Resist composition and pattern forming method

Abstract

The invention relates to a resist composition and a pattern forming method. The present invention addresses the problem of providing a non-chemically amplified resist composition having excellent sensitivity and limit resolution in optical lithography using high-energy rays, and a pattern forming method using the resist composition. [Solution] A resist composition containing at least one type of a superatomic iodine compound represented by any one of formulae (1) to (4), a carboxyl group-containing polymer, and a solvent; the carboxyl group-containing polymer contains a repeating unit represented by the following formula (5) and at least one member selected from the group consisting of a repeating unit represented by the following formula (6), a repeating unit represented by the following formula (7), a repeating unit represented by the following formula (8), a repeating unit represented by the following formula (9), and a repeating unit represented by the following formula (10).

Description

TECHNICAL FIELD

[0001] The present application relates to a resist composition and a pattern forming method. BACKGROUND

[0002] With the expansion of the IoT market, further demands are made for high integration, high speed, and low power consumption of LSIs, and the miniaturization of pattern rules is also rapidly progressing. In particular, logic devices are leading the miniaturization. As for the most advanced miniaturization technology, mass production of 10-nm-node devices by double patterning, triple patterning, and quadruple patterning of ArF immersion lithography is underway, and in addition, the exploration of 7-nm-node devices by the next-generation wavelength 13.5-nm extreme ultraviolet (EUV) lithography is progressing.

[0003] With the progress of miniaturization, blurring of images due to diffusion of acid also becomes a problem (Non-Patent Literature 1). In order to ensure resolution of fine patterns of 45 nm or less in processing size, it has been proposed that not only improvement of the dissolution contrast, which has been advocated in the past, but also control of acid diffusion is important (Non-Patent Literature 2). However, since a chemically amplified resist composition improves sensitivity and contrast by diffusion of acid, if acid diffusion is suppressed to the limit by lowering the post-exposure bake (PEB) temperature or shortening the PEB time, etc., the sensitivity and contrast will be significantly reduced.

[0004] It is effective to suppress acid diffusion by adding an acid generator that generates a bulky acid. Thus, it has been proposed to copolymerize an onium salt of a polymerizable olefin in a polymer to provide an acid generator. However, in pattern formation of resist films of 16 nm or less in processing size, it is considered that from the viewpoint of acid diffusion, a chemically amplified resist composition cannot perform pattern formation, and development of a non-chemically amplified resist composition is expected.

[0005] A material for a non-chemically amplified resist composition can be exemplified by polymethyl methacrylate (PMMA). PMMA is a positive resist material that improves the solubility in a developer of an organic solvent by cleavage of the main chain and reduction of the molecular weight due to EUV irradiation.

[0006] Hydrogensiloxane (HSQ) is crosslinked by condensation reaction of silanol generated by EUV irradiation, and thereby becomes a negative resist material that is insoluble in an alkali developer. Also, a calixarene substituted with chlorine functions as a negative resist material. These negative resist materials, since the molecular size before crosslinking is small and there is no blurring due to acid diffusion, can be used as a pattern transfer material that is small in edge roughness and very high in resolution, and exhibits the resolution limit of an exposure device. However, these materials are insufficient in sensitivity, and further improvement is required.

[0007] A major cause of difficulty in developing materials for EUV lithography applications can be listed as the small number of photons in EUV exposure. The energy of EUV is much higher than that of ArF excimer laser, and the number of photons in EUV exposure is 1 / 14 of that in ArF exposure. In addition, the size of the pattern formed by EUV exposure is less than half of that by ArF exposure. Therefore, EUV exposure is easily affected by variations in the number of photons. The variation in the number of photons in the region of the emitted light of the extremely short wavelength is shot noise, a physical phenomenon, and the effect cannot be eliminated. Therefore, so-called Stochastics is of concern. Although the effect of shot noise cannot be eliminated, how to reduce the effect is discussed. Due to the effect of shot noise, not only the size uniformity (CDU) and the line width roughness (LWR) become large, but there is also a probability of several millionths that a hole blocking phenomenon will be observed. If the hole is blocked, the transistor does not operate due to poor conduction, and therefore the performance of the entire device is adversely affected. When considering the sensitivity in practical use, the resist composition using PMMA and HSQ as the main components is greatly affected by Stochastics, and the desired resolution performance cannot be obtained.

[0008] As a method for reducing the effect of shot noise from the resist aspect, the introduction of an element having a large absorption of EUV light is of concern. Patent Literature 1 proposes a chemical amplification resist composition containing an iodine atom having a large absorption of EUV light. However, as described above, the chemical amplification resist composition cannot achieve excellent resolution performance in EUV lithography in which the processing size is increasingly miniaturized in the future. In particular, in a line and space pattern, as the pattern size becomes smaller, pattern collapse and line breakage also significantly increase, and therefore reducing these cases is closely related to improvement in the limit of resolution.

[0009] Patent Literature 2 proposes a negative resist composition using a tin compound. It is a composition in which tin, which has a large absorption of EUV light, is used as the main component, and therefore Stochastics is improved, and high sensitivity and high resolution can be achieved. However, such a metal resist has many problems such as insufficient solubility in a solvent for the resist, storage stability, defects due to residues after etching, and the like. In addition, the metal resist is mainly negative in which the exposed portion becomes a metal oxide and is not soluble in a developer, and therefore when used for patterning of a contact hole, an additional reversal processing step is required, and there are concerns in terms of cost.

[0010] Prior Art Documents

[0011] Patent Literature

[0012] [Patent Literature 1] Japanese Patent Application Publication No. 2018-5224

[0013] [Patent Literature 2] Japanese Patent Application Laid-Open No. 2021-503482

[0014] Non-Patent Literature

[0015] [Non-Patent Literature 1] SPIE Vol. 5039 p1 (2003)

[0016] [Non-Patent Literature 2] SPIE Vol. 6520 p65203L-1 (2007) SUMMARY

[0017] [Problems to be Solved by the Invention]

[0018] The present invention has been achieved in view of the foregoing circumstances, and aims to provide a non-chemically amplified resist composition which is excellent in sensitivity and in limit resolution in optical lithography using high-energy rays, particularly in electron beam (EB) lithography and EUV lithography, and to provide a pattern forming method using the resist composition.

[0019] [Means of Solving the Problems]

[0020] As a result of repeated and intensive studies in order to achieve the foregoing object, the present inventors have obtained the following insight, and thus completed the present invention: a resist composition in which a predetermined hypervalent iodine compound and a polymer having a carboxyl group and a photo-acid generating site are used as main components can provide a resist film which is high in sensitivity and exhibits excellent resolution, and is extremely effective for precision fine processing.

[0021] That is, the present invention provides the following resist composition and pattern forming method.

[0022] 1. A resist composition comprising:

[0023] a hypervalent iodine compound, at least one of which is represented by any one of the following formulas (1) to (4),

[0024] a carboxyl group-containing polymer, and

[0025] a solvent;

[0026] the carboxyl group-containing polymer contains a repeating unit represented by the following formula (5) and at least one selected from the group consisting of a repeating unit represented by the following formula (6), a repeating unit represented by the following formula (7), a repeating unit represented by the following formula (8), a repeating unit represented by the following formula (9), and a repeating unit represented by the following formula (10).

[0027] [Chemical Formula 1]

[0028]

[0029] wherein m1 is 0, 1 or 2. When m1 is 0, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4 or 5, and 1≤n1+n2≤6. When m1 is 1, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4, 5, 6 or 7, and 1≤n1+n2≤8. When m1 is 2, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and 1≤n1+n2≤10. n3 is 1 or 2. n4 is 0, 1, 2, 3 or 4. However, 1≤n3+n4≤5. n5 is 1 or 2. n6 is 0, 1, 2, 3 or 4. However, 1≤n5+n6≤5. n7 is 0, 1, 2, 3 or 4. n8 is 1, 2, 3 or 4.

[0030] m2 is 0, 1 or 2. When m2 is 0, n9 is 0, 1, 2, 3 or 4. When m2 is 1, n9 is 0, 1, 2, 3, 4, 5 or 6. When m2 is 2, n9 is 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0031] R 1 ~R 8 are each independently a halogen atom or a hydrocarbon group having a carbon number of 1 to 10 which can also contain a hetero atom. Also, R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , or R 7 and R 8 may be bonded to each other and form a ring together with the carbon atom to which they are bonded and the atoms between the carbon atoms.

[0032] R 11 ~R 14 are each independently a halogen atom or a hydrocarbon group having a carbon number of 1 to 40 which can also contain a hetero atom. When n2 is 2 or more, each R 11 may be the same or different, and a plurality of R 11 may be bonded to each other and form a ring together with the carbon atom of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 12 may be the same or different, and a plurality of R 12 may be bonded to each other and form a ring together with the carbon atom of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 13 may be the same or different, and a plurality of R 13 may be bonded to each other and form a ring together with the carbon atom of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 14 may be the same or different, and a plurality of R 14 may be bonded to each other and form a ring together with the carbon atom of the aromatic ring to which they are bonded.

[0033] R15 is a (n8) valent hydrocarbon group having a carbon number of 1 to 40 or a (n8) valent heterocyclic group having a carbon number of 2 to 40, and when n8 is 2, R 15 may also be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamato bond, a sulfinyl group, a sulfonyl group, or a thione bond. Also, a part or all of the hydrogen atoms of the aforementioned (n8) valent hydrocarbon group or (n8) valent heterocyclic group can be substituted with a heteroatom-containing group, and a part of -CH2- of the aforementioned (n8) valent hydrocarbon group can also be substituted with a heteroatom-containing group, and R 14 and R 15 may also be bonded to each other and form a ring together with the carbon atoms to which they are bonded and the atoms between the carbon atoms.

[0034] R 16 is a halogen atom or a hydrocarbon group having a carbon number of 1 to 10 which can also contain a heteroatom.

[0035] R 17 is a halogen atom or a hydrocarbon group having a carbon number of 1 to 40 which can also contain a heteroatom. When n9 is 2 or more, each R 17 may be the same or different. Also, a plurality of R 17 may also be bonded to each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded.

[0036] R 18 is a carbonyl group or a hydrocarbon group having a carbon number of 1 to 10 which can also contain a heteroatom.

[0037] *1 and *2 represent atomic bonds to the carbon atoms of the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms in the aromatic ring.

[0038] [Chemical Formula 2]

[0039]

[0040] in the formula, R A are each independently a hydrogen atom or a methyl group.

[0041] R B are each independently a hydrogen atom, or can also be bonded to Z 6 and form a ring.

[0042] X 1 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-X 11 -. X 11 is a saturated hydrocarbylene group having a carbon number of 1 to 10, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group can also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. * represents an atomic bond to the carbon atom of the main chain.

[0043] Z 1a single bond, an aliphatic hydrocarbylene group having a carbon number of 1 to 6, a phenylene group, a naphthylene group, or a group having a carbon number of 7 to 18 obtained by combining them, or -O-Z 11 -C(=O)-O-Z 11 -C(=O)-NH-Z 11 Z 11 an aliphatic hydrocarbylene group having a carbon number of 1 to 6, a phenylene group, a naphthylene group, or a group having a carbon number of 7 to 18 obtained by combining them, and can also have a carbonyl group, an ester bond, an ether bond, or a hydroxyl group.

[0044] Z 2 a single bond or an ester bond.

[0045] Z 3 a single bond, -Z 31 -C(=O)-O- or -Z 31 -O-Z 31 an aliphatic hydrocarbylene group having a carbon number of 1 to 12, a phenylene group, or a group having a carbon number of 7 to 18 obtained by combining them, and can also have a carbonyl group, a nitro group, a cyano group, an ester bond, an ether bond, a urethane bond, a fluorine atom, an iodine atom, or a bromine atom.

[0046] Z 4 a single bond, methylene, or ethylene.

[0047] Z 5 a single bond, methylene, ethylene, a phenylene group, a methylphenylene group, a dimethylphenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, -O-Z 51 -C(=O)-O-Z 51 -C(=O)-NH-Z 51 Z 51 an aliphatic hydrocarbylene group having a carbon number of 1 to 6, a phenylene group, a methylphenylene group, a dimethylphenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and can also have a carbonyl group, an ester bond, an ether bond, a hydroxyl group, or a halogen atom.

[0048] Z 6 a single bond, a phenylene group, a naphthylene ring, an ester bond, or an amide bond.

[0049] Z 7A a single bond or a divalent organic group having a carbon number of 1 to 24, and can also have at least one selected from a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom.

[0050] Z 7B a monovalent organic group having a carbon number of 1 to 10, and can also have at least one selected from a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom.

[0051] Z 8 a single bond, an ether bond, an ester bond, a thioether bond, or an alkanediyl group having a carbon number of 1 to 6.

[0052] Z 9 is a trivalent organic group having 1 to 12 carbon atoms, and can also have at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom.

[0053] Rf 1 ~Rf 4 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 may also be combined to form a carbonyl group.

[0054] R 21 and R 22 are each independently a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which can also contain a hetero atom.

[0055] R 23 is a saturated hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a fluorine atom, an iodine atom, a trifluoromethoxy group, a difluoromethoxy group, a cyano group, or a nitro group.

[0056] the circle R is an (a+2)-valent aromatic hydrocarbon group having 6 to 10 carbon atoms.

[0057] a is 0, 1, 2, 3, 4, or 5.

[0058] X - is a non-nucleophilic counter ion.

[0059] M + is a sulfonium cation or a sulfoxonium cation.

[0060] 2. The resist composition of 1, wherein the carboxyl group-containing polymer does not contain an acid-labile group.

[0061] 3. A laminate, comprising:

[0062] a substrate, and

[0063] a resist film on the substrate obtained from the resist composition of 1 or 2.

[0064] 4. The laminate of 3, comprising a resist underlayer film between the substrate and the resist film.

[0065] 5. The laminate of 3 or 4, wherein the resist film is formed by ligand exchange of the hypervalent iodine compound with the carboxyl group-containing polymer.

[0066] 6. A pattern forming method, comprising the steps of:

[0067] forming a resist film on a substrate or a substrate having an underlayer film laminated thereon using the resist composition of 1 or 2,

[0068] The aforementioned resist film is exposed to i-ray, KrF excimer laser, ArF excimer laser, electron beam, or extreme ultraviolet, and

[0069] The aforementioned exposed resist film is developed using a developer.

[0070] [Effects of the Invention]

[0071] The resist composition of the present application is extremely useful when high sensitivity and high resolution are taken into account and fine patterns are formed in i-ray, KrF excimer laser, ArF excimer laser, EB lithography, and EUV lithography. DETAILED DESCRIPTION

[0072] [Resist Composition]

[0073] The resist composition of the present application contains a predetermined hypervalent iodine compound and a carboxyl group-containing polymer as main components.

[0074] [Hypervalent Iodine Compound]

[0075] The aforementioned hypervalent iodine compound is at least one kind of tri-coordinated hypervalent iodine compound represented by any one of the following formulas (1) to (4).

[0076] [Chemical 3]

[0077]

[0078] In formulas (1) to (4), ml is 0, 1, or 2. When ml is 0, nl is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, or 5, and 1 ≤ nl + n2 ≤ 6. When ml is 1, nl is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1 ≤ nl + n2 ≤ 8. When ml is 2, nl is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1 ≤ nl + n2 ≤ 10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4. However, 1 ≤ n3 + n4 ≤ 5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4. However, 1 ≤ n5 + n6 ≤ 5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. m2 is 0, 1, or 2. When m2 is 0, n9 is 0, 1, 2, 3, or 4. When m2 is 1, n9 is 0, 1, 2, 3, 4, 5, or 6. When m2 is 2, n9 is 0, 1, 2, 3, 4, 5, 6, 7, or 8.

[0079] In formulas (1) to (3), R 1 to R 8 are each independently a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms which can also contain a hetero atom. Also, R 1 and R2 R 3 and R 4 R 5 and R 6 R 7 and R 8 may be bonded to each other and form a ring together with the carbon atoms to which they are bonded and the atoms between the carbon atoms.

[0080] R 1 ~R 8 represent a halogen atom. The halogen atom represented by R 1 ~R 8 represents a hydrocarbon group having a carbon number of 1 to 10. The hydrocarbon group having a carbon number of 1 to 10 represented by R 2,6 may be saturated or unsaturated, and can be any one of a straight chain, a branched chain, and a cyclic structure. Specific examples thereof can include alkyl groups having a carbon number of 1 to 10 such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, a t-pentyl group, a n-hexyl group, a n-octyl group, a 2-ethylhexyl group, a n-nonyl group, a n-decyl group, and the like; cyclic saturated hydrocarbon groups having a carbon number of 3 to 10 such as a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclopentylbutyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylbutyl group, a norbornyl group, a tricyclo[5.2.1.02'6]decyl group, an adamantyl group, and the like; alkenyl groups such as a vinyl group, an allyl group, and the like; aryl groups having a carbon number of 6 to 10 such as a phenyl group, a naphthyl group, and the like; and a group obtained by combining them. Also, a part or all of the hydrogen atoms of the aforementioned hydrocarbon group can be substituted with a group containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, a halogen atom, and the like, and a part of -CH2- of the aforementioned hydrocarbon group can be substituted with a group containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, and the like. As a result, it can contain a hydroxyl group, a cyano group, a halogen atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate ester bond, a carbamate ester bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-O-C(=O)-), and the like. 1 ~R 8 preferably represents a hydrocarbon group having a carbon number of 1 to 4.

[0081] In formulae (1) to (3), R 11 ~R 14 represents a halogen atom or a hydrocarbon group having a carbon number of 1 to 40 which can also contain a hetero atom. When n2 is 2 or more, each R 11 may be the same or different, and a plurality of R 11 may be bonded to each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 12 may be the same or different, and a plurality of R 12 may be bonded to each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 13 may be the same or different, and a plurality of R 13They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R 14 They can be the same or different, and there are multiple Rs. 14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0082] R 11 ~R 14 Examples of halogen atoms that can be represented include: fluorine, chlorine, bromine, and iodine atoms. R 11 ~R 14 The hydrocarbon groups representing 1 to 40 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, these groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.]

[0083] In equation (3), R 15 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When (n8) is 2, R 15 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl bond. Furthermore, some or all of the hydrogen atoms of the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, and R... 14 and R 15 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0084] R 15The (n8) valent hydrocarbon group represented by the formula (n8) can be either saturated or unsaturated, and can be any one of linear, branched, or cyclic. The aforementioned (n8) valent hydrocarbon group is a group obtained by removing (n8) hydrogen atoms from a hydrocarbon. The aforementioned hydrocarbon can include, for example, an alkane having 1 to 40 carbons, an alkene having 2 to 40 carbons, an alkyne having 2 to 40 carbons, a cyclic saturated hydrocarbon having 3 to 40 carbons, a cyclic unsaturated hydrocarbon having 3 to 40 carbons, and an aromatic hydrocarbon having 6 to 40 carbons.

[0085] Specific examples of the aforementioned alkane having 1 to 40 carbons can include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, structural isomers thereof, and the like.

[0086] Specific examples of the aforementioned alkene having 2 to 40 carbons can include ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, structural isomers thereof, and the like.

[0087] Specific examples of the aforementioned alkyne having 2 to 40 carbons can include acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, structural isomers thereof, and the like.

[0088] Specific examples of the aforementioned cyclic saturated hydrocarbon having 3 to 40 carbons can include cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, and the like.

[0089] Specific examples of the aforementioned cyclic unsaturated hydrocarbon having 3 to 40 carbons can include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, and the like.

[0090] Specific examples of the aforementioned aromatic hydrocarbon having 6 to 40 carbons can include benzene, naphthalene, biphenyl, and the like.

[0091] R 15 The (n8) valent heterocyclic group represented by the formula (n8) is a group obtained by removing (n8) hydrogen atoms from a heterocyclic compound. The aforementioned heterocyclic compound can include, for example, furan, pyridine, pyrazole, tetrahydrothiazole, and the like.

[0092] R 15 A part or all of the hydrogen atoms of the (n8) valent hydrocarbon group or the (n8) valent heterocyclic group represented by the formula (n8) can also be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, a halogen atom, and the like, and as a result, can also contain a hydroxyl group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Also, in the aforementioned (n8) valent hydrocarbon group, a part of -CH2- constituting it can also be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, and the like, and as a result, can also contain a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate ester bond, a carbamate ester bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-O-C(=O)-), and the like.

[0093] In the formula (4), R 16A hydrocarbon group having 1 to 10 carbon atoms which can be a halogen atom or can also contain a hetero atom. R 16 Specific examples of the halogen atom and the hydrocarbon group represented by R 1 ~R 8 are the same as those of R

[0094] In formula (4), R 17 is a halogen atom or a hydrocarbon group having 1 to 40 carbon atoms which can contain a hetero atom. When n9 is 2 or more, each R 17 may be the same or different. Also, a plurality of R 17 may be bonded to each other and form a ring together with the carbon atom of the aromatic ring to which they are bonded. R 17 Specific examples of the halogen atom and the hydrocarbon group represented by R 11 ~R 14 are the same as those of R

[0095] In formula (4), R 18 is a carbonyl group or a hydrocarbon group having 1 to 10 carbon atoms which can contain a hetero atom. The hydrocarbon group having 1 to 10 carbon atoms can be either saturated or unsaturated, and can be linear, branched or cyclic. Specific examples thereof include methanediyl, ethane-l, l-diyl, ethane-l,2-diyl, propane-l, l-diyl, propane-l,2-diyl, propane-l,3-diyl, propane-2,2-diyl, butane-2,3-diyl, butane-l,4-diyl, 2-methylpropane-l,2-diyl, pentane-l,5-diyl, hexane-l,6-diyl, heptane-l,7-diyl, octane-l,8-diyl, nonane-l,9-diyl, decane-l, lO-diyl and the like alkylene groups having 1 to 10 carbon atoms; cyclopentanediyl, cyclohexanediyl, norbornanediyl, adamantanediyl, tricyclo[5.2.1.0 2,6 ]decane-diyl and the like cyclic saturated hydrocarbon groups having 3 to 10 carbon atoms; ethenylene, propenylene and the like alkenylene groups having 2 to 10 carbon atoms; phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, naphthylene and the like arylene groups having 6 to 10 carbon atoms; and groups obtained by combining these groups. Also, part or all of the hydrogen atoms of the aforementioned hydrocarbon groups can be substituted with groups containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and part of the -CH2- groups of the aforementioned hydrocarbon groups can also be substituted with groups containing a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the aforementioned hydrocarbon groups can also contain a hydroxyl group, a cyano group, a halogenated alkyl group, a halogen atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate ester bond, a carbamate ester bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-O-C(=O)-) and the like. R 18 is preferably a carbonyl group, a hydrocarbon group having 1 to 4 carbon atoms or a fluorinated hydrocarbon group having 1 to 4 carbon atoms.

[0096] In formula (4), *1 and *2 represent atomic bonds to carbon atoms of the aromatic ring in formula (4). However, *1 and *2 are bonded to adjacent carbon atoms in the aromatic ring. Combinations of *1, *2, and m2 can be considered in the following 7 patterns.

[0097] [Chemical Formula 4]

[0098]

[0099] In the formula, n9, R 17 and R 18 are the same as described above. The dotted line indicates an atomic bond to -C(=O)-O-. 16

[0100] Specific examples of the hyperhalogen compound represented by formula (1) can include, but are not limited to, the following.

[0101] [Chemical Formula 5]

[0102]

[0103] [Chemical Formula 6]

[0104]

[0105] [Chemical Formula 7]

[0106]

[0107] [Chemical Formula 8]

[0108]

[0109] [Chemical Formula 9]

[0110]

[0111] [Chemical Formula 10]

[0112]

[0113] [Chemical Formula 11]

[0114]

[0115] [Chemical Formula 12]

[0116]

[0117] [Chemical Formula 13]

[0118]

[0119] [Chemical Formula 14] ​

[0120]

[0121] [Chemical Formula 15]

[0122]

[0123] [Chemical Formula 16]

[0124]

[0125] Specific examples of the hypercoordinated iodine compound represented by formula (2) can include, but are not limited to, the following.

[0126] [Chemical Formula 17]

[0127]

[0128] [Chemical Formula 18]

[0129]

[0130] [Chemical Formula 19]

[0131]

[0132] [Chemical Formula 20]

[0133]

[0134] Specific examples of the hypercoordinated iodine compound represented by formula (3) can include, but are not limited to, the following.

[0135] [Chemical Formula 21]

[0136]

[0137] [Chemical Formula 22]

[0138]

[0139] [Chemical Formula 23]

[0140]

[0141] [Chemical Formula 24]

[0142]

[0143] [Chemical Formula 25]

[0144]

[0145] [Chemical Formula 26]

[0146]

[0147] Specific examples of the superatomic valence iodine compound represented by formula (4) can include, but are not limited to, the following. In the following formulae, Me is a methyl group.

[0148] [Chem. 27]

[0149]

[0150] [Chem. 28]

[0151]

[0152] [Chem. 29]

[0153]

[0154] [Chem. 30]

[0155]

[0156] [Chem. 31]

[0157]

[0158] [Chem. 32]

[0159]

[0160] [Chem. 33]

[0161]

[0162] [Chem. 34]

[0163]

[0164] [Chem. 35]

[0165]

[0166] [Chem. 36]

[0167]

[0168] [Chem. 37]

[0169]

[0170] [Chem. 38]

[0171]

[0172] [Chem. 39]

[0173]

[0174] [Chem. 40]

[0175]

[0176] [Chem. 41]

[0177]

[0178] [Chem. 42]

[0179]

[0180] [Chem. 43]

[0181]

[0182] [Chem. 44]

[0183]

[0184] [Chem. 45]

[0185]

[0186] [Chem. 46]

[0187]

[0188] [Chem. 47]

[0189]

[0190] [Chem. 48]

[0191]

[0192] [Chem. 49]

[0193]

[0194] [Chem. 50]

[0195]

[0196] [Chem. 51]

[0197]

[0198] [Chem. 52]

[0199]

[0200] [Chem. 53]

[0201]

[0202] [Chem. 54]

[0203]

[0204] [Chemical Formula 55]

[0205]

[0206] [Chemical Formula 56]

[0207]

[0208] [Chemical Formula 57]

[0209]

[0210] [Chemical Formula 58]

[0211]

[0212] [Chemical Formula 59]

[0213]

[0214] [Chemical Formula 60]

[0215]

[0216] [Chemical Formula 61]

[0217]

[0218] [Chemical Formula 62]

[0219]

[0220] [Chemical Formula 63]

[0221]

[0222] [Chemical Formula 64]

[0223]

[0224] [Chemical Formula 65]

[0225]

[0226] [Chemical Formula 66]

[0227]

[0228] [Chemical Formula 67]

[0229]

[0230] [Chemical Formula 68]

[0231]

[0232] [Chemical Formula 69]

[0233]

[0234] [Chemical Formula 70]

[0235]

[0236] [Chemical Formula 71]

[0237]

[0238] [Chemical Formula 72]

[0239]

[0240] [Chemical Formula 73]

[0241]

[0242] [Chemical Formula 74]

[0243]

[0244] [Chemical Formula 75]

[0245]

[0246] [Chemical Formula 76]

[0247]

[0248] [Chemical Formula 77]

[0249]

[0250] [Chemical Formula 78]

[0251]

[0252] [Chemical Formula 79]

[0253]

[0254] [Chemical Formula 80]

[0255]

[0256] [Chemical Formula 81]

[0257]

[0258] [Chemical Formula 82]

[0259]

[0260] [Polymer containing carboxyl group]

[0261] The aforementioned polymer containing carboxyl group contains a repeating unit represented by the following formula (5), and further contains at least one kind selected from a repeating unit represented by the following formula (6), a repeating unit represented by the following formula (7), a repeating unit represented by the following formula (8), a repeating unit represented by the following formula (9), and a repeating unit represented by the following formula (10). The repeating units represented by the following formulas (6) to (10) function as a photoacid generator.

[0262] [Chemical 83]

[0263]

[0264] In the formulas (5) to (10), R A are each independently a hydrogen atom or a methyl group. R B are each independently a hydrogen atom, or can also be bonded to Z 6 and form a ring.

[0265] In the formula (5), X 1 is a single bond, a phenylene group, a naphthylene group, or a group represented by *-C(=O)-O-X 11 -. X 11 is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group can also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. * represents an atomic bond to a carbon atom of the main chain.

[0266] Specific examples of the repeating unit containing carboxyl group represented by the formula (5) can be exemplified by the following, but are not limited thereto. In the following formulas, R A are the same as the aforementioned.

[0267] [Chemical 84]

[0268]

[0269] [Chemical 85]

[0270]

[0271] In the formula (6), Z 1 is a single bond, an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining them, or -O-Z 11 , -C(=O)-O-Z 11 , or -C(=O)-NH-Z 11 . Z 11 is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining them, and can also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group.

[0272] in formula (6), R 21 and R 22 are each independently a halogen atom or a hydrocarbon group having a carbon number of 1 to 20 which can also contain a hetero atom. The aforementioned hydrocarbon group can be either saturated or unsaturated, and can be any one of linear, branched, or cyclic. Specific examples thereof can be exemplified by the hydrocarbon groups represented by R 41 to R 45 having a carbon number of 1 to 20 as exemplified in the following formulae (Ml) and (M2) in the following description.

[0273] The cation of the monomer providing the repeating unit represented by formula (6) can be exemplified by the following, but is not limited thereto. In the following formulae, R A are the same as the aforementioned.

[0274] [Chem. 86]

[0275]

[0276] in formula (6), X - is a non-nucleophilic counter ion. Specific examples of the aforementioned non-nucleophilic counter ion can be exemplified by halogen ions such as chloride ions, bromide ions; fluorinated alkyl sulfonate ions such as triflate ions, 1,1,1-trifluoroethanesulfonate ions, nonafluorobutanesulfonate ions; aryl sulfonate ions such as tosylate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, 1,2,3,4,5-pentafluorobenzenesulfonate ions; alkyl sulfonate ions such as methanesulfonate ions, butanesulfonate ions; imide ions such as bis(trifluoromethylsulfonyl)imide ions, bis(perfluoroethylsulfonyl)imide ions, bis(perfluorobutylsulfonyl)imide ions; and methide ions such as tris(trifluoromethylsulfonyl)methide ions, tris(perfluoroethylsulfonyl)methide ions.

[0277] The aforementioned non-nucleophilic counter ion can further be exemplified by sulfonic acid ions in which the α-position is substituted with a fluorine atom represented by the following formula (6-1), and sulfonic acid ions in which the α-position is substituted with a fluorine atom and the β-position is substituted with a trifluoromethyl group represented by the following formula (6-2).

[0278] [Chem. 87]

[0279]

[0280] in formula (6-1), R 31 is a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20, and the hydrocarbon group can also contain an ether bond, an ester bond, a carbonyl group, a lactone ring, or a fluorine atom. The aforementioned hydrocarbon group can be either saturated or unsaturated, and can be any one of linear, branched, or cyclic.

[0281] in formula (6-2), R 32hydrogen atom, a hydrocarbon group having a carbon number of 1 to 30, or a hydrocarbon carbonyl group having a carbon number of 2 to 30, and the hydrocarbon group and the hydrocarbon carbonyl group can also have an ether bond, an ester bond, a carbonyl group, or a lactone ring. The aforementioned hydrocarbon group and the hydrocarbon carbonyl group can be either saturated or unsaturated, and can be any of linear, branched, or cyclic.

[0282] The aforementioned non-nucleophilic counter ion can also be represented by an anion having an aromatic ring substituted with a bromine atom or an iodine atom, as represented by the following formula (6-3).

[0283] [Chemical Formula 88]

[0284]

[0285] In formula (6-3), p is 1, 2, or 3. q is 1, 2, 3, 4, or 5. r is 0, 1, 2, or 3. However, 1 ≤ q + r ≤ 5. q is preferably 1, 2, or 3, more preferably 2 or 3. r is preferably 0, 1, or 2.

[0286] In formula (6-3), X BI is an iodine atom or a bromine atom, and p and / or q can be the same as each other or different from each other when p and / or q are 2 or more.

[0287] In formula (6-3), L 1 is a single bond, an ether bond, or an ester bond, or a saturated hydrocarbylene group having a carbon number of 1 to 6 that can also have an ether bond or an ester bond. The aforementioned saturated hydrocarbylene group can be any of linear, branched, or cyclic.

[0288] In formula (6-3), L 2 is a single bond or a divalent linking group having a carbon number of 1 to 20 when p is 1, and is a (p + 1)-valent linking group having a carbon number of 1 to 20 when p is 2 or 3, and the linking group can also have an oxygen atom, a sulfur atom, or a nitrogen atom.

[0289] In formula (6-3), R 33 is a hydroxyl group, a carboxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an amino group, or a hydrocarbon group having a carbon number of 1 to 20, a hydrocarbon oxy group having a carbon number of 1 to 20, a hydrocarbon carbonyl group having a carbon number of 2 to 20, a hydrocarbon oxy carbonyl group having a carbon number of 2 to 20, a hydrocarbon carbonyl oxy group having a carbon number of 2 to 20, or a hydrocarbon sulfonyl oxy group having a carbon number of 1 to 20, which can also have a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, an amino group, or an ether bond, or -N(R 33A )(R 33B ), -N(R 33C )-C(=O)-R 33D , or -N(R 33C )-C(=O)-O-R 33D . R 33A and R 33B are each independently a hydrogen atom or a saturated hydrocarbon group having a carbon number of 1 to 6. R 33CIt is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms. R 33D It is an aliphatic hydrocarbon group with 1 to 16 carbon atoms, an aryl group with 6 to 14 carbon atoms, or an aralkyl group with 7 to 15 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxy group with 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group with 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl oxy group with 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned hydrocarbon group, hydrocarbon oxy group, hydrocarbon oxycarbonyl group, hydrocarbon carbonyl group, hydrocarbon carbonyl oxy group, and hydrocarbon sulfonyl oxy group can be linear, branched, or cyclic. When p and / or r is 2 or more, each R 33 They can be the same or different.

[0290] Among them, R 33 It is advisable to use hydroxyl groups, -N(R) 33C )-C(=O)-R 33D -N(R) 33C )-C(=O)-OR 33D Fluorine atoms, chlorine atoms, bromine atoms, methyl groups, methoxy groups, etc.

[0291] In equation (6-3), Rf 11 ~Rf 14 Each of these atoms can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of them must be a fluorine atom or a trifluoromethyl group. Also, Rf 11 With Rf 12 They can also combine to form carbonyl groups. Rf 13 and Rf 14 All of them are fluorine atoms, which is of excellent quality.

[0292] The anions represented by equation (6-3) can be listed below, but are not limited to these. Additionally, in the following equation, X... BI Same as above.

[0293] [Chemistry 89]

[0294]

[0295] [Chemistry 90]

[0296]

[0297] [Chemistry 91]

[0298]

[0299] [Chemistry 92]

[0300]

[0301] [Chemical Formula 93]

[0302]

[0303] [Chemical Formula 94]

[0304]

[0305] [Chemical Formula 95]

[0306]

[0307] [Chemical Formula 96]

[0308]

[0309] [Chemical Formula 97]

[0310]

[0311] [Chemical Formula 98]

[0312]

[0313] [Chemical Formula 99]

[0314]

[0315] [Chemical Formula 100]

[0316]

[0317] [Chemical Formula 101]

[0318]

[0319] [Chemical Formula 102]

[0320]

[0321] [Chemical Formula 103]

[0322]

[0323] [Chemical Formula 104]

[0324]

[0325] [Chemical Formula 105]

[0326]

[0327] [Chemical Formula 106]

[0328]

[0329] [Chem. 107]

[0330]

[0331] [Chem. 108]

[0332]

[0333] [Chem. 109]

[0334]

[0335] [Chem. 110]

[0336]

[0337] [Chem. 111]

[0338]

[0339] [Chem. 112]

[0340]

[0341] [Chem. 113]

[0342]

[0343] [Chem. 114]

[0344]

[0345] [Chem. 115]

[0346]

[0347] [Chem. 116]

[0348]

[0349] [Chem. 117]

[0350]

[0351] [Chem. 118]

[0352]

[0353] [Chem. 119]

[0354]

[0355] [Chem. 120]

[0356]

[0357] [Chemical Formula 121]

[0358]

[0359] [Chemical Formula 122]

[0360]

[0361] [Chemical Formula 123]

[0362]

[0363] [Chemical Formula 124]

[0364]

[0365] [Chemical Formula 125]

[0366]

[0367] In Formula (7), Z 2 is a single bond or an ester bond. Z 3 is a single bond, -Z 31 -C(=O)-O- or -Z 31 -O-. Z 31 is an alkylenyl group having 1 to 12 carbons, a phenylene group, or a group having 7 to 18 carbons obtained by combining them, and can also contain a carbonyl group, a nitro group, a cyano group, an ester bond, an ether bond, a urethane bond, a fluorine atom, an iodine atom, or a bromine atom. Z 4 is a single bond, a methylene group, or an ethylene group.

[0368] In Formula (7), Rf 1 to Rf 4 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 may also combine to form a carbonyl group.

[0369] Anions of the monomer providing the repeating unit represented by Formula (7) can be exemplified by those shown below, but are not limited thereto. In the following formulae, R A are the same as described above.

[0370] [Chemical Formula 126]

[0371]

[0372] [Chemical Formula 127]

[0373]

[0374] [Chemical Formula 128]

[0375]

[0376] [Chemical Formula 129]

[0377]

[0378] [Chemical Formula 130]

[0379]

[0380] [Chemical Formula 131]

[0381]

[0382] [Chemical Formula 132]

[0383]

[0384] [Chemical Formula 133]

[0385]

[0386] [Chemical Formula 134]

[0387]

[0388] [Chemical Formula 135]

[0389]

[0390] [Chemical Formula 136]

[0391]

[0392] [Chemical Formula 137]

[0393]

[0394] [Chemical Formula 138]

[0395]

[0396] [Chemical Formula 139]

[0397]

[0398] [Chemical Formula 140]

[0399]

[0400] [Chemical Formula 141]

[0401]

[0402] [Chemical Formula 142]

[0403]

[0404] [Chemical Formula 143]

[0405]

[0406] [Chemical Formula 144]

[0407]

[0408] [Chemical Formula 145]

[0409]

[0410] [Chemical Formula 146]

[0411]

[0412] [Chemical Formula 147]

[0413]

[0414] [Chemical Formula 148]

[0415]

[0416] [Chemical Formula 149]

[0417]

[0418] [Chemical Formula 150]

[0419]

[0420] In Formula (8), Z 5 is a single bond, methylene, ethylene, phenylene, methylphenylene, dimethylphenylene, fluorinated phenylene, phenylene substituted with a trifluoromethyl group, -0-Z 51 -, -C(=0)-0-Z 51 or -C(=0)-NH-Z 51 . Z 51 is an aliphatic hydrocarbylene group having a carbon number of 1 to 6, phenylene, methylphenylene, dimethylphenylene, fluorinated phenylene, or phenylene substituted with a trifluoromethyl group, and can also contain a carbonyl group, an ester bond, an ether bond, a hydroxyl group, or a halogen atom.

[0421] An anion of a monomer providing a repeating unit represented by Formula (8) can be exemplified by those shown below, but is not limited thereto. In addition, in the following formulae, R A is the same as described above.

[0422] [Chemical Formula 151]

[0423]

[0424] [Chemistry 152]

[0425]

[0426] In equations (9) and (10), Z 6 It can be a single bond, a phenylene ring, a naphthoid ring, an ester bond, or an amide bond.

[0427] In equation (9), Z 7A It is a single bond or a divalent organic group having 1 to 24 carbon atoms, and may also have at least one of the following: halogen atom, oxygen atom, nitrogen atom and sulfur atom.

[0428] Z 7A The divalent organic group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include hydrocarbon groups with 1 to 24 carbon atoms in which some or all of the hydrogen atoms are replaced by iodine or bromine atoms. The aforementioned alkylene groups with 1 to 24 carbon atoms can be listed as follows: methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, octadecane-1,18-diyl, nonadecane-1,19-diyl, eicosane-1,20-diyl, etc.; cyclopentanediyl... Cyclic saturated hydrocarbon groups such as methylcyclopentanediyl, dimethylcyclopentanediyl, trimethylcyclopentanediyl, tetramethylcyclopentanediyl, cyclohexanediyl, methylcyclohexanediyl, dimethylcyclohexanediyl, trimethylcyclohexanediyl, tetramethylcyclohexanediyl, norcamphenediyl, adamantanediyl, etc.; aryl groups such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, isobutylphenylene, sec-butylphenylene, tert-butylphenylene, naphthylene, methylnaphthylene, ethylnaphthylene, n-propylnaphthylene, isopropylnaphthylene, n-butylnaphthylene, isobutylnaphthylene, sec-butylnaphthylene, tert-butylnaphthylene, biphenyl diyl, methylbiphenyl diyl, dimethylbiphenyl diyl, etc.; and groups obtained by combining them. Also, Z 7A Some or all of the hydrogen atoms may be substituted by groups containing at least one of the following: oxygen, nitrogen, and sulfur atoms, and Z 7A A portion of the -CH2- group may also be substituted with a group containing at least one of oxygen, nitrogen, and sulfur atoms, resulting in the presence of hydroxyl, ester, ether, amide, carbamate, urea, etc.

[0429] In formula (10), Z 7B is a monovalent organic group having 1 to 10 carbon atoms, and can also have at least one selected from a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom.

[0430] Z 7B The monovalent organic group represented by Z 7B may be saturated or unsaturated, and can be any of linear, branched, or cyclic. Specific examples thereof can include a hydrocarbon group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms are substituted with iodine atoms or bromine atoms. The aforementioned hydrocarbon group having 1 to 10 carbon atoms can include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, sec-pentyl, 3-pentyl, t-pentyl, neopentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, and the like; cyclic saturated hydrocarbon groups having 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, methylcyclopropyl, methylcyclobutyl, methylcyclopentyl, methylcyclohexyl, ethylcyclopropyl, ethylcyclobutyl, ethylcyclopentyl, ethylcyclohexyl, and the like; alkenyl groups having 2 to 10 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, decenyl, and the like; alkynyl groups having 2 to 10 carbon atoms such as ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, and the like; cyclic unsaturated aliphatic hydrocarbon groups having 3 to 10 carbon atoms such as cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexenyl, ethylcyclopentenyl, ethylcyclohexenyl, norbornenyl, and the like; aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, t-butylphenyl, naphthyl, and the like; aralkyl groups having 7 to 10 carbon atoms such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, and the like; and combinations thereof. Also, some or all of the hydrogen atoms of Z 7B may be substituted with a group containing at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and as a result, Z 7B may also contain a hydroxyl group, an ester bond, an ether bond, an amide bond, a urethane bond, a urea bond, and the like.

[0431] In formulae (9) and (10), Z 8 is a single bond, an ether bond, an ester bond, a thioether bond, or an alkanediyl group having 1 to 6 carbon atoms.

[0432] In formula (10), Z 9 is a trivalent organic group having 1 to 12 carbon atoms, and can also have at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom. Z 9The 3-valent organic group represented by the formula: -Z- can be saturated or unsaturated, and can be any one of linear, branched, and cyclic. Specific examples thereof can include groups obtained by removing one hydrogen atom from a hydrocarbylene group having 1 to 12 carbon atoms. The hydrocarbylene group having 1 to 12 carbon atoms can include those having 1 to 12 carbon atoms among the hydrocarbylene groups having 1 to 24 carbon atoms described above. Also, Z 9 may be substituted with a group containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, and Z 9 may be substituted with a group containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, and as a result, can contain a hydroxyl group, an ester bond, an ether bond, an amide bond, a urethane bond, a urea bond, and the like.

[0433] In the formulae (9) and (10), R 23 is a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a fluorine atom, an iodine atom, a trifluoromethoxy group, a difluoromethoxy group, a cyano group, or a nitro group.

[0434] In the formulae (9) and (10), R is an (a+2)-valent aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of the (a+2)-valent aromatic hydrocarbon group can include groups obtained by removing (a+2) hydrogen atoms from an aromatic hydrocarbon such as benzene or naphthalene.

[0435] In the formulae (9) and (10), a is an integer of 0 to 5.

[0436] Specific examples of the anion of the repeating unit represented by the formula (9) and the repeating unit represented by the formula (10) can include those shown below, but are not limited thereto. In the formulae below, R A is the same as described above, and X BI is an iodine atom or a bromine atom.

[0437] [Chemical Formula 153]

[0438]

[0439] [Chemical Formula 154]

[0440]

[0441] [Chemical Formula 155]

[0442]

[0443] [Chemical Formula 156]

[0444]

[0445] [Chemical Formula 157]

[0446]

[0447] [Chemical Formula 158]

[0448]

[0449] [Chemical Formula 159]

[0450]

[0451] [Chemical Formula 160]

[0452]

[0453] [Chemical Formula 161]

[0454]

[0455] [Chemical Formula 162]

[0456]

[0457] [Chemical Formula 163]

[0458]

[0459] [Chemical Formula 164]

[0460]

[0461] [Chemical Formula 165]

[0462]

[0463] [Chemical Formula 166]

[0464]

[0465] [Chemical Formula 167]

[0466]

[0467] [Chemical Formula 168]

[0468]

[0469] [Chemical Formula 169]

[0470]

[0471] [Chemical Formula 170]

[0472]

[0473] [Chemical Formula 171]

[0474]

[0475] [Chemical structure 172]

[0476]

[0477] [Chemical structure 173]

[0478]

[0479] [Chemical structure 174]

[0480]

[0481] [Chemical structure 175]

[0482]

[0483] [Chemical structure 176]

[0484]

[0485] [Chemical structure 177]

[0486]

[0487] [Chemical structure 178]

[0488]

[0489] [Chemical structure 179]

[0490]

[0491] [Chemical structure 180]

[0492]

[0493] [Chemical structure 181]

[0494]

[0495] [Chemical structure 182]

[0496]

[0497] [Chemical structure 183]

[0498]

[0499] [Chemical structure 184]

[0500]

[0501] [Chemical structure 185]

[0502]

[0503] [Chemical 186]

[0504]

[0505] [Chemical 187]

[0506]

[0507] [Chemical 188]

[0508]

[0509] [Chemical 189]

[0510]

[0511] [Chemical 190]

[0512]

[0513] [Chemical 191]

[0514]

[0515] [Chemical 192]

[0516]

[0517] [Chemical 193]

[0518]

[0519] [Chemical 194]

[0520]

[0521] [Chemical 195]

[0522]

[0523] [Chemical 196]

[0524]

[0525] [Chemical 197]

[0526]

[0527] [Chemical 198]

[0528]

[0529] [Chemical 199]

[0530]

[0531] [Chemical Formula 2]

[0532]

[0533] [Chemical Formula 3]

[0534]

[0535] [Chemical Formula 4]

[0536]

[0537] [Chemical Formula 5]

[0538]

[0539] [Chemical Formula 6]

[0540]

[0541] In formulae (7) to (10), M + is a sulfonium cation or a sulfoxonium cation. The aforementioned sulfonium cation is preferably represented by the following formula (M-1), and the aforementioned sulfoxonium cation is preferably represented by the following formula (M-2).

[0542] [Chemical Formula 7]

[0543]

[0544] In formulae (M-1) and (M-2), R 41 ~R 45 are each independently a halogen atom or a hydrocarbon group having a carbon number of 1 to 20 which can also contain a hetero atom.

[0545] R 41 ~R 45 Specific examples of the halogen atom represented by R

[0546] R 41 ~R 45The hydrocarbon group represented by the formula: -CnH2n+1- (wherein n represents an integer of 1 to 20) can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and the like; cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl, and the like; alkenyl groups having 2 to 20 carbon atoms such as vinyl, propenyl, butenyl, hexenyl, and the like; alkynyl groups having 2 to 20 carbon atoms such as ethynyl, propynyl, butynyl, and the like; cyclic unsaturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms such as cyclohexenyl, norbornenyl, and the like; aryl groups having 6 to 20 carbon atoms such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, t-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butyl- naphthyl, isobutylnaphthyl, sec-butylnaphthyl, t-butylnaphthyl, and the like; aralkyl groups having 7 to 20 carbon atoms such as benzyl, phenethyl, and the like; and groups obtained by combining these groups.

[0547] Further, a part or all of the hydrogen atoms of the aforementioned hydrocarbon group can be substituted with a group containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, a halogen atom, or the like, and a part of the -CH2- groups of the aforementioned hydrocarbon group can be substituted with a group containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or the like. As a result, the aforementioned hydrocarbon group can contain a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a mercapto group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate ester bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-O-C(=O)-), a haloalkyl group, or the like.

[0548] Further, R 41 and R 42 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. In this case, the aforementioned ring is preferably a structure represented by the following formula.

[0549] [Chemical Formula 206]

[0550]

[0551] In the formula, the dotted line represents a bond between atoms.

[0552] M + Specific examples of the sulfonium cation represented by the formula: -S+R1R2R3 (wherein R1, R2, and R3 each independently represent a hydrocarbon group having 1 to 20 carbon atoms) include, but are not limited to, the following.

[0553] [Chemical Formula 207]

[0554]

[0555] [Chemical Formula 208]

[0556]

[0557] [Chemical Formula 209]

[0558]

[0559] [Chemical Formula 210]

[0560]

[0561] [Chemical Formula 211]

[0562]

[0563] [Chemical Formula 212]

[0564]

[0565] [Chemical Formula 213]

[0566]

[0567] [Chemical Formula 214]

[0568]

[0569] [Chemical Formula 215]

[0570]

[0571] [Chemical Formula 216]

[0572]

[0573] [Chemical Formula 217]

[0574]

[0575] [Chemical Formula 218]

[0576]

[0577] [Chemical Formula 219]

[0578]

[0579] [Chemical Formula 220]

[0580]

[0581] [Chemical Formula 221]

[0582]

[0583] [Chemical Formula 222]

[0584]

[0585] [Chemical Formula 223]

[0586]

[0587] [Chemical Formula 224]

[0588]

[0589] [Chemical Formula 225]

[0590]

[0591] [Chemical Formula 226]

[0592]

[0593] [Chemical Formula 227]

[0594]

[0595] [Chemical Formula 228]

[0596]

[0597] [Chemical Formula 229]

[0598]

[0599] [Chemical Formula 230]

[0600]

[0601] [Chemical Formula 231]

[0602]

[0603] [Chemical Formula 232]

[0604]

[0605] [Chemical Formula 233]

[0606]

[0607] [Chemical Formula 234]

[0608]

[0609] [Chemical Formula 235]

[0610]

[0611] [Chemical Formula 236]

[0612]

[0613] [Chemical Formula 237]

[0614]

[0615] [Chemical Formula 238]

[0616]

[0617] [Chemical Formula 239]

[0618]

[0619] [Chemical Formula 240]

[0620]

[0621] [Chemical Formula 241]

[0622]

[0623] [Chemical Formula 242]

[0624]

[0625] M + Specific examples of the sulfonium cation represented by the formula (M-1) and the sulfo cation represented by the formula (M-2) can include, but are not limited to, the following.

[0626] [Chemical Formula 243]

[0627]

[0628] [Chemical Formula 244]

[0629]

[0630] The aforementioned carboxyl group-containing polymer can further contain a repeating unit other than the aforementioned carboxyl group-containing repeating unit (hereinafter also referred to as other repeating unit). A desirable other repeating unit can include a unit that initiates salt exchange with a sulfonic acid generated from the photoacid generator unit at the exposed portion and generates a carboxylic acid, and functions as a quencher.

[0631] The monomer that provides such a repeating unit that functions as a quencher is desirably an onium salt of a carboxylic acid having a polymerizable group. Specific examples of the cation of the aforementioned onium salt are a sulfonium cation represented by the formula (M-1) and a sulfo cation represented by the formula (M-2). Specific examples of the anion of the aforementioned onium salt can include, but are not limited to, the following. Note that, in the following formulae, R A and the aforementioned.

[0632] [Chemical Formula 245]

[0633]

[0634] [Chemical Formula 246]

[0635]

[0636] [Chemical Formula 247]

[0637]

[0638] [Chemical Formula 248]

[0639]

[0640] [Chemical Formula 249]

[0641]

[0642] [Chemical Formula 250]

[0643]

[0644] [Chemical Formula 251]

[0645]

[0646] [Chemical Formula 252]

[0647]

[0648] [Chemical Formula 253]

[0649]

[0650] [Chemical Formula 254]

[0651]

[0652] [Chemical Formula 255]

[0653]

[0654] [Chemical Formula 256]

[0655]

[0656] [Chemical Formula 257]

[0657]

[0658] [Chemical Formula 258]

[0659]

[0660] [Chemical Formula 259]

[0661]

[0662] [Chemical Formula 260]

[0663]

[0664] [Chemical Formula 261]

[0665]

[0666] [Chemical Formula 262]

[0667]

[0668] [Chemical Formula 263]

[0669]

[0670] [Chemical Formula 264]

[0671]

[0672] [Chemical Formula 265]

[0673]

[0674] [Chemical Formula 266]

[0675]

[0676] [Chemical Formula 267]

[0677]

[0678] [Chemical Formula 268]

[0679]

[0680] [Chemical Formula 269]

[0681]

[0682] [Chemical Formula 270]

[0683]

[0684] [Chemical Formula 271]

[0685]

[0686] [Chemical Formula 272]

[0687]

[0688] [Chemical Formula 273]

[0689]

[0690] [Chemical Formula 274]

[0691]

[0692] [Chemical Formula 275]

[0693]

[0694] [Chemical Formula 276]

[0695]

[0696] [Chemical Formula 277]

[0697]

[0698] [Chemical Formula 278]

[0699]

[0700] Other examples of the other repeating unit can include one that improves the solubility of a polymer that is hardly soluble in a solvent when only a repeating unit having a carboxyl group is contained. Also, a repeating unit having a cyclic structure that is expected to have high etching resistance due to a rigid skeleton, a repeating unit having a styrene skeleton can be exemplified as a main component.

[0701] Specific examples of the other repeating unit described above can include the following, but are not limited thereto. In the following formulae, R A and the above, X B are each independently -CH2- or -O-.

[0702] [Chemical Formula 279]

[0703]

[0704] [Chemical Formula 280]

[0705]

[0706] [Chemical Formula 281]

[0707]

[0708] [Chemical Formula 282]

[0709]

[0710] [Chemical Formula 283]

[0711]

[0712] [Chem. 284]

[0713]

[0714] [Chem. 285]

[0715]

[0716] [Chem. 286]

[0717]

[0718] [Chem. 287]

[0719]

[0720] [Chem. 288]

[0721]

[0722] [Chem. 289]

[0723]

[0724] [Chem. 290]

[0725]

[0726] [Chem. 291]

[0727]

[0728] [Chem. 292]

[0729]

[0730] [Chem. 293]

[0731]

[0732] [Chem. 294]

[0733]

[0734] [Chem. 295]

[0735]

[0736] [Chem. 296]

[0737]

[0738] [Chem. 297]

[0739]

[0740] [Chem. 298]

[0741]

[0742] [Chemical Formula 299]

[0743]

[0744] [Chemical Formula 300]

[0745]

[0746] [Chemical Formula 301]

[0747]

[0748] [Chemical Formula 302]

[0749]

[0750] [Chemical Formula 303]

[0751]

[0752] [Chemical Formula 304]

[0753]

[0754] [Chemical Formula 305]

[0755]

[0756] [Chemical Formula 306]

[0757]

[0758] [Chemical Formula 307]

[0759]

[0760] [Chemical Formula 308]

[0761]

[0762] Specific examples of the repeating unit represented by formulae (6) to (10) can include any combination of the aforementioned anions and cations.

[0763] The repeating unit represented by formulae (6) to (10) can be used alone as one kind, or two or more kinds in combination.

[0764] The photoacid generator, by being bonded to the polymer, inhibits diffusion of the acid generated at the exposed portions, so a pattern of excellent resolution can be formed. Also, when the photoacid generator is bonded to the polymer, the photoacid generator is uniformly dispersed in the resist film and the glass transition temperature of the resist is also increased, compared to the case where the photoacid generator is not bonded to the polymer, so a high-resolution pattern with reduced roughness can be formed.

[0765] When the repeating units represented by formulae (6) to (10) have elements such as fluorine atoms and iodine atoms that have a high absorption effect for EUV light, the amount of secondary electrons generated increases, and the decomposition of cations is promoted, so this is ideal for high-sensitivity fine pattern formation.

[0766] The content of the carboxyl group-containing repeating unit represented by formula (5) in the aforementioned carboxyl group-containing polymer is preferably 10 to 95 mol%, and more preferably 20 to 80 mol%. The content of the photoacid generator repeating unit represented by formulae (6) to (10) is preferably 5 to 40 mol%, and more preferably 10 to 30 mol%. The content of other repeating units is preferably 0 to 50 mol%, and more preferably 10 to 40 mol%.

[0767] The weight average molecular weight (Mw) of the aforementioned carboxyl group-containing polymer is preferably 1000 to 500000, and more preferably 3000 to 100000. Note that the Mw in the present application is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the solvent.

[0768] Also, in the aforementioned carboxyl group-containing polymer, when the molecular weight distribution (Mw / Mn) is wide, there are concerns that low-molecular-weight and high-molecular-weight polymers will be present, and that foreign matter will be observed on the pattern after exposure, and the pattern shape will deteriorate. Therefore, as the pattern becomes more regular and finer, the influence of Mw and Mw / Mn tends to increase, so in order to obtain a resist composition that can be ideally used for fine pattern sizes, the Mw / Mn of the aforementioned carboxyl group-containing polymer is preferably narrow, and is preferably 1.0 to 2.0.

[0769] In the resist composition of the present application, the ratio of the super-valent iodine compound to the carboxylic acid-containing repeating unit in the carboxyl group-containing polymer is preferably, in terms of the molar ratio, super-valent iodine compound: carboxyl group-containing polymer = 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30. The aforementioned super-valent iodine compound can be used alone or in combination with two or more. The aforementioned carboxyl group-containing polymer can be used alone or in combination with two or more having different composition ratios, Mw, and / or Mw / Mn.

[0770] As a method for synthesizing the aforementioned carboxyl group-containing polymer, for example, a method in which a monomer that provides the aforementioned repeating unit is added with a radical polymerization initiator in an organic solvent and heated to polymerize can be exemplified.

[0771] As a specific example of the organic solvent used in the polymerization reaction, toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, cyclopentanone, cyclohexanone, methyl ethyl ketone (MEK), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), and the like can be exemplified. As a specific example of the aforementioned polymerization initiator, 2,2'-azobis isobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2-azobis (2-methylpropanoate), 1,1'-azobis (1-acetoxy-1-phenylethane), benzoyl peroxide, lauroyl peroxide, and the like can be exemplified. The amount of addition of these initiators is preferably 0.01 to 25 mol% with respect to the total of the monomers to be polymerized. The reaction temperature is preferably 50 to 150°C, and more preferably 60 to 100°C. The reaction time is preferably 2 to 24 hours, and more preferably 2 to 12 hours from the viewpoint of production efficiency.

[0772] The aforementioned polymerization initiator can be added to the aforementioned monomer solution and supplied to the reaction vessel, or an initiator solution different from the aforementioned monomer solution can be prepared separately and supplied to the reaction vessel independently. Since there is a possibility that the polymerization reaction proceeds due to the radicals generated from the initiator during the standby time and an ultrahigh molecular weight substance is generated, the monomer solution and the initiator solution are preferably prepared and added separately independently from the viewpoint of quality management. Also, in order to adjust the molecular weight, a known chain transfer agent such as dodecyl mercaptan or 2-mercaptoethanol can be used in combination. At this time, the amount of addition of these chain transfer agents is preferably 0.01 to 20 mol% with respect to the total of the monomers to be polymerized.

[0773] In addition, the amount of each monomer in the aforementioned monomer solution can be appropriately set so as to become the desired content ratio of the aforementioned repeating unit.

[0774] [Solvent]

[0775] The aforementioned resist composition contains a solvent. The aforementioned solvent is not particularly limited as long as it can dissolve the aforementioned hypervalent iodine compound, the carboxyl group-containing polymer, and other components described later and form a film. Such a solvent is preferably an organic solvent, and specific examples thereof include ketones such as cyclohexanone, methyl-2-n-pentyl ketone, and methyl isobutyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, 4-methyl-2-pentanol, and methyl 2-hydroxyisobutyrate; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, and propylene glycol mono-t-butyl ether acetate; carboxylic acids such as formic acid, acetic acid, and propionic acid; lactones such as γ-butyrolactone; and a mixture solvent thereof.

[0776] In the resist composition of the present application, the content of the aforementioned solvent is preferably an amount in which the concentration of solid components in the resist composition becomes 0.1 to 20% by mass, more preferably an amount in which the concentration of solid components becomes 0.1 to 15% by mass, and still more preferably an amount in which the concentration of solid components becomes 0.1 to 10% by mass. Note that the solid components in the present application refer to the total of components other than the solvent among all components of the resist composition. The aforementioned solvent can be used alone as one kind or in combination with two or more kinds.

[0777] [Other components]

[0778] The resist composition of the present application can also contain a quencher. The aforementioned quencher can include basic compounds. Known types of basic compounds can include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, carbamates, and the like. In particular, primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103, amine compounds having a hydroxyl group, an ether bond, an ester bond, a lactone ring, a cyano group, a sulfonate bond, or compounds having a carbamate group described in Japanese Patent No. 3790649, and the like are preferable. By adding such a basic compound, for example, the diffusion speed of acid in a resist film can be further controlled, or the shape can be corrected.

[0779] Further, the aforementioned quencher can include sulfonium salts, phosphonium salts, ammonium salts, and the like of sulfonic acids and carboxylic acids in which the α-position is not fluorinated, as described in Japanese Patent Application Publication No. 2008-158339. Sulfonic acids, imide acids, and methylated acids in which the α-position is fluorinated release sulfonic acids and carboxylic acids in which the α-position is not fluorinated by salt exchange with onium salts in which the α-position is not fluorinated. Sulfonic acids and carboxylic acids in which the α-position is not fluorinated are less likely to cause ligand exchange with hypervalent iodine compounds, and thus function as a quencher. Further, other quenchers can include onium salts of carboxylic acids in which the α-position is fluorinated, as described in Japanese Patent No. 5904180. α-Fluorocarboxylic acids are less acidic than sulfonic acids, and thus have a high quencher ability, and can form patterns with good roughness and resolution.

[0780] The resist composition of the present application preferably contains the aforementioned quencher in an amount of 0 to 10 parts by mass, more preferably 0 to 7 parts by mass, relative to 100 parts by mass of the resist material. The other quencher can be used alone or in combination with two or more kinds.

[0781] The resist composition of the present application can further contain a surfactant. The aforementioned surfactant is preferably a fluorine-based and / or silicone-based surfactant. Such a surfactant can include those described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. In addition, a surfactant other than the fluorine-based and / or silicone-based surfactants described in paragraph

[0280] of U.S. Patent Application Publication No. 2008 / 0248425 can be used.

[0782] The resist composition of the present application preferably contains the aforementioned surfactant in an amount of 0.0001 to 2% by mass, relative to the total solid content. The aforementioned surfactant can be used alone or in combination with two or more kinds.

[0783] The resist composition of the present application can further contain a radical scavenger. By adding a radical scavenger, the light reaction during photolithography can be controlled and the sensitivity can be adjusted.

[0784] The aforementioned radical scavenger can include hindered phenols, quinones, hindered amines, thiol compounds, and the like. Specifically, the hindered phenols can include dibutylhydroxytoluene (BHT), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and the like. The quinones can include 4-methoxyphenol (metoquinone), hydroquinone, and the like. The hindered amines can include 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethylpiperidine-N-oxyl, and the like. The thiol compounds can include dodecanethiol, hexadecanethiol, and the like.

[0785] The content of the aforementioned radical scavenger in the resist composition of the present application is preferably 0.01 to 10% by mass, based on the total solid content. One kind of the aforementioned radical scavenger can be used alone, or two or more kinds thereof can be used in combination.

[0786] The resist composition of the present application can further contain a crosslinking agent. By adding the crosslinking agent, crosslinking reaction during photolithography can be promoted, and the glass transfer point of a pattern can be improved, and a fine line resolution excellent pattern can be obtained.

[0787] The aforementioned crosslinking agent can include a compound having a carbon-carbon unsaturated bond such as a vinyl group, a (meth)acrylate group, an allyl group, an alkynyl group, an aromatic ring, or the like as a functional group. Specifically, the compound having a vinyl group can include a chain olefin, a branched olefin, a cyclic olefin, or the like, which can also have a substituent. The compound having a (meth)acrylate group can include acrylic acid, methacrylic acid, an acrylate ester, a methacrylate ester, or the like, which can also have a substituent. The compound having an allyl group can include an allyl alcohol, an allyl ether, an allyl ester, an allyl amide, an allyl amine, an allyl-containing isocyanurate, or the like, which can also have a substituent. The compound having an alkynyl group can include a chain alkyne, a branched alkyne, a cyclic alkyne, an alkynyl alcohol, an alkynyl ether, an alkynyl ester, an alkynyl amide, an alkynyl amine, an alkynyl-containing isocyanurate, or the like, which can also have a substituent. The compound having an aromatic ring can include an aromatic hydrocarbon, a heteroaromatic hydrocarbon, a styrene, a stilbene, a phenylacetylene, an acenaphthene, a Chalcone, or the like, which can also have a substituent. The crosslinking agent can have only one of the aforementioned functional groups, or can have a plurality thereof. The number of the aforementioned functional groups contained in the crosslinking agent is preferably 1 or more and 10 or less, more preferably 2 or more and 8 or less.

[0788] The content of the aforementioned crosslinking agent in the resist composition of the present application is preferably 0.01 to 50% by mass, based on the total solid content. One kind of the aforementioned crosslinking agent can be used alone, or two or more kinds thereof can be used in combination.

[0789] The resist composition of the present application, when containing the aforementioned crosslinking agent, can further contain a photopolymerization initiator. The photopolymerization initiator can generate a radical by irradiation of high-energy rays, and promote crosslinking of the aforementioned crosslinking agent.

[0790] Specific examples of the aforementioned photopolymerization initiator can include: benzophenone, O-benzoyl methyl benzoate, 4-benzoyl-4'-methylbenzophenone, dibenzyl ketone, fluorenone and other benzophenone derivatives; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)-benzyl]-phenyl}-2-methylpropane-1-one, methyl phenylglyoxylate and other acetophenone derivatives; thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone and other thioxanthone derivatives; benzoin, benzoin dimethyl ketal, benzoin-β-methoxyethyl acetal and other benzoin derivatives; benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropane-1-one and other benzoin derivatives; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetone-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetone-2-(O-benzoyl)oxime-1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)]ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and other oxime-based compounds; 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)-benzyl]phenyl}-2-methylpropane and other α-hydroxy ketone-based compounds; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butanone and other α-aminoalkyl phenyl ketone-based compounds; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide and other phosphine oxide-based compounds; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and other titanocene compounds and the like.

[0791] The content of the aforementioned photopolymerization initiator in the resist composition of the present application is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and most preferably 0.1 to 1% by mass, in the total solid content. If it is 0.1% by mass or more, the blending effect can be sufficiently obtained.

[0792] The resist composition of the present application contains, as main components, the hypervalent iodine compound and the carboxyl group-containing polymer as described above, but does not contain the acid-labile group-containing polymer contained in known chemically amplified resist compositions. However, the resist composition of the present application can form a positive pattern in which the exposed portion is soluble in a developer, particularly using EB or EUV exposure. The mechanism thereof has not been fully elucidated, but is presumed as follows.

[0793] The hypervalent iodine compound represented by formula (1), (2), (3) or (4) is a tricoordinated compound having an aryl group and a carboxylate ligand. It is considered that such a tricoordinated iodine compound, by mixing with a carboxyl group-containing polymer, undergoes exchange of the carboxylate ligand in an equilibrium reaction. At this time, if the original carboxylate ligand is removed by any means, a hypervalent iodine compound having a new ligand is generated. For example, if 1-iodonaphthylene diacetate as a hypervalent iodine compound is mixed with a carboxyl group-containing polymer, and the generated low-boiling acetic acid is removed, the ligand exchange is completed. Here, the carboxyl group-containing polymer becomes a crosslinked polymer by the hypervalent iodine compound.

[0794] The polymer crosslinked with the hypervalent iodine compound is generated at the time of film formation. The reason is that even if such a crosslinked polymer is synthesized in advance, it is not soluble in almost all organic solvents, and thus a solution cannot be prepared. It is presumed that this is because the hypervalent iodine compound, which originally has low solvent solubility due to large polarity, uses the carboxyl group-containing polymer as a ligand, and thus the solubility is further deteriorated. Therefore, it is desirable to provide a step of removing the original low-molecular carboxylic acid component at the time of film formation and in a baking step thereafter, thereby completing the ligand exchange reaction, and simultaneously forming a resist film.

[0795] In the resist film obtained from the resist composition of the present application, the hypervalent iodine compound as a main component thereof is decomposed by light, whereby the polarity changes, and a pattern is formed using a developing step. The mechanism thereof has not been fully elucidated, but is presumed as follows, for example.

[0796] The resist film obtained from the resist composition of the present application contains a polymer to which the hypervalent iodine compound is bonded at the time of film formation. However, by being decomposed by light, it becomes a monovalent iodine compound, and the bonding of the carboxyl group-containing polymer and the hypervalent iodine compound is released, and the molecular weight is also reduced. As a result, a positive pattern in which the exposed portion is removed by an organic solvent is formed. It is presumed that this functions as a positive resist composition.

[0797] The resist composition of the present application contains a hypervalent iodine compound and a carboxyl group-containing polymer having a photoacid generator unit, whereby a positive pattern can be formed with high sensitivity compared to a resist composition to which no photoacid generator is added. The mechanism thereof is not yet fully elucidated, but is presumed as follows.

[0798] In the resist composition of the present application, the aforementioned carboxyl group-containing polymer, by containing a photoacid generator unit, the acid generated from the photoacid generator unit at the exposure step of the resist reacts with the ligand of the hypervalent iodine compound to induce exchange and become a new ligand, whereby the bonding of the carboxyl group-containing polymer and the hypervalent iodine compound is released. Therefore, in addition to the cleavage of the I-O bond by light, a polarity change or a decrease in molecular weight due to the exchange of the new ligand by the acid generated from the photoacid generator occurs, and it is presumed that a positive pattern can be formed with high sensitivity by development with an organic solvent.

[0799] From the aforementioned presumption, the resist composition of the present application is a non-chemically amplified resist composition containing a polymer having a photoacid generator unit, and the acid-labile group-containing polymer of the known chemically amplified resist composition is not necessary. Therefore, the acid generated from the photoacid generator reacts with the ligand of the hypervalent iodine compound at the exposed portion and becomes a new ligand of the hypervalent iodine. That is, since there is no amplification mechanism of regenerating acid by reacting with the acid-labile group as in the chemically amplified resist composition, adverse effects due to acid diffusion (such as blur) do not occur, and a fine pattern can be resolved.

[0800] The resist composition of the present application is particularly effective in EUV lithography. This is due to the fact that the iodine atom has a high absorption ability for EUV light. That is, shot noise can be reduced and higher resolution and lower LWR can be achieved.

[0801] As for an EUV resist composition in which a fine pattern can be formed, there has been a report of a metal resist (for example, Patent Literature 2) in which a metal tin compound having a high absorption ability for EUV light as well as the iodine atom is used as a main component. However, as described above, such a metal resist has many problems such as insufficient solubility to a solvent, storage stability, and defects due to post-etching residue caused by the presence of a metal element. On the other hand, since the resist composition of the present application does not use a metal element, it is more advantageous than the metal resist in terms of defects, and there is no problem in terms of solubility to a solvent. Furthermore, the resist composition of the present application can be applied to a positive type. For example, a metal resist developed in a negative type in a contact hole forming step requires a reverse processing step after a column pattern is formed, but a positive resist does not require such a step. Therefore, from the viewpoint of process simplicity, the resist composition of the present application can also be said to be more useful than the metal resist.

[0802] Patent Documents 1 and 2 describe a resist composition containing a hypervalent iodine compound as an additive or a resist composition in which a hypervalent iodine compound is incorporated into the polymer skeleton of a base polymer. However, as for the characteristics of the resist compositions described in these patent documents, only a chemically amplified resist composition in which an acid-labile group in a polymer unit is essential is described, and the line edge roughness can be improved, but there is no mention at all of the possibility that the hypervalent iodine compound can be photodecomposed or the possibility that the material functions as a non-chemically amplified resist composition. Furthermore, according to the description and examples related to the blending amount, the hypervalent iodine compound is not a main component. Therefore, it is believed that the materials described in these patent documents cannot be conceived as the material that can reduce shot noise in EUV lithography and, at the same time, form a fine pattern as a material for a non-chemically amplified resist composition. That is, it can be said that the present application is to provide a novel resist composition and a pattern forming method.

[0803] [Pattern forming method]

[0804] When the resist composition of the present application is used in the manufacture of various integrated circuits, a known photolithography technique can be used. For example, as for the pattern forming method, a method including the following steps can be exemplified:

[0805] forming a resist film on a substrate or the underlayer film of a substrate having an underlayer film laminated thereon using the aforementioned resist composition,

[0806] exposing the aforementioned resist film to high-energy rays, and

[0807] developing the aforementioned exposed resist film as necessary using a developing solution.

[0808] First, the resist composition of the present application is applied to a substrate for integrated circuit manufacture or the underlayer film of a substrate (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, an organic antireflection film, etc.) having an underlayer film laminated thereon or a substrate for shield circuit manufacture or the underlayer film of a substrate (Cr, CrO, CrON, MoSi2, SiO2, etc.) having an underlayer film laminated thereon by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, etc. so that the coating film thickness becomes 0.01 to 2 μm. It is prebaked on a hot plate at preferably 60 to 200°C for 10 seconds to 30 minutes and more preferably 80 to 180°C for 30 seconds to 20 minutes, and a resist film is formed. In addition, the underlayer film means a film formed between a substrate and a resist film in a multilayer resist process. The aforementioned underlayer film is not particularly limited, and a known one can be used.

[0809] Then, the aforementioned resist film is exposed to high energy rays. The aforementioned high energy rays can include ultraviolet rays, far ultraviolet rays, EB, EUV, X-rays, soft X-rays, excimer laser, gamma rays, synchrotron radiation, and the like. When the aforementioned high energy rays are ultraviolet rays, far ultraviolet rays, EUV, X-rays, soft X-rays, excimer laser, gamma rays, synchrotron radiation, and the like, the exposure dose is preferably about 1 to 300 mJ / cm 2 and more preferably about 10 to 200 mJ / cm 2 . When the high energy rays are EB, the exposure dose is preferably about 0.1 to 8000 μC / cm 2 and more preferably about 0.5 to 5000 μC / cm 2 . In addition, the resist composition of the present application is particularly suitable for fine patterning by EB or EUV among high energy rays.

[0810] After exposure, PEB is performed as necessary. At this time, it is preferable to perform heating at 30 to 200°C for 10 seconds to 30 minutes, and more preferably at 60 to 120°C for 30 seconds to 20 minutes on a hot plate or in an oven after exposure.

[0811] After the exposure or after the PEB, development is performed as necessary using a developer to implement the patterning. The developer used at this time can include: an aqueous tetramethylammonium hydroxide solution, an aqueous tetrabutylammonium hydroxide solution, and the like; 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, 5-methyl-2-hexanone, methylcyclohexanone, acetophenone, methylacetophenone, isopropyl alcohol, isoamyl alcohol, n-butyl alcohol, t-butyl alcohol, t-amyl alcohol, n-amyl alcohol, cyclohexanol, formic acid, acetic acid, propionic acid, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butenyl acetate, isoamyl acetate, cyclohexyl acetate, 4-t-butylcyclohexyl acetate, octyl acetate, isocamphyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl pentanoate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, phenethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, 2-propanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methyl-1-butanol, diacetone alcohol, 4-methyl-2-pentanol, 3-methylcyclohexanol, 3,5,5-trimethylhexanol, 2,6-dimethyl-4-heptanol, toluene, anisole, ε-caprolactone, and the like. These developers can be used singly or in a mixture of two or more.

[0812] After the development, if necessary, a rinse is performed. The rinse liquid is preferably a solvent that is miscible with the developer and does not dissolve the resist film. Such a solvent can desirably be used: an alcohol having a carbon number of 3 to 10, an ether compound having a carbon number of 8 to 12, an alkane, alkene, alkyne, or aromatic solvent having a carbon number of 6 to 12.

[0813] By performing the rinse, the collapse of the resist pattern and the occurrence of defects can be reduced. Also, the rinse is not essential, and by not performing the rinse, the amount of solvent used can be reduced.

[0814] Examples

[0815] Hereinafter, the present application is specifically described by way of synthesis examples, examples, and comparative examples, but the present application is not limited to the following examples.

[0816] [1] Synthesis of Resist Polymers The monomers used for the synthesis of polymers P-1 to P-8 are as described below.

[0817] [Chemical Formula 309]

[0818]

[0819] [Chemical Formula 310]

[0820]

[0821] [Chemical Formula 311]

[0822]

[0823] [Chemical Formula 312]

[0824]

[0825] [Synthesis Example 1-1] Synthesis of Polymer P-1

[0826] A monomer-polymerization initiator solution was prepared by measuring monomer b-1 (44 g), monomer c-1 (21 g), monomer d-1 (35 g), V-601 (Fuji Photo Film Co., Ltd. and Wako Pure Chemical Industries, Ltd.) 5.4 g, and MEK (180 g) in a flask under a nitrogen atmosphere. In another flask adjusted to a nitrogen atmosphere, MEK (55 g) was measured and heated to 80°C while stirring, and then the above monomer-polymerization initiator solution was added dropwise over 4 hours. After the dropwise addition was completed, the temperature of the polymerization solution was maintained at 80°C and stirring was continued for 2 hours, and then it was cooled to room temperature. The resulting polymerization solution was added dropwise to hexane 4000 g stirred vigorously, and the precipitated polymer was separated by filtration. The resulting polymer was washed twice with hexane (1200 g), and then vacuum dried at 50°C for 20 hours to obtain polymer P-1 as a white powder (yield 98 g, yield 98%). The Mw of polymer P-1 was 7500, and Mw / Mn was 1.41. In addition, the Mw was a polystyrene conversion value measured by GPC using THF as a solvent.

[0827] [Chemical Formula 313]

[0828]

[0829] [Synthesis Examples 2 to 8] Synthesis of Polymers P-2 to P-8

[0830] By changing the kind and blending ratio of each monomer, the polymers shown in Table 1 below were synthesized in the same manner as in Synthesis Example 1.

[0831] [Table 1]

[0832]

[0833]

[0834] [2] Preparation of Resist Composition

[0835] [Examples 1-1 to 1-12, Comparative Examples 1-1 to 1-6]

[0836] An ultrahalogen compound, a carboxyl group-containing polymer, and a sensitivity adjuster were dissolved in a solvent containing 0.01 mass% of a surfactant (PF-636, manufactured by OMNOVA) in the composition shown in Table 2 below, and the obtained solution was filtered with a Teflon (registered trademark) filter of 0.2 μm, whereby a resist composition (R-01 to R-12 and CR-01 to CR-04) was produced. Also, a polymer, a photoacid generator, and a sensitivity adjuster were dissolved in a solvent containing 0.01 mass% of a surfactant (PF-636, manufactured by OMNOVA) in the composition shown in Table 3 below, and the obtained solution was filtered with a Teflon (registered trademark) filter of 0.2 μm, whereby a resist composition (CR-05 and CR-06) was produced.

[0837] [Table 2]

[0838]

[0839]

[0840] [Table 3]

[0841]

[0842] In Tables 2 and 3, the ultrahalogen compounds I-1 to I-3, the photoacid generators PAG-1 to PAG-3, the sensitivity adjusters Q-1 to Q-2, and the solvents are as described below.

[0843] [Chemical Formula 314]

[0844]

[0845] [Chemical Formula 315]

[0846]

[0847] [Chemical Formula 316]

[0848]

[0849] • Solvent: PGMEA (propylene glycol monomethyl ether acetate)

[0850] AcOH (acetic acid)

[0851] GBL (γ-butyrolactone)

[0852] [3] EUV lithography evaluation (line and space pattern)

[0853] [Examples 2-1 to 2-12, Comparative Examples 2-1 to 2-6]

[0854] Each of the resist compositions (R-01 to R-12, CR-01 to CR-06) was spin-coated on a Si substrate on which a silicon-containing spin-on hard mask SHB-A940 (silicon content: 43 mass%) manufactured by Showa Denko K.K. was formed in a film thickness of 20 nm, and prebaking (PAB) was performed at the temperature described in Table 4 for 60 seconds using a hot plate to produce a resist film having a film thickness of 40 nm. After the aforementioned resist film was exposed to light using an EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9, 90-degree dipole illumination) manufactured by ASML, which was set to a 36-nm line-and-space (LS) pattern at a 1:1 pitch, PEB was performed on a hot plate at the temperature described in Table 4 for 60 seconds, and then development was performed using the developer described in Table 4 for 30 seconds to form an LS pattern having a space width of 18 nm and a pitch of 36 nm.

[0855] The following evaluations were performed on the obtained resist pattern. The results are shown in Table 4.

[0856] [Sensitivity Evaluation]

[0857] The aforementioned LS pattern was observed using a length measuring SEM (CG-6300) manufactured by Hitachi High-Technologies Corporation, and the optimum exposure amount Eop (mJ / cm2) at which an LS pattern having a space width of 18 nm and a pitch of 36 nm could be obtained was determined and used as the sensitivity. 2 ) and was used as the sensitivity.

[0858] [LWR Evaluation]

[0859] The dimensions of 10 places of the LS pattern obtained by irradiation at the optimum exposure amount were measured in the length direction of the space width using a length measuring SEM (CG-6300) manufactured by Hitachi High-Technologies Corporation, and the value 3 times the standard deviation (σ) obtained from the results thereof (3σ) was used as the LWR. The smaller this value, the more uniform the space width of the pattern and the smaller the roughness.

[0860] [Limit of Resolution Evaluation]

[0861] The limit line width (nm) at which analysis was performed when a pattern was formed by gradually increasing the exposure amount in small increments from the optimum exposure amount at which the aforementioned LS pattern was formed was determined using a length measuring SEM (CG-6300) manufactured by Hitachi High-Technologies Corporation, and was used as the limit of resolution (nm). The smaller this value, the better the limit of resolution, and the finer the pattern that can be formed.

[0862] [Table 4]

[0863]

[0864]

[0865] Developer: nBA (butyl acetate)

[0866] TMAH (2.38 mass% aqueous tetramethylammonium hydroxide solution)

[0867] As is apparent from the results shown in Table 4, when comparing Example 2-1 and Comparative Example 2-1, a pattern can be formed with high sensitivity by introducing a photoacid generator unit into a polymer. When comparing Example 2-1 and Comparative Example 2-2, Example 2-4 and Comparative Example 2-3, and Example 2-11 and Comparative Example 2-4, it is apparent that the resolution limit is more excellent when a photoacid generator unit is introduced into a polymer than when a photoacid generator is added. When comparing Comparative Examples 2-1 to 2-3, it is apparent that the more the proportion of the photoacid generator unit in the polymer, the more a pattern can be formed with high sensitivity. When comparing Example 2-1 and Examples 2-11 to 2-12, it is apparent that the sensitivity can be adjusted to a lower sensitivity and excellent resolution can be obtained by adding a sensitivity adjustor. It is apparent that the resist composition of the present application is excellent in sensitivity, resolution, and LWR even when compared with Comparative Examples 2-5 and 2-6, which are chemical amplification resist compositions using an acid catalyst reaction. It is therefore apparent that the resist composition of the present application can form a resist pattern with excellent sensitivity in LS pattern formation by EUV exposure.

[0868] [4] Evaluation of EUV lithography (contact hole pattern)

[0869] [Examples 3-1 to 3-12, Comparative Examples 3-1 to 3-6]

[0870] Each of the resist compositions (R-01 to R-12, CR-01 to CR-06) was spin-coated on a Si substrate on which a silicon-containing spin-on hard mask SHB-A940 (silicon content: 43 mass%) manufactured by Showa Denko K.K. was formed in a film thickness of 20 nm, and PAB was performed for 60 seconds at the temperature described in Table 5 using a hot plate to produce a resist film in a film thickness of 50 nm. Then, the aforementioned resist film was exposed using an EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, a mask pattern with a pitch of 64 nm, a +20% offset hole pattern on a wafer) manufactured by ASML, and PEB was performed for 60 seconds at the temperature described in Table 5 on a hot plate, and development was performed for 30 seconds using the developing solution described in Table 5 to obtain a hole pattern in a size of 32 nm.

[0871] Evaluation was performed on the obtained resist pattern as follows. The results are shown in Table 5.

[0872] [Evaluation of sensitivity]

[0873] The aforementioned contact hole pattern was observed using a Hitachi High-Technologies (GK) length SEM (CG-6300), and the optimum exposure amount Eop (mJ / cm2) for which a hole pattern of 32 nm in size could be obtained was determined and made the sensitivity. 2 ) and made the sensitivity.

[0874] [CDU evaluation]

[0875] The size of 50 holes of the hole pattern obtained by irradiation at the optimum exposure amount was measured, and the value 3 times the standard deviation (σ) obtained from the results was made the CDU. The smaller this value, the more uniform the hole diameter pattern that can be obtained.

[0876] [Limit of resolution evaluation]

[0877] Using a Hitachi High-Technologies (GK) length SEM (CG-6300), the limit hole diameter (nm) analyzed when a hole pattern was formed by gradually decreasing the exposure amount from the optimum exposure amount for forming the aforementioned hole pattern was determined, and made the limit of resolution (nm). The smaller this value, the better the limit of resolution, and the more fine the hole diameter pattern that can be formed.

[0878] [Table 5]

[0879]

[0880]

[0881] As is clear from the results shown in Table 5, when comparing Example 3-1 and Comparative Example 3-1, a pattern can be formed at a high sensitivity by introducing a photoacid generator unit into a polymer. When comparing Example 3-1 and Comparative Example 3-2, Example 3-4 and Comparative Example 3-3, and Example 3-11 and Comparative Example 3-4, it is clear that the limit of resolution is better when a photoacid generator unit is introduced into a polymer than when a photoacid generator is added. When comparing Comparative Examples 3-1 to 3-3, it is clear that the more the proportion of the photoacid generator unit in the polymer, the more a pattern can be formed at a high sensitivity. When comparing Example 3-1 and Examples 3-11 to 3-12, it is clear that by adding a sensitivity adjustor, the sensitivity can be adjusted to a lower sensitivity, and a good resolution is obtained. It is clear that the resist composition of the present application is excellent in sensitivity, resolution, and CDU even when compared with Comparative Examples 3-5 and 3-6, which are chemical amplification resist compositions using an acid catalyst reaction. It is therefore clear that the resist composition of the present application can form a resist pattern at a good sensitivity in the formation of a contact hole pattern by EUV exposure.

Claims

1. A resist composition comprising: The superatomic iodine compound is at least one of any of the following formulas (1) to (4). Polymers containing carboxyl groups, and Solvent; The carboxyl-containing polymer contains a repeating unit represented by formula (5) and at least one of the repeating units represented by formula (6), formula (7), formula (8), formula (9) and formula (10). In the formula, m1 is 0, 1, or 2; when m1 is 0, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, or 5, and 1≤n1+n2≤6; when m1 is 1, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≤n1+n2≤8; when m1 is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1≤n1+n2≤10; n3 is 1 or 2; n4 is 0, 1, 2, 3, or 4; but 1≤n3+n4≤5; n5 is 1 or 2; n6 is 0, 1, 2, 3, or 4; but 1≤n5+n6≤5; n7 is 0, 1, 2, 3, or 4; n8 is 1, 2, 3, or 4. When m2 is 0, 1, or 2; when m2 is 0, n9 is 0, 1, 2, 3, or 4; when m2 is 1, n9 is 0, 1, 2, 3, 4, 5, or 6; when m2 is 2, n9 is 0, 1, 2, 3, 4, 5, 6, 7, or 8. R 1 ~R 8 Each is an independent hydrocarbon group consisting of halogen atoms or may contain heteroatoms, having 1 to 10 carbon atoms; also, R 1 and R 2 R 3 and R 4 R 5 and R 6 、or R 7 and R 8 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms; R 11 ~R 14 Each R is an independent hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms; when n2 is 2 or more, each R 11 They can be the same or different, and there are multiple Rs. 11 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n4 is 2 or more, each R 12 They can be the same or different, and there are multiple Rs. 12 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n6 is 2 or more, each R 13 They can be the same or different, and there are multiple Rs. 13 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n7 is 2 or more, each R 14 They can be the same or different, and there are multiple Rs. 14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; R 15 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 15 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl bond; furthermore, part or all of the hydrogen atoms of the (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be replaced by a group containing a heteroatom, and part of the -CH2- of the (n8) valence hydrocarbon group can also be replaced by a group containing a heteroatom, and R 14 and R 15 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms; R 16 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms; R 17 It is a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms; when n9 is 2 or more, each R 17 They can be the same or different; also, multiple Rs 17 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; R 18 It is a carbonyl group or may contain a hydrocarbon group with 1 to 10 carbon atoms; *1 and *2 represent the atomic bonds of the carbon atoms in the aromatic ring in the formula; however, *1 and *2 are bonded to adjacent carbon atoms in the aromatic ring. In the formula, R A Each can be independently a hydrogen atom or a methyl group; R B Each can be independently a hydrogen atom, or may be combined with Z. 6 Bonding and forming loops; X 1 It is a single bond, phenylene, naphthylene, or *-C(=O)-OX 11 -;X 11 It is a saturated alkylene group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring; * indicates an atomic bond with a carbon atom in the main chain; Z 1 It is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining them, or -OZ. 11 -、-C(=O)-OZ 11 -or-C(=O)-NH-Z 11 -;Z 11 It is an aliphatic hydrocarbon group, phenylene group, naphthylene group or a combination thereof with 7 to 18 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond or hydroxyl group; Z 2 It is a single bond or an ester bond; Z 3 For single key, -Z 31 -C(=O)-O- or -Z 31 -O-;Z 31 It is a hydrocarbon group, a phenylene group, or a group with 7 to 18 carbon atoms obtained by combining them, and may also contain a carbonyl group, a nitro group, a cyano group, an ester bond, an ether bond, a carbamate bond, a fluorine atom, an iodine atom, or a bromine atom; Z 4 It is a single bond, methylene, or ethylene; Z 5 Single bond, methylene, ethylene, phenylene, methylphenylene, dimethylphenylene, fluorinated phenylene, phenylene substituted with trifluoromethyl, -OZ 51 -、-C(=O)-OZ 51 -or-C(=O)-NH-Z 51 -;Z 51 It is an aliphatic alkylene group, phenylene, methylphenylene, dimethylphenylene, fluorinated phenylene, or phenylene substituted with trifluoromethyl, having 1 to 6 carbon atoms, and may also contain carbonyl groups, ester bonds, ether bonds, hydroxyl groups, or halogen atoms; Z 6 It can be a single bond, a phenylene ring, a naphthoid ring, an ester bond, or an amide bond; Z 7A It is a single bond or a divalent organic group having 1 to 24 carbon atoms, and may also have at least one selected from halogen atoms, oxygen atoms, nitrogen atoms and sulfur atoms; Z 7B It is a monovalent organic group having 1 to 10 carbon atoms, and may also have at least one selected from halogen atoms, oxygen atoms, nitrogen atoms and sulfur atoms; Z 8 It is a single bond, ether bond, ester bond, thioether bond, or an alkyl diel with 1 to 6 carbon atoms; Z 9 It is a trivalent organic group having 1 to 12 carbon atoms, and may also have at least one selected from oxygen, nitrogen and sulfur atoms; Rf 1 ~Rf 4 Each of the following is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of them is a fluorine atom or a trifluoromethyl group; also, Rf 1 and Rf 2 They can also combine to form carbonyl groups; R 21 and R 22 Each is an independent halogen atom or may contain a hydrocarbon group with 1 to 20 carbon atoms; R 23 It can be a saturated hydrocarbon group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, a fluorine atom, an iodine atom, a trifluoromethoxy group, a difluoromethoxy group, a cyano group, or a nitro group; Circle R represents an aromatic hydrocarbon group with 6 to 10 carbon atoms and a (a+2) valence. a can be 0, 1, 2, 3, 4, or 5; X - It is a non-nucleophilic relative ion; M + It is a sulfonium cation or a sulfonium cation.

2. The resist composition according to claim 1, wherein, This carboxyl-containing polymer does not contain acid-labile groups.

3. A layered body, comprising: substrate, and A resist film on the substrate obtained from the resist composition according to claim 1 or 2.

4. The laminate according to claim 3, wherein a photoresist underlayer is provided between the substrate and the photoresist film.

5. The laminated body according to claim 3, wherein, The resist film is formed by ligand exchange between the superatomic iodine compound and a carboxyl-containing polymer.

6. A pattern forming method, comprising the following steps: A resist film is formed on a substrate or a substrate having a lower layer film laminated using the resist composition according to claim 1 or 2. The resist film was exposed using i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet light. The exposed resist film was developed using a developer.

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