecanyl, and icosyl; and cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl. Specific examples of aryl groups with 6 to 14 carbon atoms as substituents include arylphenyl, arylnaphthyl, phenanthrenediyl, anthracenediyl, etc.

[0555] The anion represented by formula (D1) is preferably represented by the anion represented by formula (D2). [Chemistry 418]

[0556] In formula (D2), p1, p2, p3, L21, LD, and R101 are as described above. q2 is 1, 2, 3, or 4. R102A is a saturated hydrocarbon group with 1 to 20 carbon atoms, a saturated hydrocarbon oxygen group with 1 to 20 carbon atoms, an aryl group with 6 to 14 carbon atoms, a halogen atom, or a hydroxyl group. Furthermore, when q2 is 2, 3, or 4, each R102A may be the same or different from the others.

[0557] Specific examples of anions represented by formula (D1) can be listed below, but are not limited to these. [Chemistry 419]

[0558] [Chem.420]

[0559] [Chemistry 421]

[0560] [Chemistry 422]

[0561] [Chemistry 423]

[0562] [Chemistry 424]

[0563] [Chemical 425]

[0564] [Chemistry 426]

[0565] [Chemistry 427]

[0566] [Chemistry 428]

[0567] [Chemistry 429]

[0568] [Chemistry 430]

[0569] [Chemistry 431]

[0570] [Chemistry 432]

[0571] [Chemistry 433]

[0572] [Chemistry 434]

[0573] [Chemistry 435]

[0574] [Chemistry 436]

[0575] [Chemistry 437]

[0576] [Chemistry 438]

[0577] [Chemistry 439]

[0578] [Chemistry 440]

[0579] [Chemistry 441]

[0580] [Chemistry 442]

[0581] [Chemistry 443]

[0582] [Chemistry 444]

[0583] [Chemistry 445]

[0584] [Chemistry 446]

[0585] [Chemistry 447]

[0586] [Chemistry 448]

[0587] [Chemistry 449]

[0588] [Chemistry 450]

[0589] [Chemistry 451]

[0590] [Chemistry 452]

[0591] [Chemistry 453]

[0592] [Chemistry 454]

[0593] [Chemistry 455]

[0594] (D) In ​​the photoacid generating agent, the cation paired with the aforementioned anion is preferably a strontium cation or a ferrophosphate cation. Specific examples of the aforementioned strontium cation may be the same as those exemplified by strontium cations represented by formulas (Z-1) and (Z-3), but are not limited to these. Specific examples of the aforementioned ferrophosphate cation may be the same as those exemplified by ferrophosphate cations represented by formula (Z-2), but are not limited to these.

[0595] For the acid produced by the aforementioned photoacid generator, a pKa of -2.0 or higher is ideal, and -1.0 or higher is even more desirable. Furthermore, an upper limit of 2.0 for the pKa is preferred. The pKa values ​​were calculated using the pKa database in ACD / Chemsketch ver: 9.04 software developed by Advanced Chemistry Development, Inc.

[0596] When the chemically amplified positive resist composition of the present invention contains a (D) photoacid generator, its content is ideally 1 to 10 parts by mass relative to 80 parts by mass of the aforementioned base polymer, and more ideally 1 to 5 parts by mass. By containing the (D) photoacid generator, the amount of acid generated in the exposed area and the solubility inhibition of the unexposed area can be appropriately adjusted. The (D) photoacid generator can be used alone or in combination of two or more.

[0597] When the chemically amplified positive resist composition of the present invention contains both (D) a photoacid generator and (A) a quencher, the ratio of the photoacid generator to the quencher (photoacid generator / quencher) is preferably less than 3 by mass, more preferably less than 2.5, and ideally less than 2. If the ratio of the photoacid generator to the quencher in the aforementioned chemically amplified positive resist composition is within the aforementioned range, acid diffusion can be sufficiently suppressed, and excellent resolution and dimensional uniformity can be obtained.

[0598] [(E) Polymers containing fluorine atoms] The chemically amplified positive resist composition of the present invention, in order to achieve high contrast, suppress the chemical flash phenomenon of acid under high-energy radiation, and shield the mixing of acid from the antistatic film during the coating of the antistatic film material onto the resist film, and prevent unintended pattern degradation, may also include a polymer containing fluorine atoms as component (E) containing at least one of the repeating units represented by formula (E1) (hereinafter also referred to as repeating unit E1.), repeating units represented by formula (E2) (hereinafter also referred to as repeating unit E2.), repeating units represented by formula (E3) (hereinafter also referred to as repeating unit E3.), and repeating units represented by formula (E4) (hereinafter also referred to as repeating unit E4.). The aforementioned polymer containing fluorine atoms also acts as a surfactant, thus preventing the re-adhesion of insoluble substances that may be generated during the development process to the substrate, and also exerting an effect on development defects. [Chemistry 456]

[0599] In formulas (E1) to (E4), k is 1, 2, or 3. RB are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R201, R202, R204, and R205 are each independently a hydrogen atom or a saturated hydrocarbon group with 1 to 10 carbon atoms. R203, R206, R207, and R208 are each independently a hydrogen atom, a hydrocarbon group with 1 to 15 carbon atoms, a fluorinated hydrocarbon group with 1 to 15 carbon atoms, or an acid-unstable group. When R203, R206, R207, and R208 are hydrocarbon groups or fluorinated hydrocarbon groups, an ether bond or a carbonyl group may be inserted between the carbon-carbon bonds. Z1 is a (k+1) valence hydrocarbon group with 1 to 20 carbon atoms or a (k+1) valence fluorinated hydrocarbon group with 1 to 20 carbon atoms.

[0600] R201, R202, R204, and R205 represent saturated hydrocarbon groups with 1 to 10 carbon atoms, which can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornel. Among these, saturated hydrocarbon groups with 1 to 6 carbon atoms are preferred.

[0601] R203, R206, R207, and R208 represent hydrocarbon groups with 1 to 15 carbon atoms that can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 15 carbon atoms, alkenyl groups with 2 to 15 carbon atoms, and alkynyl groups with 2 to 15 carbon atoms, but alkyl groups with 1 to 15 carbon atoms are preferred. In addition to the aforementioned alkyl groups, examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, and n-pentadecayl. Furthermore, fluorinated hydrocarbon groups can be groups in which one or all of the hydrogen atoms bonded to the carbon atoms of the aforementioned hydrocarbon groups are replaced by fluorine atoms.

[0602] Z1 represents a (k+1) valence hydrocarbon group with 1 to 20 carbon atoms, which can be exemplified by alkyl groups with 1 to 20 carbon atoms or cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, having removed k hydrogen atoms. Furthermore, Z1 represents a (k+1) valence fluorinated hydrocarbon group with 1 to 20 carbon atoms, which can be exemplified by groups in which at least one hydrogen atom of the aforementioned (k+1) valence hydrocarbon group is replaced by a fluorine atom.

[0603] Specific examples of repeating units E1 to E4 can be listed below, but are not limited to these. Also, in the following formula, RB is as described above. [Chemistry 457]

[0604] [Chemistry 458]

[0605] [Chemistry 459]

[0606] Furthermore, the aforementioned polymer containing fluorine atoms preferably contains at least one of the repeating units represented by the following formula (E5) (hereinafter also referred to as repeating unit E5.) and the repeating units represented by the following formula (E6) (hereinafter also referred to as repeating unit E6.). [Chemistry 460]

[0607] In formulas (E5) and (E6), j1 is 1, 2, or 3. j2 is an integer satisfying 0 ≤ j2 ≤ 5 + 2(j3) - j1. j3 is 0 or 1. RC are each independently a hydrogen atom or a methyl group. R209 is a hydrogen atom, or a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms, which may also have heteroatoms inserted between carbon-carbon bonds. R210 is a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms, which may also have heteroatoms inserted between carbon-carbon bonds. R211 is a saturated hydrocarbon group with 1 to 20 carbon atoms, in which at least one hydrogen atom is replaced by a fluorine atom, and part of the -CH2- of the aforementioned saturated hydrocarbon group may also be replaced by an ester bond or an ether bond. Z2 is a single bond, *-C(=O)-O-, or *-C(=O)-NH-. Z3 is a single bond, -O-, *-C(=O)-O-Z31-Z32-, or *-C(=O)-NH-Z31-Z32-. Z31 is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms. Z32 is a single bond, ester bond, ether bond, or sulfonamide bond. * is an atomic bond with a carbon atom in the main chain.

[0608] R209 and R210 represent hydrocarbon groups with 1 to 5 carbon atoms, including alkyl, alkenyl, and ynyl groups, but alkyl is preferred. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, and n-pentyl. Furthermore, heteroatoms containing oxygen, sulfur, or nitrogen atoms can be inserted between the carbon-carbon bonds of the aforementioned hydrocarbon groups.

[0609] In formula (E5), -OR209 is preferably a hydrophilic group. In this case, R209 is preferably a hydrogen atom or an alkyl group with 1 to 5 carbon atoms with an oxygen atom inserted between carbon-carbon bonds.

[0610] R211 indicates that at least one hydrogen atom of a saturated hydrocarbon group with 1 to 20 carbon atoms is replaced by a fluorine atom. It can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms or cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom.

[0611] Z2 is preferably *-C(=O)-O- or *-C(=O)-NH-. Furthermore, RC is preferably methyl. The presence of a carbonyl group in Z2 enhances its ability to capture acids from the antistatic film. Also, if RC is methyl, it becomes a rigid polymer with a higher glass transition temperature (Tg), thus inhibiting acid diffusion. Consequently, the antistatic film exhibits good long-term stability, and its resolution and pattern shape do not deteriorate.

[0612] Z3 indicates that the saturated extended hydrocarbon group with 1 to 10 carbon atoms can be straight-chain, branched, or cyclic. Specific examples include methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, and 1,1-dimethylethane-1,2-diyl.

[0613] Repeating unit E5 can be listed below, but is not limited to these. Also, in the following formula, RC is as described above. [Chemistry 461]

[0614] [Chemistry 462]

[0615] Repeating unit E6 can be listed below, but is not limited to these. Also, in the following formula, RC is as described above. [Chemistry 463]

[0616] [Chemistry 464]

[0617] [Chemistry 465]

[0618] [Chemistry 466]

[0619] The content of repeating units E1 to E4 is ideally 15 to 95 mol% of all repeating units in the aforementioned polymer containing fluorine atoms, and more ideally 20 to 85 mol%. The content of repeating units E5 and / or E6 is ideally 5 to 85 mol% of all repeating units in the aforementioned polymer containing fluorine atoms, and more ideally 15 to 80 mol%. Repeating units E1 to E6 can be used alone or in combination of two or more.

[0620] (E) Polymers containing fluorine atoms may also contain other repeating units besides the aforementioned repeating units. Examples of such repeating units can be found in paragraphs

[0046] to

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

[0621] (E) Polymers containing fluorine atoms can be synthesized by copolymerizing monomers, which are protected by protecting groups as needed, using known methods, followed by deprotection reactions as required. The copolymerization reaction is not particularly limited, but free radical polymerization and anionic polymerization are preferred. For reference to such methods, see Japanese Patent Application Publication No. 2004-115630.

[0622] (E) For polymers containing fluorine atoms, a Mw of 2000~50000 is preferred, and 3000~20000 is even better. If the Mw is above 2000, acid does not diffuse, resolution does not deteriorate, and long-term stability is not compromised. If the Mw is below 50000, the solubility in solvents is sufficient, and coating defects do not occur. Furthermore, for polymers containing fluorine atoms, an Mw / Mn ratio of 1.0~2.2 is preferred, and 1.0~1.7 is even better.

[0623] When the chemical amplification positive inhibitor composition of the present invention includes (E) a polymer containing fluorine atoms, its content is ideally 0.01 to 30 parts by mass relative to 80 parts by mass of the base polymer (B), and more ideally 0.1 to 20 parts by mass. The polymer containing fluorine atoms (E) can be used alone or in combination of two or more.

[0624] [(F) Other quenching agents] The chemical amplification positive inhibitor composition of the present invention may also contain quenchers other than component (A) (hereinafter also referred to as other quenchers) as component (F) as required.

[0625] Other quenching agents mentioned above include conventional basic compounds. Conventional basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds with carboxyl groups, nitrogen-containing compounds with sulfonyl groups, nitrogen-containing compounds with hydroxyl groups, nitrogen-containing compounds with hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amides, amides, and carbamates. In particular, the primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103, especially amine compounds with hydroxyl groups, ether bonds, ester bonds, lactone rings, cyano groups, or sulfonate bonds, or compounds with carbamate groups described in Japanese Patent No. 3790649, are preferred. Ideal examples include tris(2-(methoxymethoxy)ethyl)amine, tris(2-(methoxymethoxy)ethyl)amine-N-oxide, dibutylaminobenzoic acid, α-line derivatives, and imidazole derivatives. Adding such basic compounds can, for example, further suppress the diffusion rate of acids within the resistive film or modify its shape.

[0626] Furthermore, other quenching agents mentioned above include onium salts such as strontium salts, ferrophosphate salts, and ammonium salts of α-unfluorinated carboxylic acids, as described in Japanese Patent Application Publication No. 2008-158339. α-fluorinated sulfonic acids, amide acids, or methylated acids are necessary for deprotecting the unstable groups of acids, but they release the α-unfluorinated carboxylic acid through salt exchange with the α-unfluorinated onium salt. Since the α-unfluorinated carboxylic acid hardly undergoes a deprotection reaction, it acts as a quenching agent.

[0627] Onium salts of carboxylic acids that are not fluorinated at the α-position, for example, those represented by the formula (F1). [Chemistry 467]

[0628] In formula (F1), R301 is a hydrogen atom or may contain a hydrocarbon group with 1 to 40 carbon atoms, except where the hydrogen atom bonded to the carbon atom at the α position of the carboxyl group is replaced by a fluorine atom or a fluorinated alkyl group.

[0629] R301 indicates that the hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 40 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tributyl, n-pentyl, tripentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclo[5.2.1.02,6]decyl, adamantyl, and adamantylmethyl; and vinyl, allyl, propenyl, butenyl, and hexenyl, etc., with 2 to 40 carbon atoms. Alkenyl; cyclohexenyl and other cyclic unsaturated aliphatic hydrocarbon groups with 3 to 40 carbon atoms; 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.) and other aryl groups with 6 to 40 carbon atoms; benzyl, 1-phenylethyl, 2-phenylethyl and other aralkyl groups with 7 to 40 carbon atoms, etc.

[0630] Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. The -CH2- portion of the aforementioned hydrocarbon group can also be replaced by a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, it may contain hydroxyl, cyano, carbonyl, ether bond, thioether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulfonolactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Examples of hydrocarbon groups containing heteroatoms include heteroaryl groups such as thiophene; alkoxyphenyl groups such as 4-hydroxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4-tert-butoxyphenyl, and 3-tert-butoxyphenyl; alkoxynaphthyl groups such as methoxynaphthyl, ethoxynaphthyl, n-propoxynaphthyl, and n-butoxynaphthyl; dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl; and aryloxyalkyl groups such as 2-phenyl-2-sideoxyethyl, 2-(1-naphthyl)-2-sideoxyethyl, and 2-(2-naphthyl)-2-sideoxyethyl.

[0631] In formula (F1), MqA+ represents an onium cation. Ideally, the onium cation should be a strontium cation, a ferromonium cation, or an ammonium cation, with strontium or ferromonium being more desirable. Specific examples of the aforementioned strontium cation are the same as those exemplified in formula (Z-1) and formula (Z-3). Similarly, specific examples of the aforementioned ferromonium cation are the same as those exemplified in formula (Z-2).

[0632] The anions of onium salts represented by formula (F1) can be listed below, but are not limited to these. [Chemistry 468]

[0633] [Chemistry 469]

[0634] [Chemistry 470]

[0635] The aforementioned quenching agent may also be suitably a strontium salt of a carboxylic acid containing an iodinated benzene ring, represented by the formula (F2). [Chemistry 471]

[0636] In equation (F2), s is 1, 2, 3, 4, or 5. t is 0, 1, 2, or 3. Only 1 ≤ s + t ≤ 5. u is 1, 2, or 3.

[0637] In formula (F2), R311 is a 1-6 carbon saturated hydrocarbon group, a 1-6 carbon saturated hydrocarbon oxygen group, a 2-6 carbon saturated hydrocarbon carbonyl oxygen group, or a 1-4 carbon saturated hydrocarbon sulfonyl oxygen group, or a hydroxyl group, fluorine atom, chlorine atom, bromine atom, amino group, nitro group, cyano group, or hydrogen atom, which may be partially or completely substituted with halogen atoms; or -N(R311A)-C(=O)-R311B or -N(R311A)-C(=O)-O-R311B. R311A is a hydrogen atom or a 1-6 carbon saturated hydrocarbon group. R311B is a 1-6 carbon saturated hydrocarbon group or a 2-8 carbon unsaturated aliphatic hydrocarbon group. When t and / or u are 2 or more, each R311 may be the same or different from the others.

[0638] In formula (F2), L21 is a single bond or a (u+1) valent linkage with 1 to 20 carbon atoms, and may also contain at least one of the following: ether bond, carbonyl group, ester bond, amide bond, sulfonyl lactone ring, amide ring, carbonate bond, halogen atom, hydroxyl group, and carboxyl group. The aforementioned saturated hydrocarbon group, saturated hydrocarbon oxy group, saturated hydrocarbon carbonyl oxy group, and saturated hydrocarbon sulfonyl oxy group may be linear, branched, or cyclic.

[0639] In formula (F2), R312, R313, and R314 are each independently a halogen atom, or may contain heteroatoms and be hydrocarbon groups with 1 to 20 carbon atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, and aralkyl groups with 7 to 20 carbon atoms. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by hydroxyl, carboxyl, halogen, oxy, cyano, nitro, sulfonyl lactone ring, sulfonyl, or strontium salt-containing groups. The -CH2- portion of the aforementioned hydrocarbon groups may also be replaced by ether, ester, carbonyl, amide, carbonate, or sulfonate bonds. Additionally, R312 and R313 may also bond to each other and form a ring together with the sulfur atoms they are bonded to.

[0640] Specific examples of compounds represented by formula (F2) can be found in Japanese Patent Application Publication No. 2017-219836. Compounds represented by formula (F2) have high absorption, high sensitization effect, and high acid diffusion control effect.

[0641] The aforementioned quenching agent can be a nitrogen-containing carboxylate compound represented by the following formula (F3). [Chemistry 472]

[0642] In formula (F3), R321 to R324 are each independently a hydrogen atom, -L31-CO2-, or may contain a heteroatom and a hydrocarbon group with 1 to 20 carbon atoms. R321 and R322, R322 and R323, or R323 and R324 may also bond to each other and form a ring together with the carbon atoms they are bonded to. L31 is a single bond or may contain a heteroatom and a hydrocarbon group with 1 to 20 carbon atoms. R325 is a hydrogen atom or may contain a heteroatom and a hydrocarbon group with 1 to 20 carbon atoms.

[0643] In formula (F3), ring Rr is a ring with 2 to 6 carbon atoms containing carbon and nitrogen atoms. Some or all of the hydrogen atoms bonded to the carbon atoms of this ring may be replaced by hydrocarbon groups with 1 to 20 carbon atoms, or by -L31-CO2-. Some of the carbon atoms of this ring may also be replaced by sulfur, oxygen, or nitrogen atoms. The aforementioned ring can be an alicyclic or aromatic ring; 5-membered or 6-membered rings are preferred. Specific examples include pyridine rings, pyrrole rings, pyrrolidinium rings, piperidine rings, pyrazole rings, imidazoline rings, pyrazine rings, pyrimidine rings, pyrazine rings, imidazoline rings, thiazole rings, thiazole rings, triazole rings, etc.

[0644] The carboxylic acid salt represented by formula (F3) has at least one -L31-CO2- group. That is, at least one of R321 to R324 is -L31-CO2-, and / or at least one of the hydrogen atoms bonded to the carbon atom of ring Rr is replaced by -L31-CO2-.

[0645] In formula (F3), MqB+ is a strontium cation, a monium cation, or an ammonium cation, with a strontium cation being preferred. Specific examples of the aforementioned strontium cations are the same as those exemplified in formula (Z-1) and formula (Z-3).

[0646] The anions of compounds represented by formula (F3) can be listed below, but are not limited to these. [Chemistry 473]

[0647] [Chemistry 474]

[0648] [Chemistry 475]

[0649] [Chemistry 476]

[0650] [Chemistry 477]

[0651] [Chemistry 478]

[0652] Furthermore, the aforementioned quenching agents can also be betaine-type compounds of weak acids. Specific examples are listed below, but are not limited to these. [Chemistry 479]

[0653] The aforementioned quenching agents can also be further exemplified by the polymer-type quenching agent disclosed in Japanese Patent Application Publication No. 2008-239918. This quenching agent enhances the rectangularity of the resist pattern by aligning to the surface of the resist film. The polymer-type quenching agent also prevents film loss and rounding of the pattern top when using a protective film for immersion exposure.

[0654] When the chemical amplification positive inhibitor composition of the present invention contains other quenchers (F), it is ideal for their content to be 0-50 parts by mass relative to 80 parts by mass of the aforementioned (B) base polymer, and even more ideal to be 0.1-40 parts by mass. The aforementioned quenchers can be used alone or in combination of two or more.

[0655] (G) Surfactants In order to improve the coating properties of the chemically amplified positive resist composition of the present invention, it may also contain a conventional surfactant as component (G). Many of the aforementioned surfactants are well known, as described in International Patent Application Publication No. 2006 / 121096, Japanese Patent Application Publication No. 2008-102383, Japanese Patent Application Publication No. 2008-304590, Japanese Patent Application Publication No. 2004-115630, and Japanese Patent Application Publication No. 2005-8766, and may be selected by referring to them.

[0656] When the chemically amplified positive inhibitor composition of the present invention contains (G) surfactant, its content relative to 80 parts by mass of (B) base polymer is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and preferably 0.01 parts by mass or more. (G) surfactant can be used alone or in combination of two or more.

[0657] [Resistant Pattern Formation Method] The resist pattern forming method of the present invention includes the following steps: forming a resist film on a substrate using the aforementioned chemically amplified positive resist composition, exposing the aforementioned resist film to high-energy rays, and developing the aforementioned irradiated resist film to obtain a resist pattern using an alkaline developer.

[0658] The aforementioned substrate can be, for example, a substrate used for integrated circuit manufacturing (Si, SiO, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective film, etc.) or a substrate used for mask circuit manufacturing (Cr, CrO, CrON, MoSi2, Si, SiO, SiO2, etc.). The aforementioned chemically amplified positive resist composition is coated onto the substrate using a spin-coating or similar method to achieve a film thickness of 0.03~2 μm. The substrate is then pre-baked on a heating plate, preferably at 60~150°C for 1~20 minutes, more preferably at 80~140°C for 1~10 minutes, to form a resist film.

[0659] Secondly, the resist film is exposed and irradiated with high-energy rays to form a pattern. Examples of such high-energy rays include ultraviolet light, far-ultraviolet light, excimer laser light (KrF, ArF, etc.), EB, EUV, X-rays, gamma rays, and synchrotron radiation.

[0660] When using ultraviolet light, far-ultraviolet light, excimer laser light, EUV, X-rays, gamma rays, or synchrotron radiation for high-energy lithography, a mask is used to form the desired pattern, with an exposure dose preferably of 1-300 mJ / cm², more preferably 10-200 mJ / cm². When using EB lithography, high-energy lithography is directly applied with an exposure dose preferably of 1-300 μC / cm², more preferably 10-200 μC / cm². Furthermore, the chemical amplification positive resist composition of this invention is particularly useful for EUV or EB lithography.

[0661] In addition to the usual exposure method, depending on the situation, an immersion method can also be used, in which a liquid is inserted between the mask and the resist film. In this case, a protective film that is insoluble in water can also be used.

[0662] Secondly, the product is exposed to heat on a heating plate at a temperature of 60-150°C for 1-20 minutes, or more preferably at 80-140°C for 1-10 minutes (PEB).

[0663] Subsequently, a developing solution containing 0.1-5% by mass, more preferably 2-3% by mass, of an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH) is used for 0.1-3 minutes, more preferably 0.5-2 minutes, using conventional methods such as dip, immersion, or spray, thereby forming the desired pattern on the substrate.

[0664] The chemically amplified positive resist composition of this invention exhibits particularly high etch resistance, and the change in pattern linewidth remains small even after prolonged exposure (PEB), making it useful when low LER (Low Etching Rate) is required. Furthermore, the resist composition of this invention is particularly suitable for use on substrates with surfaces made of materials where pattern peeling and collapse are prone to occur due to difficulty in achieving good adhesion of the resist pattern. Examples of such substrates include substrates sputtered with chromium compounds containing metallic chromium or chromium compounds selected from one or more light elements selected from oxygen, nitrogen, and carbon. The chemically amplified positive resist composition of this invention is particularly useful for pattern formation using a blank photomask as the substrate. [Example]

[0665] The following examples, embodiments, and comparative examples illustrate the present invention in detail, but the present invention is not limited to the following embodiments. Furthermore, the apparatus used is shown below. MALDI TOF-MS: S3000 manufactured by Nippon Electronics Co., Ltd.

[0666] [1] Synthesis of ferrous salts [Example 1-1] Synthesis of SQ-1 (a type of zinc salt) [Chemistry 480]

[0667] (1) Synthesis of intermediate In-1 Phenol (94.1 g), potassium carbonate (165.9 g), and sodium iodide (15.0 g) were dissolved in DMF (500 g) in a reaction vessel under nitrogen atmosphere. The temperature inside the reaction vessel was raised to 70°C, and n-octyl bromide (231.7 g) was added dropwise. After the addition, the reaction vessel was heated / cured at 80°C for 12 hours. After curing, the reaction solution was cooled, water (500 g) was added, and the reaction was stopped. The target compound was extracted with hexane (700 g). Subsequently, a conventional aqueous work-up was performed, the solvent was distilled off, and the solution was purified using a silicone column to obtain 204.3 g of intermediate In-1 in oily form (99% yield).

[0668] (2) Synthesis of intermediate In-2 Under nitrogen atmosphere, methyl 2-iodobenzoate (5.2 g) was dissolved in acetic acid (60 g) in a reaction vessel, and the mixture was stirred at 40°C. Periodate tetrahydrate (31.7 g) was slowly added over 1 hour, and the mixture was stirred at 40°C–45°C for 6 hours. After standing at room temperature for 12 hours, acetonitrile (90 g) was added, and the mixture was cooled to below 5°C. After cooling, intermediate In-1 (4.1 g) was added, followed by the dissolution of p-toluenesulfonic acid monohydrate (1.9 g) in acetonitrile (90 g) and dropwise addition. The mixture was then matured at below 5°C for 2 hours. After maturation, the reaction mixture was injected into ice water (500 g) and extracted with dichloromethane (500 g). The extracted organic layer was washed with an aqueous solution obtained by dissolving sodium sulfite (50g) in water (500g), and then washed with water (500g). The solvent volume of the organic layer was concentrated to 1 / 10, ethyl acetate (100g) was added, and the solution was concentrated again to obtain 4.6g of intermediate In-2 in oily form (yield 36%).

[0669] (3) Synthesis of SQ-1 salt Under nitrogen atmosphere, intermediate In-2 (4.6 g) was dissolved in methanol (20 g) in a reaction vessel. A 25% (w / w) aqueous solution of sodium hydroxide (1.5 g) was added, and the mixture was allowed to mature for 4 hours. After maturation, water (30 g) was added, and the reaction was stopped. Dichloromethane (40 g) was added, and the target compound was extracted. Then, a standard aqueous work-up was performed to distill off the solvent. The residue was then washed with diisopropyl ether to obtain 2.4 g of the target compound SQ-1 in oily form (73% yield).

[0670] The results of SQ-1 TOF-MS are shown below. MALDI TOF-MS: POSITIVE M+453 (equivalent to C21H26IO3+)

[0671] [Examples 1-2~1-6] Synthesis of Zinc Salts SQ-2~SQ-6 Using the corresponding raw materials and known organic synthesis reactions, zirconia salts SQ-2 to SQ-6 represented by the following formulas were synthesized. [Chemistry 481]

[0672] [2] Synthesis of basic polymers [Synthetic Example] Synthesis of basic polymers (P-1~P-6) The monomers were combined using a known formulation and copolymerized in a solvent. The reaction solution was then added to hexane, and the precipitated solid was washed with hexane, isolated, and dried to obtain the base polymers (P-1 to P-6) with the compositions shown below. The composition of the obtained base polymers was confirmed using 1H-NMR and 13C-NMR, and Mw and Mw / Mn were determined using GPC (solvent: THF, standard: polystyrene). [Chemistry 482]

[0673] [3] Preparation of chemically amplified positive inhibitor composition [Examples 2-1 to 2-42, Comparative Examples 1-1 to 1-35] The components were dissolved in an organic solvent according to the compositions shown in Lists 1-3. The resulting solutions were filtered through a 5 nm nylon filter and a 1 nm UPE filter to prepare a chemically amplified positive inhibitor composition. The aforementioned organic solvent was a mixture of 940 parts by mass of PGMEA, 1870 parts by mass of EL, and 1870 parts by mass of PGME.

[0674] [Table 1] inhibitor Composition Basic polymers (parts by weight) Quenching agent (parts by weight) Photoacid generator (parts by weight) Polymers containing fluorine atoms (parts by weight) Example 2-1 R-1 P-1(80) SQ-1(7.0) - FP-1(1.5) Example 2-2 R-2 P-1(80) SQ-1(7.0) - - Example 2-3 R-3 P-1(80) SQ-2(7.0) - FP-1(1.5) Examples 2-4 R-4 P-1(80) SQ-3(7.0) - FP-1(1.5) Examples 2-5 R-5 P-1(80) SQ-4(7.0) - FP-1(1.5) Examples 2-6 R-6 P-1(80) SQ-5(7.0) - FP-1(1.5) Examples 2-7 R-7 P-1(80) SQ-6(7.0) - FP-1(1.5) Examples 2-8 R-8 P-1(80) SQ-1(7.0) - FP-2(1.5) Examples 2-9 R-9 P-1(80) SQ-1(7.0) - FP-3(1.5) Example 2-10 R-10 P-1(80) SQ-1(7.0) - FP-4(1.5) Example 2-11 R-11 P-1(80) SQ-1(7.0) - FP-5(1.5) Example 2-12 R-12 P-1(80) SQ-1(7.0) PAG-1(3) FP-1(1.5) Example 2-13 R-13 P-1(80) SQ-2(7.0) PAG-2(3) FP-1(1.5) Example 2-14 R-14 P-1(80) SQ-3(7.0) PAG-3(3) FP-1(1.5) Example 2-15 R-15 P-1(80) SQ-4(7.0) PAG-4(3) FP-1(1.5) Example 2-16 R-16 P-1(80) SQ-5(7.0) PAG-5(3) FP-1(1.5) Example 2-17 R-17 P-1(80) SQ-6(7.0) PAG-6(3) FP-1(1.5) Example 2-18 R-18 P-2(80) SQ-1(7.0) - FP-1(1.5) Example 2-19 R-19 P-2(80) SQ-2(7.0) - FP-1(1.5) Example 2-20 R-20 P-2(80) SQ-3(7.0) - FP-1(1.5) Example 2-21 R-21 P-2(80) SQ-1(7.0) PAG-1(3) FP-1(1.5) Example 2-22 R-22 P-2(80) SQ-2(7.0) PAG-2(3) FP-1(1.5) Example 2-23 R-23 P-2(80) SQ-6(7.0) PAG-3(3) FP-1(1.5)

[0675] [Table 2] inhibitor Composition Basic polymers (parts by weight) Quenching agent (parts by weight) Photoacid generator (parts by weight) Polymers containing fluorine atoms (parts by weight) Example 2-24 R-24 P-3(80) SQ-1(7.0) PAG-1(8) PAG-6(4) FP-1(1.5) Example 2-25 R-25 P-3(80) SQ-2(7.0) PAG-2(8) PAG-6(4) FP-1(1.5) Example 2-26 R-26 P-3(80) SQ-3(7.0) PAG-3(8) PAG-6(4) FP-1(1.5) Example 2-27 R-27 P-3(80) SQ-1(7.0) PAG-1(12) FP-1(1.5) Example 2-28 R-28 P-4(80) SQ-1(7.0) PAG-1(8) PAG-6(4) FP-1(1.5) Example 2-29 R-29 P-4(80) SQ-2(7.0) PAG-2(8) PAG-6(4) FP-1(1.5) Examples 2-30 R-30 P-4(80) SQ-4(7.0) PAG-3(8) PAG-6(4) FP-1(1.5) Example 2-31 R-31 P-4(80) SQ-5(7.0) PAG-4(8) PAG-6(4) FP-1(1.5) Example 2-32 R-32 P-4(80) SQ-6(7.0) PAG-5(8) PAG-6(4) FP-1(1.5) Example 2-33 R-33 P-5(80) SQ-1(7.0) PAG-1(8) PAG-6(4) FP-1(1.5) Examples 2-34 R-34 P-5(80) SQ-2(7.0) PAG-3(8) PAG-6(4) FP-1(1.5) Example 2-35 R-35 P-5(80) SQ-3(7.0) PAG-3(8) PAG-6(4) FP-1(1.5) Examples 2-36 R-36 P-5(80) SQ-5(7.0) PAG-5(8) PAG-6(4) FP-1(1.5) Example 2-37 R-37 P-5(80) SQ-6(7.0) PAG-5(8) PAG-6(4) FP-1(1.5) Example 2-38 R-38 P-6(80) SQ-1(7.0) PAG-1(8) PAG-6(4) FP-1(1.5) Example 2-39 R-39 P-6(80) SQ-2(7.0) PAG-2(8) PAG-6(4) FP-1(1.5) Example 2-40 R-40 P-6(80) SQ-3(7.0) PAG-3(8) PAG-6(4) FP-1(1.5) Example 2-41 R-41 P-6(80) SQ-4(7.0) PAG-4(8) PAG-6(4) FP-1(1.5) Example 2-42 R-42 P-6(80) SQ-6(7.0) PAG-1(8) PAG-6(4) FP-1(1.5)

[0676] [Table 3]

[0677] Tables 1-3 show the photoacid generators PAG-1 to PAG-6, the comparative quenchers SQ-A to SQ-D, and the polymers containing fluorine atoms FP-1 to FP-5. [Chemistry 483]

[0678] [Chemistry 484]

[0679] [Chemistry 485]

[0680] [4] EB Microfilm Review [Examples 3-1 to 3-42, Comparative Examples 2-1 to 2-35] Each chemically amplified positive resist composition (R-1~R-42, CR-1~CR-35) was spin-coated onto a 152mm square EUV exposure mask with a chromium compound outermost surface using ACT-M (manufactured by Tokyo Power Technology Co., Ltd.). The mask was then pre-baked at 110°C for 600 seconds on a heated plate to produce a resist film with a thickness of 80nm. The thickness of the obtained resist film was measured using an optical measuring instrument, NANOSPEC (manufactured by NANOMETRICS). Measurements were taken at 81 points in-plane, extending from the outer perimeter of the blank substrate to the outer edge within 10mm, and the average film thickness and thickness range were calculated.

[0681] Then, an electron beam exposure device (NUFLARE TECHNOLOGY EBM-5000plus, accelerating voltage 50kV) was used for exposure, and PEB was performed at 110°C for 600 seconds. The pattern was then developed with 2.38% TMAH aqueous solution to obtain a positive pattern.

[0682] The obtained resist patterns were evaluated as follows. The patterned blank mask was observed using an overhead SEM (scanning electron microscope). The optimal exposure (μC / cm²) for 1:1 line-to-spacing (LS) at 200 nm was determined using the exposure at 1:1 resolution. The minimum size of the 1:1 exposure for 200 nm LS was determined as the resolution limit (LER). The LER of 200 nm LS was measured using SEM. For the isolation spacing (IS), the minimum size of the 9:1 line-to-spacing (LS) at 9:1 resolution was determined as the resolution limit. The pattern shape was visually assessed to determine if it was rectangular. The results are shown in Tables 4 and 5.

[0683] [Table 4] inhibitor Composition Optimal exposure (µC / cm 2 ) L / S resolution (nm) Limiting IS resolution (nm) LER (nm) Pattern Shape Example 3-1 R-1 205 30 16 2.8 rectangle Example 3-2 R-2 205 30 16 2.9 rectangle Example 3-3 R-3 200 28 18 2.9 rectangle Examples 3-4 R-4 210 30 20 3 rectangle Examples 3-5 R-5 200 32 18 2.9 rectangle Examples 3-6 R-6 200 28 20 2.7 rectangle Examples 3-7 R-7 205 30 20 2.8 rectangle Examples 3-8 R-8 200 28 18 2.8 rectangle Examples 3-9 R-9 205 28 16 2.9 rectangle Examples 3-10 R-10 200 32 20 2.7 rectangle Example 3-11 R-11 210 30 18 2.8 rectangle Example 3-12 R-12 200 30 20 3 rectangle Example 3-13 R-13 205 28 16 2.8 rectangle Example 3-14 R-14 200 30 20 3 rectangle Example 3-15 R-15 205 32 18 2.9 rectangle Example 3-16 R-16 200 30 16 2.7 rectangle Example 3-17 R-17 200 30 18 2.8 rectangle Example 3-18 R-18 205 28 18 2.9 rectangle Example 3-19 R-19 200 28 16 3 rectangle Example 3-20 R-20 205 28 18 2.7 rectangle Example 3-21 R-21 200 30 16 2.9 rectangle Example 3-22 R-22 205 28 18 2.9 rectangle Example 3-23 R-23 205 28 20 2.9 rectangle Example 3-24 R-24 205 30 16 2.7 rectangle Example 3-25 R-25 210 30 18 2.8 rectangle Example 3-26 R-26 205 28 18 2.9 rectangle Example 3-27 R-27 205 32 18 2.8 rectangle Example 3-28 R-28 200 30 20 2.7 rectangle Example 3-29 R-29 205 28 16 2.9 rectangle Examples 3-30 R-30 205 28 16 2.8 rectangle Example 3-31 R-31 200 30 16 2.9 rectangle Example 3-32 R-32 200 30 18 3 rectangle Example 3-33 R-33 205 28 20 2.8 rectangle Examples 3-34 R-34 200 28 18 2.7 rectangle Examples 3-35 R-35 210 30 18 2.9 rectangle Examples 3-36 R-36 205 30 20 2.8 rectangle Examples 3-37 R-37 200 28 16 3.1 rectangle Examples 3-38 R-38 205 32 16 2.8 rectangle Examples 3-39 R-39 205 28 16 2.9 rectangle Examples 3-40 R-40 200 30 20 2.8 rectangle Examples 3-41 R-41 205 30 20 3 rectangle Examples 3-42 R-42 200 28 18 2.9 rectangle

[0684] [Table 5] inhibitor Composition Optimal exposure (µC / cm 2 ) L / S resolution (nm) Limiting IS resolution (nm) LER (nm) Pattern Shape Comparative Example 2-1 CR-1 200 34 twenty two 3.4 Top circle Comparative Example 2-2 CR-2 210 34 twenty four 3.3 Trail Comparative Examples 2-3 CR-3 200 36 twenty two 3.4 Top circle Comparative Examples 2-4 CR-4 205 34 twenty two 3.3 Trail Comparative Examples 2-5 CR-5 200 34 twenty two 3.3 Top circle Comparative Examples 2-6 CR-6 210 36 twenty four 3.4 Top circle Comparative Examples 2-7 CR-7 205 36 twenty four 3.4 Top circle Comparative Examples 2-8 CR-8 200 34 twenty two 3.4 Top circle Comparative Examples 2-9 CR-9 210 36 twenty two 3.3 Top circle Comparative Example 2-10 CR-10 205 36 twenty four 3.4 Trail Comparative Example 2-11 CR-11 200 36 twenty two 3.5 rectangle Comparative Example 2-12 CR-12 205 34 twenty four 3.6 Top circle Comparative Example 2-13 CR-13 210 34 twenty four 3.6 Top circle Comparative Example 2-14 CR-14 200 36 twenty two 3.4 Top circle Comparative Example 2-15 CR-15 210 36 twenty four 3.6 Top circle Comparative Example 2-16 CR-16 200 34 twenty two 3.5 Trail Comparative Example 2-17 CR-17 205 34 twenty four 3.3 Top circle Comparative Example 2-18 CR-18 200 36 twenty two 3.4 Top circle Comparative Example 2-19 CR-19 210 36 twenty four 3.5 Trail Comparative Example 2-20 CR-20 205 36 twenty two 3.4 Top circle Comparative Example 2-21 CR-21 200 34 twenty two 3.6 Trail Comparative Example 2-22 CR-22 210 34 twenty four 3.3 Top circle Comparative Example 2-23 CR-23 200 36 twenty four 3.6 Trail Comparative Example 2-24 CR-24 200 34 twenty two 3.4 Top circle Comparative Example 2-25 CR-25 210 38 twenty four 3.4 Top circle Comparative Example 2-26 CR-26 210 36 twenty two 3.6 Top circle Comparative Example 2-27 CR-27 200 34 twenty two 3.4 Trail Comparative Example 2-28 CR-28 205 34 twenty two 3.3 Top circle Comparative Example 2-29 CR-29 200 36 twenty two 3.5 Top circle Comparative Example 2-30 CR-30 210 34 twenty two 3.6 Top circle Comparative Example 2-31 CR-31 205 36 twenty four 3.6 Trail Comparative Example 2-32 CR-32 200 34 twenty two 3.5 Top circle Comparative Example 2-33 CR-33 210 34 twenty four 3.6 Top circle Comparative Example 2-34 CR-34 205 34 twenty two 3.4 Top circle Comparative Example 2-35 CR-35 200 36 twenty four 3.3 Trail

[0685] The chemically amplified positive resist composition (R-1 to R-42) of the present invention all exhibit good resolution, LER, and pattern rectangularity. On the other hand, the resist composition of the comparative examples (CR-1 to CR-35) did not achieve ideal optimization of acid diffusion, and deterioration was observed in resolution, LER, and pattern rectangularity.

[0686] The resist patterning method using the chemically amplified positive resist composition of the present invention is useful in the photolithography process of semiconductor device manufacturing, especially in the processing of transmissive and reflective blank photomasks.

Claims

1. A chemically amplified positive inhibitor composition comprising a quencher and a base polymer containing a polymer that decomposes under acid action and has increased solubility in alkaline developing solutions; the quencher is a quencher composed of a zirconia salt represented by the following formula (A), wherein the base polymer contains at least 60 mol% of repeating units having an aromatic ring skeleton in all repeating units of the polymer; wherein n1 is 0 or 1, n2 is 0, 1, 2, 3 or 4, n3 is 0 or 1, n4 is 0, 1, 2, 3 or 4, and LA is a single bond, ether bond, ester bond, sulfonate bond, carbonate bond or carbamate bond. Ralk is an alkyl group having 6 to 18 carbon atoms or a fluorinated alkyl group having 4 to 18 carbon atoms. When Ralk is an alkyl group having 6 to 18 carbon atoms, the alkyl group has at least one straight-chain structure with 6 or more carbon atoms. When Ralk is a fluorinated alkyl group having 4 to 18 carbon atoms, the fluorinated alkyl group has at least two groups selected from -CF2- and -CF3. Furthermore, one of the -CH2- groups of the alkyl group and the fluorinated alkyl group may be replaced by an ether bond or a carbonyl group. The terminal or carbon-carbon bond may also contain a ring structure selected from cyclopentane ring, cyclohexane ring, adamantane ring, norcamphenic ring and benzene ring. R1 can be a halogen atom, nitro, cyano, hydroxyl, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. When n2 is 2, 3, or 4, each R1 can be the same or different from the others. Multiple R1s can also bond to each other and form a ring together with the carbon atoms they are bonded to. R2 can be a halogen atom, nitro, cyano, hydroxyl, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. When n4 is 2, 3, or 4, each R2 can be the same or different from the others. Multiple R2s can also bond to each other and form a ring together with the carbon atoms they are bonded to. Furthermore, the two aromatic rings bonded by I+ in the formula can also bond to each other and form a ring together with the iodine atoms they are bonded to.

2. The chemical amplification positive inhibitor composition of claim 1, wherein the zirconia salt represented by formula (A) is represented by formula (A1), wherein n2, n4, LA, Ralk, R1 and R2 are as described in claim 1.

3. The chemical amplification positive inhibitor composition as described in claim 1, wherein, The polymer contains repeating units represented by the following formula (B1), where 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, RA is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R11 is a halogen atom, a nitro group, a carboxyl group, or a 1-6 carbon saturated hydrocarbon group that can be substituted with a halogen atom, or a 2-8 carbon saturated hydrocarbon carbonyl group that can be substituted with a halogen atom, A1 is a single bond or a 1-10 carbon saturated hydrocarbon group, and a portion of the -CH2- of the saturated hydrocarbon group can also be substituted with -O-.

4. The chemical amplification positive inhibitor composition as described in claim 1, wherein, The polymer contains repeating units represented by the following formula (B2-1), where RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; 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 or 1; R21 is a halogen atom, or a 1-6 carbon saturated hydrocarbon group that may be substituted with a halogen atom, or a 1-6 carbon saturated hydrocarbon oxygen group that may be substituted with a halogen atom, or a 2-8 carbon saturated hydrocarbon carbonyl oxygen group that may be substituted with a halogen atom; A2 is a single bond or a 1-10 carbon saturated hydrocarbon group, and a portion of the -CH2- of the saturated hydrocarbon group may also be substituted with -O-; X is an acid-unstable group when b4 is 1, and a hydrogen atom or an acid-unstable group when b4 is 2 or 3, but at least one is an acid-unstable group.

5. The chemical amplification positive inhibitor composition as claimed in claim 1, wherein, The polymer contains repeating units represented by the following formula (B2-2), where c1 is 0, 1, or 2; c2 is 0, 1, or 2; c3 is 0, 1, 2, 3, 4, or 5; c4 is 0, 1, or 2; RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R22 and R23 are each independently a hydrocarbon group with 1 to 10 carbon atoms, and may also contain heteroatoms; R22 and R23 may also be bonded to each other and form a ring with the carbon atoms they are bonded to; R24 is each independently a fluorine atom, a fluorinated alkyl group with 1 to 5 carbon atoms, or a fluorinated alkoxy group with 1 to 5 carbon atoms; and R35 is each independently a hydrocarbon group with 1 to 10 carbon atoms, and may also contain heteroatoms. A3 is a single bond, phenyl, naphthyl or *-C(=O)-O-A31-, A31 is an aliphatic alkyl group with 1 to 20 carbon atoms, which may also contain hydroxyl, ether bond, ester bond or lactone ring, or phenyl or naphthyl, and * is an atomic bond with the carbon atom of the main chain.

6. The chemical amplification positive inhibitor composition as claimed in claim 1, wherein, The polymer contains at least one of the repeating units represented by formula (B3), formula (B4), and formula (B5), wherein d is 0, 1, 2, 3, 4, 5, or 6; e is 0, 1, 2, 3, or 4; f1 is 0 or 1; f2 is 0, 1, or 2; f3 is 0, 1, 2, 3, 4, or 5; RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; and R31 and R32 are each independently a hydroxyl group, a halogen atom, a 1-6 carbon saturated hydrocarbon group that may be substituted with a halogen atom, a 1-6 carbon saturated hydrocarbon oxygen group that may be substituted with a halogen atom, or a 2-8 carbon saturated hydrocarbon carbonyl group that may be substituted with a halogen atom. R33 is a saturated hydrocarbon group with 1 to 20 carbon atoms, a saturated hydrocarbon oxygen group with 1 to 20 carbon atoms, a saturated hydrocarbon carbonyl group with 2 to 20 carbon atoms, a saturated hydrocarbon oxy group with 2 to 20 carbon atoms, a saturated hydrocarbon thio group with 2 to 20 carbon atoms, a halogen atom, a nitro group, or a cyano group. When f2 is 1 or 2, it can also be a hydroxyl group. A4 is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms. Part of the -CH2- of the saturated hydrocarbon group can also be replaced by -O-.

7. The chemical amplification positive inhibitor composition as claimed in claim 1, wherein, The polymer contains at least one of the repeating units selected from the following formulas (B6, B7, B8, B9, and B10): g1 and g2 are each independently 0, 1, 2, or 3; h1 is 0 or 1; h2 is 0, 1, 2, 3, or 4; h3 is 0, 1, 2, 3, or 4, except that when h1 is 0, 0 ≤ h2 + h3 ≤ 4, and when h1 is 1, 0 ≤ h2 + h3 ≤ 6; RA are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; and Z1 is a single bond or may have substituents, such as a phenyl group. Z2 is a single bond, **-C(=O)-O-Z21-, **-C(=O)-NH-Z21-, or **-O-Z21-, where Z21 is a divalent group obtained by aliphatic alkyl group, phenyl group, or combinations thereof with 1 to 6 carbon atoms, and may also contain a halogen atom, carbonyl group, ester bond, ether bond, or hydroxyl group. Z3 is a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Z4 is a single bond, or a divalent group obtained by aliphatic alkyl group, phenyl group, or combinations thereof with 1 to 6 carbon atoms, and may also contain a halogen atom, carbonyl group, ester bond, ether bond, or hydroxyl group. Z5 is independently a single bond, or may contain substituents such as phenyl, naphthyl, or *-C(=O)-O-Z51-. Z51 is an aliphatic alkyl group, phenyl, or naphthyl with 1 to 10 carbon atoms, and this aliphatic alkyl group may also contain halogen atoms, hydroxyl groups, ether bonds, ester bonds, or lactone rings. Z6 is a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Z7 is independently a single bond, ***-Z71-C(=O)-O-, ***-C(=O)-NH-Z71-, or ***-O-Z71-. Z71 may also contain heteroatoms and is an alkyl group with 1 to 20 carbon atoms. Z8 can be a single bond, ****-Z81-C(=O)-O-, ****-C(=O)-NH-Z81-, or ****-O-Z81-. Z81 can be a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms. Z9 can be a single bond, methylene, ethyl, phenyl, fluorinated phenyl, trifluoromethyl-substituted phenyl, *-C(=O)-O-Z91-, *-C(=O)-N(H)-Z91-, or *-O-Z91-. Z91 can be an aliphatic hydrocarbon group with 1 to 6 carbon atoms, phenyl, fluorinated phenyl, or trifluoromethyl-substituted phenyl. It may also contain carbonyl, ester, ether, or hydroxyl groups. * indicates an atomic bond with the carbon atom of the main chain, ** indicates an atomic bond with Z1, *** indicates an atomic bond with Z6, and **** indicates an atomic bond with Z7. L1 can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond; Rf1 and Rf2 are each independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms.Rf3 and Rf4 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Rf5 and Rf6 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. However, not all Rf5 and Rf6 are hydrogen atoms simultaneously. Rf7 is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated alkyl thio group having 1 to 6 carbon atoms. R41 and R42 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms. Furthermore, R41 and R42 can also bond with each other and form a ring with the sulfur atoms they are bonded to. R43 is a halogen atom other than a fluorine atom, or may also contain a hydrocarbon group having 1 to 20 carbon atoms, and when h3 is 2, 3, or 4, each R43 can be the same or different from the others. Multiple R43s can also bond with each other and form a ring with the carbon atoms they are bonded to. M- is a non-nucleophilic relative ion. A+ is an onium cation.

8. The chemical amplification positive inhibitor composition of claim 1 further includes an organic solvent.

9. The chemical amplification positive inhibitor composition of claim 1 further includes a photoacid generator.

10. The chemical amplification positive inhibitor composition of claim 1 further comprises a polymer containing fluorine atoms, wherein the polymer containing fluorine atoms contains at least one of the repeating units represented by formula (E1), formula (E2), formula (E3), and formula (E4), and may further contain at least one of the repeating units represented by formula (E5) and formula (E6), wherein j1 is 1, 2, or 3, j2 is an integer satisfying 0 ≤ j2 ≤ 5 + 2(j3) - j1, j3 is 0 or 1, k is 1, 2, or 3, RB are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, RC are each independently a hydrogen atom or a methyl group, and R201, R202, R204, and R205 are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. R203, R206, R207, and R208 are each independently a hydrogen atom, a hydrocarbon group with 1 to 15 carbon atoms, a fluorinated hydrocarbon group with 1 to 15 carbon atoms, or an acid-destabilized group. When R203, R206, R207, and R208 are hydrocarbon groups or fluorinated hydrocarbon groups, ether bonds or carbonyl groups may be inserted between carbon-carbon bonds. R209 is a hydrogen atom, or a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms containing a heteroatom may be inserted between carbon-carbon bonds. R210 is a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms containing a heteroatom may be inserted between carbon-carbon bonds. R211 is a saturated hydrocarbon group with 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and part of the -CH2- of this saturated hydrocarbon group may also be replaced by an ester bond or an ether bond. Z1 is a (k+1) valence hydrocarbon group with 1 to 20 carbon atoms or a (k+1) valence fluorinated hydrocarbon group with 1 to 20 carbon atoms; Z2 is a single bond, *-C(=O)-O- or *-C(=O)-NH-, where * is an atomic bond with a carbon atom in the main chain; Z3 is a single bond, -O-, *-C(=O)-O-Z31-Z32- or *-C(=O)-NH-Z31-Z32-, where Z31 is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms; Z32 is a single bond, ester bond, ether bond or sulfonamide bond, where * is an atomic bond with a carbon atom in the main chain.

11. The chemical amplification positive inhibitor composition of claim 1 further includes a quencher other than the quencher composed of the zirconia salt represented by formula (A).

12. A method for forming a resist pattern, comprising the following steps: forming a resist film on a substrate using a chemically amplified positive resist composition as claimed in any one of claims 1 to 11, irradiating the resist film with a pattern using high-energy rays, and developing the irradiated resist film with an alkaline developer.

13. The method for forming the resist pattern as described in claim 12, wherein, The high-energy rays are extreme ultraviolet rays or electron beams with wavelengths of 3 to 15 nm.

14. The method for forming a resist pattern as described in claim 12, wherein, The outermost surface of the substrate is made of a chromium-containing material.

15. The method for forming a resist pattern as described in claim 12, wherein, The substrate is a blank photomask.