Resist composition and pattern forming process

Abstract

The objective of the present invention is to provide a resist material that is highly sensitive, whether positive or negative, and has improved LWR or CDU, and a pattern forming method using the same. A resist material comprising a sulfonium salt of an iodinated phenol compound.

Description

Technology Field

[0001] The present invention relates to a resist material and a pattern forming method. Background Technology

[0002] Along with the high integration and high speed of LSIs, the miniaturization of pattern rules is progressing rapidly. This is because the widespread adoption of 5G high-speed communication and artificial intelligence (AI) is increasing, and high-performance devices are required to process them. As a cutting-edge miniaturization technology, mass production of 5 nm node devices is being carried out using extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm. Furthermore, the use of EUV lithography is being considered for next-generation 3 nm node and next-next-generation 2 nm node devices, and IMEC of Belgium has announced the development of 2 Å devices.

[0003] With the progress of miniaturization, image blurring caused by acid diffusion is becoming a problem. It has been suggested that in order to secure resolution for fine patterns with a size of 45 nm or larger, control of acid diffusion is important, in addition to the improvement of dissolution contrast that has been conventionally proposed (Non-patent Literature 1). However, since chemical amplification resist materials increase sensitivity and contrast through acid diffusion, if acid diffusion is suppressed to the extreme by lowering the post-exposure baking (PEB) temperature or shortening the time, sensitivity and contrast are significantly reduced.

[0004] The relationship of the triangle trade-off between sensitivity, resolution, and edge roughness (LWR) is shown. To improve resolution, it is necessary to suppress acid diffusion, but sensitivity decreases as the acid diffusion distance becomes shorter.

[0005] It is effective to suppress acid diffusion by adding an acid-generating agent that generates bulky acid. Therefore, it has been proposed to include repeating units derived from onium salts having polymerizable unsaturated bonds in a polymer. In this case, the polymer also functions as an acid-generating agent (polymer-bound acid-generating agent). Patent Document 1 proposes a sulfonium salt or iodonium salt having polymerizable unsaturated bonds that generates a specific sulfonic acid. Patent Document 2 proposes a sulfonium salt in which a sulfonic acid is directly linked to the main chain.

[0006] The acid instability group used in (meth)acrylate polymers for ArF resist materials undergoes a deprotection reaction when using a photoacid generator that generates a sulfonic acid with the α-position substituted with a fluorine atom, but the deprotection reaction does not proceed with an acid generator that generates a sulfonic acid or carboxylic acid with the α-position not substituted with a fluorine atom. When a sulfonium salt or iodonium salt that generates a sulfonic acid with the α-position substituted with a fluorine atom is mixed with a sulfonium salt or iodonium salt that generates a sulfonic acid with the α-position not substituted with a fluorine atom, the sulfonium salt or iodonium salt that generates a sulfonic acid with the α-position not substituted with a fluorine atom undergoes ion exchange with the sulfonic acid with the α-position substituted with a fluorine atom. Since sulfonic acids in which the α-position is substituted with a fluorine atom by light are converted back into sulfonium or iodonium salts by ion exchange, sulfonium or iodonium salts of sulfonic acids or carboxylic acids in which the α-position is not substituted with a fluorine atom function as quenchers. A resist material has been proposed that uses a sulfonium or iodonium salt that generates a carboxylic acid as a quencher (Patent Document 3).

[0007] Resist materials have been proposed that use a sulfonium salt of a phenol compound with a fluorinated benzene ring as a quencher (Patent Documents 4 and 5). Although phenol is produced after the decomposition of the sulfonium salt of a phenol compound, the phenol compound has a small swelling in the alkaline developer, so it has the effect of preventing pattern collapse due to swelling. However, since fluorine has a low effect in inhibiting acid diffusion, acid diffusion increases as a result, and LWR or dimensional uniformity (CDU) deteriorates. In addition, the sulfonium salt of a fluorinated phenol compound is prone to thermal decomposition when converted into a sulfonium salt because the acidity of the fluorinated phenol is low, and there was a problem that the sensitivity of the resist material to which this was added increased during storage. Prior art literature

[0008] Japanese Patent Publication No. 2006-045311 Japanese Patent Publication No. 2006-178317 Japanese Patent Publication No. 2007-114431 Japanese Patent Publication No. 2016-6495 Japanese Patent Publication No. 2019-191578

[0009] SPIE Vol. 6520 65203L-1(2007) The problem to be solved

[0010] In resist materials, there is a demand for the development of a quencher that can improve the LWR of line patterns or the CDU of hole patterns, and also improve sensitivity. To achieve this, it is necessary to further reduce the blurring of the image caused by diffusion.

[0011] The present invention has been made in consideration of the above circumstances and aims to provide a resist material that is highly sensitive, whether positive or negative type, and has improved LWR or CDU, and a pattern forming method using the same. means of solving the problem

[0012] The inventors, having repeatedly examined the above objective, discovered that the sulfonium salt of an iodinated phenol compound is a quencher that inhibits acid diffusion, and that the LWR and CDU are improved by the excellent acid diffusion inhibition effect, prevention of pattern collapse due to reduced swelling, and improvement of contrast due to strong absorption of iodine atoms, thereby obtaining a resist material with excellent resolution and a wide process margin. Furthermore, they discovered that because the acidity of iodinated phenol is high, its sulfonium salt is difficult to decompose by heat, and that the resist material with this added has excellent storage stability, and thus completed the present invention.

[0013] That is, the present invention provides the following resist material and pattern forming method.

[0014] 1. A resist material comprising a sulfonium salt of an iodized phenol compound.

[0015] 2. A resist material of 1 in which the above sulfonium salt is represented by the following formula (1).

[0016]

[0017] (In the equation, m is 1, 2, 3, 4 or 5. n is 0, 1, 2, 3 or 4. provided that 1 ≤ m + n ≤ 5.

[0018] R 1 Each of the following is independently a halogen atom other than an iodine atom, a hydroxyl group, a nitro group, a cyano group, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms, or a hydrocarbylsulfonyloxy group having 1 to 20 carbon atoms, and the hydrocarbyl group, hydrocarbyloxy group, hydrocarbylcarbonyloxy group and hydrocarbylsulfonyloxy group may have at least one selected from a halogen atom, an oxygen atom, a sulfur atom and a nitrogen atom.

[0019] R 2 to R 4is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a halogen atom or a heteroatom. Also, R 2 and R 3 These may combine with each other to form a ring together with the sulfur atom to which they combine.

[0020] 3. Additionally, a resist material of 1 or 2 comprising a base polymer.

[0021] 4. A resist material of 3 in which the base polymer comprises at least one selected from a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (a2).

[0022]

[0023] (during food, R A Each is independently a hydrogen atom or a methyl group.

[0024] X 1 The linker has 1 to 12 carbon atoms and comprises at least one selected from a single bond, a phenylene group or a naphthylene group, or an ester bond, an ether bond, and a lactone ring, and the phenylene group, naphthylene group and the linker may have at least one selected from a halogen atom, a hydroxyl group, a saturated hydrocarbyloxy group having 1 to 8 carbon atoms, and a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms.

[0025] X 2 is a single bond, an ester bond, or an amide bond.

[0026] X 3 It is a single bond, an ether bond, or an ester bond.

[0027] R 11 and R 12 Each is, independently, an acid instability phase.

[0028] R 13It is silver, a hydroxyl group, a halogen atom, a trifluoromethyl group, a cyano group, or a saturated hydrocarbyl group having 1 to 6 carbon atoms.

[0029] R 14 The group is a single bond or an alkandyl group having 1 to 6 carbon atoms, and a portion of the -CH2- of the alkandyl group may be substituted by an ether bond or an ester bond.

[0030] a is 1 or 2. b is an integer from 0 to 4. Provided that 1 ≤ a + b ≤ 5.

[0031] 5. Resist material of 4, which is a chemically amplified positive type resist material.

[0032] 6. A resist material of 3 in which the base polymer does not contain acid unstable groups.

[0033] 7. Resist material of 6, which is a chemically amplified negative type resist material.

[0034] 8. A resist material of any one of 3 to 7, wherein the base polymer comprises at least one selected from a repeating unit represented by the following formula (f1), a repeating unit represented by the following formula (f2), a repeating unit represented by the following formula (f3), a repeating unit represented by the following formula (f4), and a repeating unit represented by the following formula (f5).

[0035]

[0036] (during food, R A Each is independently a hydrogen atom or a methyl group.

[0037] Z 1 Silver, single bonds, 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 a combination thereof, or -OZ 11 -, -C(=O)-OZ 11 - or -C(=O)-NH-Z 11 -is. Z 11It 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 these, and may include a carbonyl group, an ester bond, an ether bond, or a hydroxyl group.

[0038] Z 2 is a single bond or an ester bond.

[0039] Z 3 Silver, single bond, -Z 31 -C(=O)-O-, -Z 31 -O- or -Z 31 -OC(=O)- is. Z 31 It is an aliphatic hydrocarbylene group having 1 to 12 carbon atoms, a phenylene group, or a group having 7 to 18 carbon atoms obtained by combining these, and may include a carbonyl group, an ester bond, an ether bond, an iodine atom, or a bromine atom.

[0040] Z 4 is a methylene group, a 2,2,2-trifluoro-1,1-ethanediyl group, or a carbonyl group.

[0041] Z 5 is, single bond, methylene group, ethylene group, phenylene group, fluorinated phenylene group, phenylene group substituted with trifluoromethyl group, -OZ 51 -, -C(=O)-OZ 51 - or -C(=O)-NH-Z 51 -is. Z 51 It is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may include a carbonyl group, an ester bond, an ether bond, a halogen atom, or a hydroxyl group.

[0042] Z 6 It is a single bond, a phenylene group, a naphthylene ring, an ester bond, or an amide bond.

[0043] Z 7AIt may have a single bond or a divalent organic group having 1 to 24 carbon atoms, and may have at least one selected from a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom.

[0044] Z 7B The is a monovalent organic group having 1 to 10 carbon atoms and may have at least one selected from a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom.

[0045] Z 8 It is a single bond, ether bond, ester bond, thioether bond, or an alkanedyl group having 1 to 6 carbon atoms.

[0046] Z 9 The is a trivalent organic group having 1 to 12 carbon atoms and may have at least one selected from oxygen, nitrogen, and sulfur atoms.

[0047] R 21 to R 25 is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a halogen atom or a heteroatom. Also, R 23 and R 24 a, they may combine with each other to form a ring together with the sulfur atom to which they combine.

[0048] R 26 Each is independently a saturated hydrocarbyl 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.

[0049] The original R is an aromatic hydrocarbon group with 6 to 10 carbon atoms (j+2).

[0050] j is an integer from 0 to 5, each independently.

[0051] M - is a non-nucleophilic counterion.)

[0052] 9. Additionally, a resist material of any one of 1 to 8 comprising an acid-generating agent that generates a strong acid.

[0053] 10. The resist material of 9 in which the above acid generating agent generates sulfonic acid, imidic acid, or methic acid.

[0054] 11. Additionally, a resist material of any one of 1 to 10 comprising an organic solvent.

[0055] 12. Additionally, a resist material of any one of 1 to 11 comprising a surfactant.

[0056] 13. A pattern forming method comprising: a process of forming a resist film on a substrate using a resist material of any one of 1 to 12; a process of exposing the resist film to high-energy rays; and a process of developing the exposed resist film using a developer.

[0057] 14. A pattern forming method of 13 in which the high-energy line is KrF excimer laser light, ArF excimer laser light, electron beam (EB), or EUV with a wavelength of 3 to 15 nm. Effects of the invention

[0058] The sulfonium salt of the above iodinated phenol compound is a quencher that inhibits acid diffusion. As a result, it becomes possible to construct a resist material with low acid diffusion characteristics, a small LWR, and improved CDU. Specific details for implementing the invention

[0059] [Resist Material]

[0060] The resist material of the present invention comprises a quencher containing a sulfonium salt of an iodinated phenolic compound.

[0061] [Quencher]

[0062] The sulfonium salt of the iodinated phenol compound is preferably represented by the following formula (1).

[0063]

[0064] In Equation (1), m is 1, 2, 3, 4 or 5. n is 0, 1, 2, 3 or 4. provided that 1 ≤ m + n ≤ 5.

[0065] In Equation (1), R 1 Each is independently a halogen atom other than an iodine atom, a hydroxyl group, a nitro group, a cyano group, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms, or a hydrocarbylsulfonyloxy group having 1 to 20 carbon atoms.

[0066] R 1 The hydrocarbyl portion of the hydrocarbyl group and hydrocarbyloxy group, hydrocarbylcarbonyloxy group and hydrocarbylsulfonyloxy group represented by may be saturated or unsaturated, and may be straight, branched, or cyclic. As a specific example, R described below 2 to R 4 Examples of hydrocarbyl groups having 1 to 20 carbon atoms, represented by [the example], may be given. In addition, the hydrocarbyl group, hydrocarbyloxy group, hydrocarbylcarbonyloxy group and hydrocarbylsulfonyloxy group may have at least one selected from a halogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom. That is, some or all of the hydrogen atoms of these groups may be substituted with a group comprising at least one selected from a halogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom, and some of the -CH2- of these groups may be substituted with a group comprising at least one selected from an oxygen atom, a sulfur atom, and a nitrogen atom, and as a result, may include a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sulfone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc.

[0067] Specific examples of the anion of the sulfonium salt represented by formula (1) include those shown below, but are not limited to these.

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080] In Equation (1), R 2 to R 4 Each is a hydrocarbyl group having 1 to 20 carbon atoms that may independently contain a halogen atom or a heteroatom.

[0081] R 2 to R 4 Specific examples of halogen atoms represented by include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0082] R 2 to R 4The hydrocarbyl group having 1 to 20 carbon atoms, represented by, may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl; Cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, propenyl, butenyl, and hexenyl groups; alkynyl groups having 2 to 20 carbon atoms, such as ethinyl, propynyl, and butynyl groups; cyclic unsaturated aliphatic hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclohexenyl and norbornenyl groups; Examples include aryl groups having 6 to 20 carbon atoms, such as phenyl groups, methylphenyl groups, ethylphenyl groups, n-propylphenyl groups, isopropylphenyl groups, n-butylphenyl groups, isobutylphenyl groups, sec-butylphenyl groups, tert-butylphenyl groups, naphthyl groups, methyl naphthyl groups, ethyl naphthyl groups, n-propyl naphthyl groups, isopropyl naphthyl groups, n-butyl naphthyl groups, isobutyl naphthyl groups, sec-butyl naphthyl groups, and tert-butyl naphthyl groups; aralkyl groups having 7 to 20 carbon atoms, such as benzyl groups and phenethyl groups; and groups obtained by combining these.

[0083] In addition, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, or halogen atoms, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, or nitrogen atoms, and as a result, may include 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 pentafluorosulfanyl group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sulfone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc.

[0084] Also, R 2 and R 3 These may combine with each other to form a ring together with the sulfur atom to which they are bonded. In this case, the ring is preferably of the structure shown below.

[0085]

[0086] (In the food, the dashed line is, R 4 It is a combined hand with.)

[0087] Specific examples of the cation of the sulfonium salt represented by formula (1) include those shown below, but are not limited thereto.

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123] Sulfonium salts represented by formula (1) can be synthesized, for example, by ion-exchanging a hydrochloride or carbonate having a sulfonium cation with an ammonium salt of an iodized phenol compound.

[0124] Among the resist materials of the present invention, the content of the sulfonium salt represented by Formula (1) is preferably 0.001 to 50 parts by mass and more preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the base polymer described below. The sulfonium salt represented by Formula (1) may be used as a single type or in combination of two or more types.

[0125] [Base Polymer]

[0126] The base polymer included in the resist material of the present invention, in the case of a positive-type resist material, comprises a repeating unit containing an acid instability group. As the repeating unit containing an acid instability group, a repeating unit represented by the following formula (a1) (hereinafter also referred to as repeating unit a1) or a repeating unit represented by the formula (a2) (hereinafter also referred to as repeating unit a2) is preferred.

[0127]

[0128] Among equations (a1) and (a2), R A is, independently, a hydrogen atom or a methyl group. X 1 It is a linker having 1 to 12 carbon atoms comprising at least one selected from a single bond, a phenylene group or a naphthylene group, or an ester bond, an ether bond, and a lactone ring, and said phenylene group, naphthylene group and linker may have at least one selected from a halogen atom, a hydroxyl group, a saturated hydrocarbyloxy group having 1 to 8 carbon atoms, and a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms. 2 is a single bond, ester bond, or amide bond. X3 It is a single bond, an ether bond, or an ester bond. R 11 and R 12 is, independently, an acid instability phase. R 13 It is silver, a hydroxyl group, a halogen atom, a trifluoromethyl group, a cyano group, or a saturated hydrocarbyl group having 1 to 6 carbon atoms. R 14 is a single bond or an alkandyl group having 1 to 6 carbon atoms, and a portion of the -CH2- of the said alkandyl group may be substituted by an ether bond or an ester bond. a is 1 or 2. b is an integer from 0 to 4. provided that 1 ≤ a + b ≤ 5.

[0129] Specific examples of monomers that provide a repeating unit a1 include those shown below, but are not limited thereto. In addition, among the following formulas, R A and R 11 It is the same as above.

[0130]

[0131]

[0132] Specific examples of monomers that impart a repeating unit a2 include those shown below, but are not limited thereto. In addition, among the following formulas, R A and R 12 It is the same as above.

[0133]

[0134] R 11 or R 12 The acid instability group represented by [this] can be selected in various ways, but for example, it can be represented by the following formulas (AL-1) to (AL-3).

[0135]

[0136] (In the formula, the dashed line is a connecting hand.)

[0137] In Equation (AL-1), c is an integer from 0 to 6. R L1It is a tertiary hydrocarbyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, a trihydrocarbylsilyl group in which each hydrocarbyl group is a saturated hydrocarbyl group having 1 to 6 carbon atoms, a carbonyl group, a saturated hydrocarbyl group having 4 to 20 carbon atoms including an ether bond or an ester bond, or a group represented by the formula (AL-3). In addition, a tertiary hydrocarbyl group means a group obtained by detaching a hydrogen atom from a tertiary carbon atom of a hydrocarbon.

[0138] R L1 The tertiary hydrocarbyl group represented by may be saturated or unsaturated, branched or cyclic. Specific examples thereof include a tert-butyl group, a tert-pentyl group, a 1,1-diethylpropyl group, a 1-ethylcyclopentyl group, a 1-butylcyclopentyl group, a 1-ethylcyclohexyl group, a 1-butylcyclohexyl group, a 1-ethyl-2-cyclopentenyl group, a 1-ethyl-2-cyclohexenyl group, a 2-methyl-2-adamantyl group, etc. Specific examples of the above trihydrocarbylsilyl group include a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, etc. The saturated hydrocarbyl group containing the carbonyl group, ether bond, or ester bond may be straight, branched, or cyclic, but is preferably cyclic, and specific examples thereof include 3-oxocyclohexyl group, 4-methyl-2-oxo-oxane-4-yl group, 5-methyl-2-oxo-oxolane-5-yl group, 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group, etc.

[0139] Specific examples of the acid instability group represented by formula (AL-1) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-pentyloxycarbonyl group, tert-pentyloxycarbonylmethyl group, 1,1-diethylpropyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group, etc.

[0140] In addition, as an acid instability group represented by formula (AL-1), groups represented by the following formulas (AL-1)-1 to (AL-1)-10 may be cited.

[0141]

[0142] (In the formula, the dashed line is a connecting hand.)

[0143] Among formulas (AL-1)-1 to (AL-1)-10, c is the same as above. R L8 Each is independently a saturated hydrocarbyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. R L9 is a hydrogen atom or a saturated hydrocarbyl group having 1 to 10 carbon atoms. R L10 It is a saturated hydrocarbyl group having 2 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. The saturated hydrocarbyl group may be straight, branched, or cyclic.

[0144] In formula (AL-2), R L2 and R L3Each is independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 18 carbon atoms, preferably 1 to 10. The saturated hydrocarbyl group may be straight, branched, or cyclic, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, an n-octyl group, etc.

[0145] In formula (AL-2), R L4 The hydrocarbyl group has 1 to 18 carbon atoms, preferably 1 to 10, and may contain heteroatoms. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples of the hydrocarbyl group include saturated hydrocarbyl groups having 1 to 18 carbon atoms, and some of these hydrogen atoms may be substituted with hydroxyl groups, alkoxy groups, oxo groups, amino groups, alkylamino groups, etc. Specific examples of such substituted saturated hydrocarbyl groups include those shown below.

[0146]

[0147] (In the formula, the dashed line is a connecting hand.)

[0148] R L2 and R L3 , R L2 and R L4 , or R L3 and R L4 They may combine with each other to form a ring with the carbon atom to which they bond, or with a carbon atom and an oxygen atom, and in this case, R involved in the formation of the ring L2 and R L3 , R L2 and R L4 , or R L3 and R L4Each is independently an alkanedyl group having 1 to 18 carbon atoms, preferably 1 to 10. The number of carbon atoms of the ring obtained by combining these is preferably 3 to 10, more preferably 4 to 10.

[0149] Specific examples of acid instability groups represented by formula (AL-2) that are linear or branched include those represented by the following formulas (AL-2)-1 to (AL-2)-69, but are not limited thereto. Additionally, in the following formulas, dashed lines represent bonding losses.

[0150]

[0151]

[0152]

[0153]

[0154] Specific examples of acid instability groups represented by formula (AL-2) that are cyclic include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2-methyltetrahydropyran-2-yl group, etc.

[0155] In addition, as an acid instability group, a group represented by the following formula (AL-2a) or (AL-2b) may be used. Due to the acid instability group, the base polymer may be cross-linked intermolecularly or intramolecularly.

[0156]

[0157] (In the formula, the dashed line is a connecting hand.)

[0158] In formula (AL-2a) or (AL-2b), R L11 and R L12 Each is independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 8 carbon atoms. The saturated hydrocarbyl group may be linear, branched, or cyclic. In addition, R L11 and R L12They may combine with each other to form a ring together with the carbon atom to which they bond, and in this case, R L11 and R L12 is, each independently, an alkanedyl group having 1 to 8 carbon atoms. R L13 Each is independently a saturated hydrocarbylene group having 1 to 10 carbon atoms. The saturated hydrocarbylene group may be straight, branched, or cyclic. d and e are each independently integers from 0 to 10, preferably integers from 0 to 5, and f is an integer from 1 to 7, preferably integers from 1 to 3.

[0159] Among formulas (AL-2a) or (AL-2b), L A is an aliphatic saturated hydrocarbon group having 1 to 50 carbon atoms of (f+1) valence, a saturating hydrocarbon group having 3 to 50 carbon atoms of (f+1) valence, an aromatic hydrocarbon group having 6 to 50 carbon atoms of (f+1) valence, or a heterocyclic group having 3 to 50 carbon atoms of (f+1) valence. Additionally, a portion of the -CH2- of these groups may be substituted with a group containing a heteroatom, and a portion of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, an acyl group, or a fluorine atom. L A Preferably, saturated hydrocarbon groups having 1 to 20 carbon atoms, trivalent saturated hydrocarbon groups, tetravalent saturated hydrocarbon groups, etc., and arylene groups having 6 to 30 carbon atoms are preferred. The above saturated hydrocarbon groups may be straight-chain, branched, or cyclic. L B is -C(=O)-O-, -NH-C(=O)-O- or -NH-C(=O)-NH-.

[0160] Specific examples of cross-linked acetal groups represented by formulas (AL-2a) or (AL-2b) include groups represented by the following formulas (AL-2)-70 to (AL-2)-77.

[0161]

[0162] (In the formula, the dashed line is a connecting hand.)

[0163] In formula (AL-3), R L5 is a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and the said hydrocarbyl group may include heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, or fluorine atoms. R L6 and R L7 Each is independently a hydrocarbyl group having 1 to 20 carbon atoms and may contain heteroatoms such as oxygen, sulfur, nitrogen, or fluorine atoms. The above hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cyclic unsaturated hydrocarbyl group having 3 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, etc. In addition, R L5 and R L6 and, R L5 and R L7 and, or R L6 and R L7 Silver may combine with each other to form a ring with 3 to 20 carbon atoms together with the carbon atoms to which they combine.

[0164] Specific examples of the group represented by formula (AL-3) include tert-butyl group, 1,1-diethylpropyl group, 1-ethylnorbornyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-isopropylcyclopentyl group, 1-methylcyclohexyl group, 2-(2-methyl)adamantyl group, 2-(2-ethyl)adamantyl group, tert-pentyl group, etc.

[0165] In addition, as a group represented by formula (AL-3), groups represented by the following formulas (AL-3)-1 to (AL-3)-22 may also be included.

[0166]

[0167] (In the formula, the dashed line is a connecting hand.)

[0168] Among formulas (AL-3)-1 to (AL-3)-22, R L14 is, each independently, a hydrogen atom, an aliphatic hydrocarbyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R L15 and R L17 Each is independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 20 carbon atoms. R L16 It is an aryl group having 6 to 20 carbon atoms. The saturated hydrocarbyl group may be straight-chain, branched, or cyclic. Additionally, a phenyl group, etc., is preferred as the aryl group. R L18 It is silver, a fluorine atom, an iodine atom, a nitro group, or a trifluoromethyl group. R L19 Each is independently a hydrogen atom, a fluorine atom, an iodine atom, a nitro group, a saturated hydrocarbyl group having 1 to 8 carbon atoms, and a hydrocarbyloxy group having 1 to 8 carbon atoms. g is an integer from 1 to 5.

[0169] In addition, as an acid instability group, a group represented by the following formula (AL-3)-23 or (AL-3)-24 may be used. Due to the acid instability group, the polymer may be cross-linked intramolecularly or intermolecularly.

[0170]

[0171] (In the formula, the dashed line is a connecting hand.)

[0172] Among formulas (AL-3)-23 and (AL-3)-24, R L14 is the same as above. R L20 The group is a saturated or unsaturated hydrocarbylene group having 1 to 20 carbon atoms (h+1) or an arylene group having 6 to 20 carbon atoms (h+1), and may contain heteroatoms such as oxygen, sulfur, and nitrogen atoms. The saturated or unsaturated hydrocarbylene group may be straight, branched, or cyclic. h is an integer from 1 to 3.

[0173] In addition to these acid instability groups, aromatic group-containing acid instability groups described in Japanese Patent Publication No. 5565293, Japanese Patent Publication No. 5434983, Japanese Patent Publication No. 5407941, Japanese Patent Publication No. 5655756, and Japanese Patent Publication No. 5655755 may also be used.

[0174] The above base polymer may include a repeating unit b comprising a phenolic hydroxyl group as an adhesion group. Specific examples of the monomer imparting the repeating unit b include those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0175]

[0176] The above base polymer may include, as other adhesion groups, a repeating unit c comprising a hydroxyl group other than a phenolic hydroxyl group, a lactone ring, a sulfone ring, an ether link, an ester link, a sulfonic acid ester link, a carbonyl group, a sulfonyl group, a cyano group, or a carboxyl group. Specific examples of the monomer imparting the repeating unit c are those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185] The above base polymer may include a repeating unit d derived from indene, benzofuran, benzothiophene, acenaphtylene, chromone, coumarin, norbornadiene, or derivatives thereof. Specific examples of monomers imparting the repeating unit d include those shown below, but are not limited thereto.

[0186]

[0187] The above base polymer may include repeating unit e derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methyleneindane, vinylpyridine, or vinylcarbazole.

[0188] The above base polymer may include a repeating unit f derived from an onium salt containing polymerizable unsaturated bonds. Specific examples of a preferred repeating unit f include a repeating unit represented by the following formula (f1) (hereinafter also referred to as repeating unit f1), a repeating unit represented by the following formula (f2) (hereinafter also referred to as repeating unit f2), a repeating unit represented by the following formula (f3) (hereinafter also referred to as repeating unit f3), a repeating unit represented by the following formula (f4) (hereinafter also referred to as repeating unit f4), and a repeating unit represented by the following formula (f5) (hereinafter also referred to as repeating unit f5). Additionally, repeating units f1 to f5 may be used individually or in combination of two or more types.

[0189]

[0190] Among equations (f1) to (f5), R A Each is independently a hydrogen atom or a methyl group.

[0191] Among equations (f1) to (f3), Z 1 Silver, single bonds, 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 a combination thereof, or -OZ 11 -, -C(=O)-OZ11 - or -C(=O)-NH-Z 11 -is. Z 11 It 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 a combination thereof, and may include a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 2 is a single bond or an ester bond. Z 3 Silver, single bond, -Z 31 -C(=O)-O-, -Z 31 -O- or -Z 31 -OC(=O)- is. Z 31 It is a carbonyl group, an aliphatic hydrocarbylene group having 1 to 12 carbon atoms, a phenylene group, or a group having 7 to 18 carbon atoms obtained by a combination thereof, and may include a carbonyl group, an ester bond, an ether bond, an iodine atom, or a bromine atom. Z 4 is a methylene group, a 2,2,2-trifluoro-1,1-ethanediyl group, or a carbonyl group. Z 5 is, single bond, methylene group, ethylene group, phenylene group, fluorinated phenylene group, phenylene group substituted with trifluoromethyl group, -OZ 51 -, -C(=O)-OZ 51 - or -C(=O)-NH-Z 51 -is. Z 51 It is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may include a carbonyl group, an ester bond, an ether bond, a halogen atom, or a hydroxyl group. In addition, Z 1 , Z 11 , Z 31 and Z 51 The aliphatic hydrocarbylene group represented by may be saturated or unsaturated, and may be straight, branched, or cyclic.

[0192] Among equations (f4) and (f5), Z 6It is a single bond, a phenylene group, a naphthylene ring, an ester bond, or an amide bond.

[0193] In equation (f4), Z 7A It may have a single bond or a divalent organic group having 1 to 24 carbon atoms, and may have at least one selected from a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom.

[0194] Z 7AThe divalent organic group represented by may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples include a hydrocarbylene group having 1 to 24 carbon atoms in which some or all of the hydrogen atoms are substituted with iodine or bromine atoms. Specific examples of the above hydrocarbylene group having 1 to 24 carbon atoms include a methane diyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, and a heptadecane-1,17-diyl group. Alkanedyl groups such as octadecane-1,18-diyl group, nonadecane-1,19-diyl group, eicosan-1,20-diyl group; cyclic saturated hydrocarbylene groups such as cyclopentanediyl group, methylcyclopentanediyl group, dimethylcyclopentanediyl group, trimethylcyclopentanediyl group, tetramethylcyclopentanediyl group, cyclohexanedyl group, methylcyclohexanedyl group, dimethylcyclohexanedyl group, trimethylcyclohexanedyl group, tetramethylcyclohexanedyl group, norbornandyl group, adamantandiyl group; Examples include arylene 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, biphenyldiyl, methylbiphenyldiyl, and dimethylbiphenyldiyl; groups obtained by combining these. Also, Z 7A Some or all of the hydrogen atoms of may be substituted with a group comprising at least one selected from oxygen, nitrogen, and sulfur atoms, and Z 7AA portion of the -CH2- may be substituted with a group comprising at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and as a result, may include a hydroxyl group, an ester bond, an ether bond, an amide bond, a carbamate bond, a urea bond, etc.

[0195] In equation (f5), Z 7B The is a monovalent organic group having 1 to 10 carbon atoms and may have at least one selected from a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom.

[0196] Z 7BThe monovalent organic group represented by may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples include a hydrocarbyl group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms are substituted with iodine or bromine atoms.Specific examples of the above hydrocarbyl group having 1 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a tert-pentyl group, a neopentyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, etc. Cyclic saturated hydrocarbyl groups having 3 to 10 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, cyclohexylethyl group, methylcyclopropyl group, methylcyclobutyl group, methylcyclopentyl group, methylcyclohexyl group, ethylcyclopropyl group, ethylcyclobutyl group, ethylcyclopentyl group, ethylcyclohexyl group, etc.; alkenyl groups having 2 to 10 carbon atoms, such as vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, nonenyl group, decenyl group, etc. Alkynyl groups having 2 to 10 carbon atoms, such as ethinyl, propynyl, butynyl, fentinyl, hexinyl, heptinyl, octinyl, noninyl, and decinyl groups; cyclic unsaturated aliphatic hydrocarbyl groups having 3 to 10 carbon atoms, such as cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexenyl, ethylcyclopentenyl, ethylcyclohexenyl, and norbornenyl groups; aryl groups having 6 to 10 carbon atoms, such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, and naphthyl groups; Examples include aralkyl groups having 7 to 10 carbon atoms, such as benzyl groups, phenethyl groups, phenylpropyl groups, and phenylbutyl groups; groups obtained by combining these. Also, Z. 7B Some or all of the hydrogen atoms of may be substituted with a group comprising at least one selected from oxygen, nitrogen, and sulfur atoms, and Z 7BA portion of the -CH2- may be substituted with a group comprising at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and as a result, may include a hydroxyl group, an ester bond, an ether bond, an amide bond, a carbamate bond, a urea bond, etc.

[0197] Among equations (f4) and (f5), Z 8 It is a single bond, ether bond, ester bond, thioether bond, or an alkanedyl group having 1 to 6 carbon atoms.

[0198] In equation (f5), Z 9 is a trivalent organic group having 1 to 12 carbon atoms and may have at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom. Z 9 The trivalent organic group represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. As a specific example, a group obtained by removing one additional hydrogen atom from a hydrocarbylene group having 1 to 12 carbon atoms may be cited. As a specific example of the hydrocarbylene group having 1 to 12 carbon atoms, among the aforementioned hydrocarbylene groups having 1 to 24 carbon atoms, those having 1 to 12 carbon atoms may be cited. Also, Z 9 Some or all of the hydrogen atoms of may be substituted with a group comprising at least one selected from oxygen, nitrogen, and sulfur atoms, and Z 9 A portion of the -CH2- may be substituted with a group comprising at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and as a result, may include a hydroxyl group, an ester bond, an ether bond, an amide bond, a carbamate bond, a urea bond, etc.

[0199] Among equations (f1) to (f5), R 21 to R 25is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a halogen atom or a heteroatom. Specific examples of the halogen atom include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include R in the explanation of Formula (1). 2 to R 4 Examples of hydrocarbyl groups represented by [ ] and similar to those exemplified may be given. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms, and as a result, may include a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sulfone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. Additionally, R 23 and R 24 a, they may combine with each other to form a ring together with the sulfur atom to which they combine. In this case, as a specific example of the above ring, R in the explanation of formula (a) 2 and R 3 Examples of rings that can be formed by combining with each other, such as those exemplified by the sulfur atoms they combine with, can be given.

[0200] Among equations (f4) and (f5), R 26 Each is independently a saturated hydrocarbyl 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.

[0201] In formulas (f4) and (f5), the element R is a (j+2) aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of the (j+2) aromatic hydrocarbon group include a group obtained by removing (j+2) hydrogen atoms from an aromatic hydrocarbon such as benzene or naphthalene.

[0202] In equations (f4) and (f5), j is an integer from 0 to 5, respectively, independently.

[0203] In equation (f1), M - ...is a non-nucleophilic counterion. Specific examples of the above non-nucleophilic counterion include halide ions such as chloride ions and bromide ions, fluoroalkylsulfonate ions such as trilate ions, 1,1,1-trifluoroethanesulfonate ions and nonafluorobutanesulfonate ions, tosylate ions, arylsulfonate ions such as benzenesulfonate ions, 4-fluorobenzenesulfonate ions and 1,2,3,4,5-pentafluorobenzenesulfonate ions, alkylsulfonate ions such as mesylate ions and butanesulfonate ions, imide ions such as bis(trifluoromethylsulfonyl)imide ions, bis(perfluoroethylsulfonyl)imide ions and bis(perfluorobutylsulfonyl)imide ions, and methide ions such as tris(trifluoromethylsulfonyl)methide ions and tris(perfluoroethylsulfonyl)methide ions.

[0204] Specific examples of the above-mentioned non-nucleophilic counter-ions include, additionally, a sulfonate ion in which the α position is substituted with a fluorine atom represented by the following formula (f1-1), and a sulfonate ion 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 (f1-2).

[0205]

[0206] In equation (f1-1), R 31It is silver, a hydrogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms, and the said hydrocarbyl group may include at least one selected from ether bonds, ester bonds, carbonyl groups, lactone rings, and fluorine atoms. The said hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. As a specific example, R in formula (2A') described below. fa1 One can cite the same as the example given as the hydrocarbyl group indicated by .

[0207] In equation (f1-2), R 32 is a hydrogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, or a hydrocarbyl carbonyl group having 2 to 30 carbon atoms, and said hydrocarbyl group and hydrocarbyl carbonyl group may include at least one selected from ether bonds, ester bonds, carbonyl groups, and lactone rings. The hydrocarbyl portion of said hydrocarbyl group and hydrocarbyl carbonyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. As a specific example, R in formula (2A') described below. fa1 One can cite the same as the example given as the hydrocarbyl group indicated by .

[0208] Specific examples of the monomer cations that impart the repeating unit f1 are those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0209]

[0210] Specific examples of the cations of repeating units f2 to f5 include those exemplified as the cations of the sulfonium salts represented by formula (1).

[0211] Specific examples of the monomer anion imparting the repeating unit f2 include those shown below, but are not limited thereto. In addition, among the following formulas, RA It is the same as above.

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227] Specific examples of the monomer anion imparting the repeating unit f3 include those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0228]

[0229] Specific examples of the monomer anion imparting the repeating unit f4 or f5 include those shown below, but are not limited thereto. In addition, among the following formulas, R A and X BI It is the same as above.

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255] Repeating units f1 to f5 function as acid generators. By binding acid generators to the polymer main chain, acid diffusion is reduced, thereby preventing a decrease in resolution caused by the blurring of acid diffusion. Additionally, LWR and CDU are improved as the acid generators are uniformly dispersed. Furthermore, when using a base polymer containing repeating units f1 to f5 (i.e., a polymer-bound acid generator), the formulation of the additive acid generator described later can be omitted.

[0256] The base polymer for positive-type resist materials requires a repeating unit a1 or a2 containing an acid-unstable group. In this case, the content ratios of repeating units a1, a2, b, c, d, e, and f are 0 ≤ a1 < 1.0, 0 ≤ a2 < 1.0, 0 <a1+a2<1.0, 0≤b≤0.9, 0≤c≤0.9, 0≤d≤0.8, 0≤e≤0.8 및 0≤f≤0.5가 바람직하고, 0≤a1≤0.9, 0≤a2≤0.9, 0.1≤a1+a2≤0.9, 0≤b≤0.8, 0≤c≤0.8, 0≤d≤0.7, 0≤e≤0.7 및 0≤f≤0.4가 보다 바람직하고, 0≤a1≤0.8, 0≤a2≤0.8, 0.1≤a1+a2≤0.8, 0≤b≤0.75, 0≤c≤0.75, 0≤d≤0.6, 0≤e≤0.6 및 0≤f≤0.3이 더욱 바람직하다. 또한, 반복 단위 f가 반복 단위 f1 내지 f5로부터 선택되는 적어도 1종인 경우, f=f1+f2+f3+f4+f5이다. 또한, a1+a2+b+c+d+e+f=1.0이다.

[0257] Meanwhile, the base polymer for negative-type resist materials does not necessarily require an acid instability group. Examples of such a base polymer include repeating unit b and, if necessary, additionally include repeating units c, d, e, and / or f. The content ratio of these repeating units is 0 <b≤1.0, 0≤c≤0.9, 0≤d≤0.8, 0≤e≤0.8 및 0≤f≤0.5가 바람직하고, 0.2≤b≤1.0, 0≤c≤0.8, 0≤d≤0.7, 0≤e≤0.7 및 0≤f≤0.4가 보다 바람직하고, 0.3≤b≤1.0, 0≤c≤0.75, 0≤d≤0.6, 0≤e≤0.6 및 0≤f≤0.3이 더욱 바람직하다. 또한, 반복 단위 f가 반복 단위 f1 내지 f5로부터 선택되는 적어도 1종인 경우, f=f1+f2+f3+f4+f5이다. 또한, b+c+d+e+f=1.0이다.

[0258] As a method for synthesizing the above base polymer, for example, a method may be used in which a monomer imparting the aforementioned repeating unit is heated in an organic solvent with a radical polymerization initiator, and polymerization is performed.

[0259] Specific examples of organic solvents used during polymerization include toluene, benzene, tetrahydrofuran (THF), diethyl ether, dioxane, propylene glycol monomethyl ether, γ-butyrolactone, and mixtures thereof. Specific examples of polymerization initiators include 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, lauroyl peroxide, etc. The temperature during polymerization is preferably 50 to 80°C. The reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

[0260] When copolymerizing monomers containing hydroxyl groups, the hydroxyl groups may be substituted with acetal groups that are easily deprotected by acids such as ethoxyethoxy groups during polymerization and deprotected with a weak acid and water after polymerization, or they may be substituted with acetyl groups, formyl groups, pivaloyyl groups, etc. and alkaline hydrolysis may be performed after polymerization.

[0261] In the case of copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, acetoxystyrene or acetoxyvinylnaphthalene may be used instead of hydroxystyrene or hydroxyvinylnaphthalene, and after polymerization, the acetoxy group may be deprotected by the above alkaline hydrolysis to obtain hydroxystyrene or hydroxyvinylnaphthalene.

[0262] As the base for alkaline hydrolysis, water ammonia, triethylamine, etc. may be used. In addition, the reaction temperature is preferably -20 to 100°C, more preferably 0 to 60°C. The reaction time is preferably 0.2 to 100 hours, more preferably 0.5 to 20 hours.

[0263] The above base polymer has a polystyrene-equivalent weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) using THF as a solvent, preferably 1,000 to 500,000, more preferably 2,000 to 30,000. When Mw is within the above range, the heat resistance of the resist film and its solubility in an alkaline developer are good.

[0264] In addition, if the molecular weight distribution (Mw / Mn) of the above base polymer is wide, there is a risk that foreign substances may be visible on the pattern or the shape of the pattern may deteriorate after exposure because low molecular weight or high molecular weight polymers are present. Since the influence of Mw or Mw / Mn tends to increase as the pattern rule becomes finer, in order to obtain a resist material suitable for use with fine pattern dimensions, it is preferable that the Mw / Mn of the above base polymer be narrowly dispersed from 1.0 to 2.0, particularly from 1.0 to 1.5.

[0265] To obtain a narrowly dispersed polymer, living radical polymerization can be used in addition to conventional radical polymerization. Specific examples of living radical polymerization include living radical polymerization using nitroxide radicals (Nitroxide-Mediated Radical Polymerization: NMP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer (RAFT) polymerization.

[0266] The above base polymer may include two or more polymers with different composition ratios, Mw, and Mw / Mn.

[0267] [Acid generator]

[0268] The resist material of the present invention may include an acid generator that generates a strong acid (hereinafter also referred to as an additive acid generator). The strong acid referred to here means, in the case of a chemically amplified positive type resist material, a compound having sufficient acidity to cause a deprotection reaction of the acid unstable group of the base polymer, and in the case of a chemically amplified negative type resist material, a compound having sufficient acidity to cause a polarity change reaction or a crosslinking reaction caused by the acid. By including such an acid generator, the sulfonium salt represented by the above-described formula (1) functions as a quencher, and the resist material of the present invention can function as a chemically amplified positive type resist material or a chemically amplified negative type resist material.

[0269] As the above acid-generating agent, for example, a compound that generates acid in response to active light or radiation (photoacid-generating agent). As for the photoacid-generating agent, any compound that generates acid upon irradiation with high-energy rays is acceptable, but it is preferable to generate sulfonic acid, imidic acid, or methic acid. Suitable photoacid-generating agents include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate type acid-generating agents. Specific examples of photoacid-generating agents include those described in paragraphs

[0122] to

[0142] of Japanese Patent Publication No. 2008-111103.

[0270] In addition, as a photoacid generator, a sulfonium salt represented by the following formula (2-1) or an iodium salt represented by the following formula (2-2) can also be suitably used.

[0271]

[0272] In equations (2-1) and (2-2), R 101 to R 105is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a halogen atom or a heteroatom. Specific examples of the halogen atom include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include R in the explanation of Formula (1). 2 to R 4 Examples of hydrocarbyl groups represented by [ ] can be given as those exemplified. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms, and as a result, may include a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sulfone ring, a carboxylic acid anhydride, a haloalkyl group, etc. Additionally, R 101 and R 102 a, they may combine with each other to form a ring together with the sulfur atom to which they combine. In this case, as a specific example of the above ring, R in the explanation of Equation (1) 2 and R 3 Examples of rings that can be formed by combining with each other, such as those exemplified by the sulfur atoms they combine with, can be given.

[0273] Specific examples of the cation of the sulfonium salt represented by Formula (2-1) include those similar to those exemplified as the cation of the sulfonium salt represented by Formula (1).

[0274] Specific examples of the cation of the iodonium salt represented by formula (2-2) include those shown below, but are not limited thereto.

[0275]

[0276]

[0277] Among equations (2-1) and (2-2), Xa - is an anion selected from the following formulas (2A) to (2D).

[0278]

[0279] In Equation (2A), R fa is a hydrocarbyl group having 1 to 40 carbon atoms, which may include a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. As a specific example, R in formula (2A') described below. fa1 One can cite the same as the example given as the hydrocarbyl group indicated by .

[0280] As for the anion represented by formula (2A), it is preferable to represent it by the following formula (2A').

[0281]

[0282] In equation (2A'), R HF is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. R fa1 It is a hydrocarbyl group having 1 to 38 carbon atoms that may include heteroatoms. As the heteroatom, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, etc. are preferred, and oxygen atoms are more preferred. As for the hydrocarbyl group, it is particularly preferred to have 6 to 30 carbon atoms in order to obtain high resolution in forming fine patterns.

[0283] R fa1The hydrocarbyl group represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include alkyl groups having 1 to 38 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, and icosyl; Examples include cyclic saturated hydrocarbyl groups having 3 to 38 carbon atoms, such as cyclopentyl groups, cyclohexyl groups, 1-adamantyl groups, 2-adamantyl groups, 1-adamantylmethyl groups, norbornyl groups, norbornylmethyl groups, tricyclodecanyl groups, tetracyclododecanyl groups, tetracyclododecanylmethyl groups, and dicyclohexylmethyl groups; unsaturated aliphatic hydrocarbyl groups having 2 to 38 carbon atoms, such as allyl groups and 3-cyclohexenyl groups; aryl groups having 6 to 38 carbon atoms, such as phenyl groups, 1-naphthyl groups, and 2-naphthyl groups; aralkyl groups having 7 to 38 carbon atoms, such as benzyl groups and diphenylmethyl groups; and groups obtained by combining these.

[0284] In addition, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, or halogen atoms, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, or nitrogen atoms, and as a result, may include a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sulfone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. Specific examples of hydrocarbyl groups containing heteroatoms include tetrahydrofuryl groups, methoxymethyl groups, ethoxymethyl groups, methylthiomethyl groups, acetamide methyl groups, trifluoroethyl groups, (2-methoxyethoxy)methyl groups, acetoxymethyl groups, 2-carboxy-1-cyclohexyl groups, 2-oxopropyl groups, 4-oxo-1-adamantyl groups, 3-oxocyclohexyl groups, etc.

[0285] The synthesis of sulfonium salts containing anions represented by formula (2A') is detailed in Japanese Patent Publication No. 2007-145797, Japanese Patent Publication No. 2008-106045, Japanese Patent Publication No. 2009-7327, Japanese Patent Publication No. 2009-258695, etc. In addition, sulfonium salts described in Japanese Patent Publication No. 2010-215608, Japanese Patent Publication No. 2012-41320, Japanese Patent Publication No. 2012-106986, Japanese Patent Publication No. 2012-153644, etc. are also suitably used.

[0286] Specific examples of anions represented by formula (2A) include those similar to the anions represented by formula (1A) in Japanese Patent Publication No. 2018-197853.

[0287] In Equation (2B), R fb1 and Rfb2 is a hydrocarbyl group having 1 to 40 carbon atoms, which may each independently contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. As a specific example, R in formula (2A'). fa1 Examples of hydrocarbyls represented by can be cited as being similar to those exemplified. R fb1 and R fb2 Preferably, it is a fluorine atom or a straight-chain fluorinated alkyl group having 1 to 4 carbon atoms. In addition, R fb1 and R fb2 They may combine with each other to form a ring together with the group to which they combine (-CF2-SO2-N--SO2-CF2-), and in this case, R fb1 and R fb2 The group obtained by combining with each other is preferably a fluorinated ethylene group or a fluorinated propylene group.

[0288] In Equation (2C), R fc1 , R fc2 and R fc3 Each is a hydrocarbyl group having 1 to 40 carbon atoms, which may independently contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. As a specific example, R in formula (2A'). fa1 Examples of hydrocarbyls represented by can be cited as being similar to those exemplified. R fc1 , R fc2 and R fc3 Preferably, as is, it is a fluorine atom or a straight-chain fluorinated alkyl group having 1 to 4 carbon atoms. Also, R fc1 and R fc2 They may combine with each other to form a ring together with the group to which they combine (-CF2-SO2-C--SO2-CF2-), and in this case, R fc1 and R fc2The group obtained by combining with each other is preferably a fluorinated ethylene group or a fluorinated propylene group.

[0289] In equation (2D), R fd is a hydrocarbyl group having 1 to 40 carbon atoms that may contain heteroatoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. As a specific example, R in formula (2A'). fa1 Examples of hydrocarbyls, such as those exemplified by [the example], can be cited.

[0290] The synthesis of a sulfonium salt containing an anion represented by formula (2D) is detailed in Japanese Patent Publication No. 2010-215608 and Japanese Patent Publication No. 2014-133723.

[0291] Specific examples of anions represented by formula (2D) include those similar to those exemplified as anions represented by formula (1D) in Japanese Patent Publication No. 2018-197853.

[0292] In addition, the photoacid generator containing an anion represented by formula (2D) has sufficient acidity to cleave acid unstable groups in the base polymer, because it does not have a fluorine atom at the α position of the sulfon group but has two trifluoromethyl groups at the β position. Therefore, it can be used as a photoacid generator.

[0293] As a light-generating agent, the one represented by the following formula (3) can also be suitably used.

[0294]

[0295] In Equation (3), R 201 and R 202 R is a hydrocarbyl group having 1 to 30 carbon atoms, which may each independently contain a halogen atom or a heteroatom. 203It is a hydrocarbylene group having 1 to 30 carbon atoms that may contain heteroatoms. Also, R 201 , R 202 and R 203 Any two of them may combine with each other to form a ring together with the sulfur atom to which they combine. In this case, as a specific example of the above ring, R in the explanation of Formula (1) 2 and R 3 Examples of rings that can be formed by combining with the sulfur atoms that combine with these can be given as examples similar to those exemplified.

[0296] R 201 and R 202 The hydrocarbyl group represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl, and tricyclo[5.2.1.0 2,6Examples include cyclic saturated hydrocarbyl groups having 3 to 30 carbon atoms, such as decyl groups and adamantyl groups; aryl groups having 6 to 30 carbon atoms, such as phenyl groups, methylphenyl groups, ethylphenyl groups, n-propylphenyl groups, isopropylphenyl groups, n-butylphenyl groups, isobutylphenyl groups, sec-butylphenyl groups, tert-butylphenyl groups, naphthyl groups, methylnaphthyl groups, ethylnaphthyl groups, n-propylnaphthyl groups, isopropylnaphthyl groups, n-butylnaphthyl groups, isobutylnaphthyl groups, sec-butylnaphthyl groups, tert-butylnaphthyl groups, and anthracenyl groups; and groups obtained by combining these. In addition, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, or halogen atoms, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, or nitrogen atoms, and as a result, may include a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sulfone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc.

[0297] R 203The hydrocarbylene group represented by may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include alkanedyl groups having 1 to 30 carbon atoms, such as methanediyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, and heptadecane-1,17-diyl group; Examples include cyclic saturated hydrocarbylene groups having 3 to 30 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norbornandiyl, and adamantandiyl; arylene groups having 6 to 30 carbon atoms, 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, and tert-butylnaphthylene; and groups obtained by combining these. In addition, some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and some of the -CH2- of the hydrocarbylene group may be substituted with a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms, and as a result, may include a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sulfone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. As the heteroatom, an oxygen atom is preferred.

[0298] In formula (3), L C is a hydrocarbylene group having 1 to 20 carbon atoms, which may include single bonds, ether bonds, or heteroatoms. The hydrocarbylene group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include R 203 Examples of hydrocarbylene groups represented as such can be given as those similar to the example.

[0299] In Equation (3), X A , X B , X C and X D is, each independently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. provided that X A , X B , X C and X D At least one of them is a fluorine atom or a trifluoromethyl group.

[0300] In equation (3), k is an integer from 0 to 3.

[0301] As for the oxidizing agent represented by formula (3), it is preferable to have it represented by the following formula (3').

[0302]

[0303] In equation (3'), L C is the same as above. X E is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. R 301 , R 302 and R 303 Each is a hydrocarbyl group having 1 to 20 carbon atoms, which may independently contain a hydrogen atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. As a specific example, R in formula (2A'). fa1Examples of hydrocarbyls represented by can be given as those exemplified. x and y are each independently integers from 0 to 5, and z is an integer from 0 to 4.

[0304] Specific examples of the light-generating agent represented by formula (3) include those similar to the light-generating agent represented by formula (2) in Japanese Patent Publication No. 2017-026980.

[0305] Among the above-mentioned photoacid generators, those containing anion represented by formula (2A') or (2D) are particularly desirable because they have low acid diffusion and excellent solubility in solvents. Additionally, those represented by formula (3') are particularly desirable because they have very low acid diffusion.

[0306] As the above-mentioned photoacid generator, a sulfonium salt or iodonium salt containing an anion having an aromatic ring substituted with an iodine atom or a bromine atom may be used. Specific examples of such salts include those represented by the following formulas (4-1) or (4-2).

[0307]

[0308] In equations (4-1) and (4-2), p is an integer satisfying 1 ≤ p ≤ 3. q and r are integers satisfying 1 ≤ q ≤ 5, 0 ≤ r ≤ 3, and 1 ≤ q + r ≤ 5. q is preferably an integer satisfying 1 ≤ q ≤ 3, and more preferably 2 or 3. r is preferably an integer satisfying 0 ≤ r ≤ 2.

[0309] Among equations (4-1) and (4-2), X BI is an iodine atom or a bromine atom, and when p and / or q are 2 or more, they may be the same or different.

[0310] Among equations (4-1) and (4-2), L 1It is a saturated hydrocarbylene group having 1 to 6 carbon atoms, which may include a single bond, an ether bond or an ester bond, or an ether bond or an ester bond. The saturated hydrocarbylene group may be straight, branched, or cyclic.

[0311] Among equations (4-1) and (4-2), L 2 When p is 1, it is a single bond or a divalent linker having 1 to 20 carbon atoms, and when p is 2 or 3, it is a (p+1)valent linker having 1 to 20 carbon atoms, and the linker may include an oxygen atom, a sulfur atom, or a nitrogen atom.

[0312] In equations (4-1) and (4-2), R 401 It may include silver, a hydroxyl group, a carboxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an amino group, or a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, an amino group, or an ether bond, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbyl carbonyl group having 2 to 20 carbon atoms, a hydrocarbyl oxycarbonyl group having 2 to 20 carbon atoms, a hydrocarbyl carbonyloxy group having 2 to 20 carbon atoms, or a hydrocarbyl sulfonyloxy group having 1 to 20 carbon atoms, or -N(R 401A )(R 401B ), -N(R 401C )-C(=O)-R 401D or -N(R 401C )-C(=O)-OR 401D is. R 401A and R 401B is, each independently, a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. R 401Cis a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms, and may include a halogen atom, a hydroxyl group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. 401D ...is an aliphatic hydrocarbyl group having 1 to 16 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, and may include a halogen atom, a hydroxyl group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. The aliphatic hydrocarbyl group may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. The hydrocarbyl group, hydrocarbyloxy group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group, hydrocarbylcarbonyloxy group, and hydrocarbylsulfonyloxy group may be straight-chain, branched, or cyclic. When p and / or r are 2 or more, each R 401 They may be identical or different.

[0313] Among these, R 401 As, hydroxyl group, -N(R 401C )-C(=O)-R 401D , -N(R 401C )-C(=O)-OR 401D Fluorine atoms, chlorine atoms, bromine atoms, methyl groups, methoxy groups, etc. are preferred.

[0314] Among equations (4-1) and (4-2), Rf 1 to Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of these is a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 They may combine to form a carbonyl group. In particular, Rf 3and Rf 4 It is desirable that all of them are fluorine atoms.

[0315] In equations (4-1) and (4-2), R 402 to R 406 Each is a hydrocarbyl group having 1 to 20 carbon atoms, which may independently contain a halogen atom or a heteroatom. Specific examples of the halogen atom include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples include R in the explanation of Formula (1). 2 to R 4 Examples of hydrocarbyl groups represented by may be those similar to those exemplified. Additionally, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, a mercapto group, a sulfonyl ring, a sulfo group, or a sulfonium salt-containing group, and some of the -CH2- of the hydrocarbyl group may be substituted with an ether bond, an ester bond, a carbonyl group, an amide bond, a carbonate bond, or a sulfonic acid ester bond. Furthermore, R 402 and R 403 These may combine with each other to form a ring together with the sulfur atom to which they combine. In this case, as a specific example of the above ring, R in the explanation of Formula (1) 2 and R 3 Examples of rings that can be formed by combining with each other, such as those exemplified by the sulfur atoms they combine with, can be given.

[0316] Specific examples of the cation of the sulfonium salt represented by Formula (4-1) include those exemplified as the cation of the sulfonium salt represented by Formula (1). Additionally, specific examples of the cation of the iodonium salt represented by Formula (4-2) include those exemplified as the cation of the iodonium salt represented by Formula (2-2).

[0317] Specific examples of the anion of the onium salt represented by formula (4-1) or (4-2) include those shown below, but are not limited thereto. In addition, among the following formulas, X BI It is the same as above.

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341] As the above-mentioned photoacid generator, a sulfonium or iodonium salt of fluorobenzenesulfonic acid combined with iodinated benzoic acid represented by the following formula (4-3) or (4-4) may also be used.

[0342]

[0343] In equations (4-3) and (4-4), s is an integer from 1 to 5. t is an integer from 0 to 3. u is an integer from 1 to 4.

[0344] Among equations (4-3) and (4-4), R 411 A saturated hydrocarbyl group having 1 to 20 carbon atoms, a saturated hydrocarbyl group having 1 to 20 carbon atoms, a saturated hydrocarbyloxy group having 1 to 20 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms, or -N(R 411A )-C(=O)-R 411B or -N(R 411A )-C(=O)-OR 411B and R 411A is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. R 411B The group is an aliphatic hydrocarbyl group having 1 to 16 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, and may include a halogen atom, a hydroxyl group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms.

[0345] Among equations (4-3) and (4-4), L 3It is a single bond or a divalent linker having 1 to 20 carbon atoms, and the linker may include an oxygen atom, a sulfur atom, or a nitrogen atom.

[0346] Among equations (4-3) and (4-4), Rf 11 It is a silver, fluorine atom, or trifluoromethyl group.

[0347] Among equations (4-3) and (4-4), R 412 to R 416 Each is a hydrocarbyl group having 1 to 20 carbon atoms, which may independently contain a halogen atom or a heteroatom. Specific examples of the halogen atom include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples include R in the explanation of Formula (1). 2 to R 4 Examples of hydrocarbyl groups represented by may be those similar to those exemplified. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, a mercapto group, a sulfonyl ring, a sulfo group, or a sulfonium salt-containing group, and some of the -CH2- of the hydrocarbyl group may be substituted with an ether bond, an ester bond, a carbonyl group, an amide bond, a carbonate bond, or a sulfonic acid ester bond. Additionally, R 402 and R 403 These may combine with each other to form a ring together with the sulfur atom to which they combine. In this case, as a specific example of the above ring, R in the explanation of Formula (1) 2 and R 3 Examples of rings that can be formed by combining with the sulfur atoms that combine with these can be given as examples similar to those exemplified.

[0348] Specific examples of the cation of the sulfonium salt represented by Formula (4-3) include those exemplified as the cation of the sulfonium salt represented by Formula (1). Specific examples of the cation of the iodonium salt represented by Formula (4-4) include those exemplified as the cation of the iodonium salt represented by Formula (2-2).

[0349] Specific examples of the anions of the onium salts represented by formulas (4-3) or (4-4) are those shown below, but are not limited to these.

[0350]

[0351]

[0352]

[0353]

[0354]

[0355] When the resist material of the present invention comprises the additive acid generator, the content thereof is preferably 0.1 to 50 parts by mass and more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the base polymer. The additive acid generator may be used alone or in combination of two or more types. The resist material of the present invention can function as a chemically amplified resist material by the base polymer comprising any one of repeating units f1 to f5 and / or by comprising the additive acid generator.

[0356] [Organic Solvents]

[0357] The resist material of the present invention may include an organic solvent. The organic solvent is not particularly limited as long as it is capable of dissolving each of the aforementioned components and each of the components described below. Specific examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone as described in paragraphs

[0144] to

[0145] of Japanese Patent Publication No. 2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; and 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. Examples include 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, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; and lactones such as γ-butyrolactone.

[0358] Among the resist materials of the present invention, the content of the organic solvent is preferably 100 to 10,000 parts by mass and more preferably 200 to 8,000 parts by mass with respect to 100 parts by mass of the base polymer. The organic solvent may be used as a single type or as a mixture of two or more types.

[0359] [Other ingredients]

[0360] The resist material of the present invention may include, in addition to the above-mentioned components, a surfactant, a dissolution inhibitor, a crosslinking agent, a quencher other than the sulfonium salt represented by formula (1) (hereinafter referred to as other quenchers), a water repellency enhancer, acetylene alcohols, etc.

[0361] Specific examples of the above surfactant include those described in paragraphs

[0165] to

[0166] of Japanese Patent Publication No. 2008-111103. By adding a surfactant, the coating properties of the resist material can be further improved or controlled. When the resist material of the present invention includes the above surfactant, the content thereof is preferably 0.0001 to 10 parts by mass per 100 parts by mass of the base polymer. The above surfactant may be used as a single type or in combination of two or more types.

[0362] When the resist material of the present invention is of the positive type, by incorporating a dissolution inhibitor, the difference in the dissolution rate between the exposed and unexposed parts can be further increased, thereby further improving the resolution. Specific examples of the dissolution inhibitor include a compound having a molecular weight preferably 100 to 1000, more preferably 150 to 800, and containing two or more phenolic hydroxyl groups in the molecule, wherein the hydrogen atoms of the corresponding phenolic hydroxyl groups are substituted by acid unstable groups in a ratio of 0 to 100 mol% in total, or a compound having a carboxyl group in the molecule, wherein the hydrogen atoms of the corresponding carboxyl groups are substituted by acid unstable groups in a ratio of 50 to 100 mol% in total. Specifically, examples include bisphenol A, trisphenol, phenolphthalein, cresol novolac, naphthalenecarboxylic acid, adamantanecarboxylic acid, compounds in which the hydrogen atoms of the hydroxyl group and carboxyl group of cholic acid are substituted with acid unstable groups, and are described, for example, in paragraphs

[0155] to

[0178] of Japanese Patent Publication No. 2008-122932.

[0363] When the resist material of the present invention is of the positive type and includes the dissolution inhibitor, the content thereof is preferably 0 to 50 parts by mass and more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the base polymer. The dissolution inhibitor may be used as a single type or in combination of two or more types.

[0364] Meanwhile, when the resist material of the present invention is of the negative type, a negative type pattern can be obtained by adding a crosslinking agent to reduce the dissolution rate of the exposed portion. Specific examples of the crosslinking agent include epoxy compounds, melamine compounds, guanamine compounds, glycoluryl compounds or urea compounds, isocyanate compounds, azide compounds, and compounds containing double bonds such as alkenyloxy groups, which are substituted with at least one group selected from methylol groups, alkoxymethyl groups, and acyloxymethyl groups. These may be used as additives, but may also be introduced as pendant groups into the polymer side chains. In addition, compounds containing hydroxyl groups may also be used as crosslinking agents.

[0365] Specific examples of the above epoxy compounds include tris(2,3-epoxypropyl)isocyanurate, trimethylolmethanetriglycidyl ether, trimethylolpropanetriglycidyl ether, triethylolethanetriglycidyl ether, etc.

[0366] Specific examples of the above melamine compounds include hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated or a mixture thereof.

[0367] Specific examples of the above guanamin compounds include tetramethylolguanamin, tetramethoxymethylguanamin, a compound in which 1 to 4 methylol groups of tetramethylolguanamin are methoxymethylated or a mixture thereof, tetramethoxyethylguanamin, tetraacyloxyguanamin, a compound in which 1 to 4 methylol groups of tetramethylolguanamin are acyloxymethylated or a mixture thereof.

[0368] Specific examples of the above glycoluryl compounds include tetramethylol glycoluryl, tetramethoxyglycoluryl, tetramethoxymethylglycoluryl, a compound in which 1 to 4 methylol groups of tetramethylol glycoluryl are methoxymethylated or a mixture thereof, a compound in which 1 to 4 methylol groups of tetramethylol glycoluryl are acyloxymethylated or a mixture thereof. Specific examples of the above urea compounds include tetramethylolurea, tetramethoxymethylurea, a compound in which 1 to 4 methylol groups of tetramethylolurea are methoxymethylated or a mixture thereof, tetramethoxyethylurea, etc.

[0369] Specific examples of the above isocyanate compounds include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, etc.

[0370] Specific examples of the above azide compounds include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, 4,4'-oxybisazide, etc.

[0371] Specific examples of compounds containing the above alkenyloxy group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol divinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane divinyl ether, etc.

[0372] When the resist material of the present invention is of the negative type and includes the crosslinking agent, the content thereof is preferably 0.1 to 50 parts by mass and more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the base polymer. The crosslinking agent may be used as a single type or in combination of two or more types.

[0373] Specific examples of the above other quenchers include conventional basic compounds. Specific examples of conventional basic compounds include primary, secondary, or tertiary aliphatic amines, hybrid 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, etc. In particular, primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Publication No. 2008-111103 are preferred, particularly amine compounds having hydroxyl groups, ether bonds, ester bonds, lactone rings, cyano groups, or sulfonic acid ester bonds, or compounds having carbamate groups described in Japanese Patent Publication No. 3790649 are preferred. By adding such basic compounds, the diffusion rate of acid in the resist film can be further suppressed, for example, or the shape can be corrected.

[0374] In addition, other quenchers include onium salts, such as sulfonium salts, iodonium salts, and ammonium salts, of sulfonic acids and carboxylic acids that are not fluorinated at the α-position, as described in Japanese Patent Publication No. 2008-158339. Sulfonic acids, imidic acids, or methic acids that are fluorinated at the α-position are required to deprotect the acid unstable groups of carboxylic acid esters, but sulfonic acids or carboxylic acids that are not fluorinated at the α-position are released through salt exchange with onium salts that are not fluorinated at the α-position. Since sulfonic acids and carboxylic acids that are not fluorinated at the α-position do not undergo a deprotection reaction, they function as quenchers.

[0375] As another example of a quencher, a polymer-type quencher described in Japanese Patent Publication No. 2008-239918 can be cited. This improves the rectangularity of the resist pattern by orienting it on the surface of the resist film. The polymer-type quencher also has the effect of preventing film reduction of the pattern or rounding of the pattern top when a protective film for immersion exposure is applied.

[0376] When the resist material of the present invention includes other quenchers, the content thereof is preferably 0 to 5 parts by mass and more preferably 0 to 4 parts by mass with respect to 100 parts by mass of the base polymer. The other quenchers may be used as a single type or in combination of two or more types.

[0377] The above-mentioned water repellency enhancer improves the water repellency of the resist film surface and can be used in immersion lithography without a top coating. As the above-mentioned water repellency enhancer, polymers containing fluoroalkyl groups, polymers containing 1,1,1,3,3,3-hexafluoro-2-propanol residues of a specific structure are preferred, and those exemplified in Japanese Patent Publication No. 2007-297590 and Japanese Patent Publication No. 2008-111103 are more preferred. The above-mentioned water repellency enhancer needs to be dissolved in an alkaline developer or an organic solvent developer. The above-mentioned water repellency enhancer having specific 1,1,1,3,3,3-hexafluoro-2-propanol residues has good solubility in the developer. As a water repellency enhancer, a polymer containing repeating units including amino groups or amine salts has a high effect of preventing the evaporation of acid in the PEB and preventing defects in the opening of the hole pattern after development. When the resist material of the present invention includes the water repellency enhancer, the content thereof is preferably 0 to 20 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the base polymer. The water repellency enhancer may be used as a single type or in combination of two or more types.

[0378] Specific examples of the above acetylene alcohols include those described in paragraphs

[0179] to

[0182] of Japanese Patent Publication No. 2008-122932. When the resist material of the present invention includes the above acetylene alcohols, the content thereof is preferably 0 to 5 parts by mass per 100 parts by mass of base polymer. The above acetylene alcohols may be used as a single type or in combination of two or more types.

[0379] [Pattern Formation Method]

[0380] When the resist material of the present invention is used in the manufacture of various integrated circuits, known lithography techniques may be applied. For example, a specific example of a pattern formation method may include a process of forming a resist film on a substrate using the aforementioned resist material, a process of exposing the resist film to high-energy rays, and a process of developing the exposed resist film using a developer.

[0381] First, the resist material of the present invention is applied to a substrate for manufacturing an integrated circuit (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.) or a substrate for manufacturing a mask circuit (Cr, CrO, CrON, MoSi2, SiO2, etc.) by a suitable application method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating so that the thickness of the coating film is 0.01 to 2 μm. This is pre-baked on a hot plate, preferably at 60 to 150°C for 10 seconds to 30 minutes, more preferably at 80 to 120°C for 30 seconds to 20 minutes, to form a resist film.

[0382] Next, the resist film is exposed using high-energy rays. Specific examples of the high-energy rays include ultraviolet rays, far-ultraviolet rays, EB, EUV with a wavelength of 3 to 15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, synchrotron radiation, etc. When ultraviolet rays, far-ultraviolet rays, EUV, X-rays, soft X-rays, excimer laser light, gamma rays, synchrotron radiation, etc. are used as the high-energy rays, the exposure amount is preferably 1 to 200 mJ / cm², more preferably 10 to 100 mJ / cm², by using a mask to form a desired pattern or directly irradiating. When EB is used as the high-energy rays, the exposure amount is preferably 0.1 to 300 μC / cm², more preferably 0.5 to 200 μC / cm², by using a mask to form a desired pattern or directly drawing. In addition, the resist material of the present invention is particularly suitable for fine patterning by high-energy rays, specifically KrF excimer laser light, ArF excimer laser light, EB, EUV, X-rays, soft X-rays, γ-rays, and synchrotron radiation, and is particularly suitable for fine patterning by EB or EUV.

[0383] After exposure, PEB may or may not be performed on a hot plate or in an oven, preferably at 30 to 150°C for 10 seconds to 30 minutes, more preferably at 50 to 120°C for 30 seconds to 20 minutes.

[0384] After exposure or after PEB, a desired pattern is formed by developing a resist film exposed by a conventional method such as a dip method, puddle method, or spray method using a developer of an alkaline aqueous solution of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc., in an amount of preferably 0.1 to 10 mass%, more preferably 2 to 5 mass%, for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes. In the case of a positive-type resist material, the portion exposed to light is dissolved in the developer, and the portion not exposed is not dissolved, and a desired positive-type pattern is formed on the substrate. In the case of a negative-type resist material, the opposite is true to the case of a positive-type resist material, where the portion exposed to light becomes insoluble in the developer, and the portion not exposed is dissolved.

[0385] By using a positive resist material containing a base polymer containing acid instability groups, a negative pattern can also be obtained by organic solvent development. Specific examples of the developer used at this time include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutylketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl penthenate, methyl crotonicate, ethyl crotonicate, methyl propionate, ethyl propionate, 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, Examples include pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, etc. These organic solvents may be used individually or in a mixture of two or more types.

[0386] When the development is finished, rinsing is performed. As for the rinsing solution, a solvent that is mixed with the developer solution and does not dissolve the resist film is preferred. As such a solvent, alcohols having 3 to 10 carbon atoms, ether compounds having 8 to 12 carbon atoms, alkanes, alkenes, alkynes, aromatic solvents having 6 to 12 carbon atoms are preferably used.

[0387] Specific examples of the above alcohol having 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, Examples include 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 1-octanol, etc.

[0388] Specific examples of the above ether compounds having 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-pentyl ether, di-n-hexyl ether, etc.

[0389] Specific examples of the above-mentioned alkanes having 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, cyclononane, etc. Specific examples of the above-mentioned alkenes having 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, cyclooctene, etc. Specific examples of the above-mentioned alkynes having 6 to 12 carbon atoms include hexine, heptene, octene, etc.

[0390] Specific examples of the above aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, mesitylene, etc.

[0391] By rinsing, the occurrence of defects or collapse of the resist pattern can be reduced. In addition, rinsing is not strictly necessary, and the amount of solvent used can be reduced by not rinsing.

[0392] The hole pattern or trench pattern after development may be shrunk using thermal flow, RELACS technology, or DSA technology. A shrinking agent is applied onto the hole pattern, and crosslinking of the shrinking agent occurs on the surface of the resist film due to the diffusion of an acid catalyst from the resist film during baking, causing the shrinking agent to adhere to the sidewalls of the hole pattern. The baking temperature is preferably 70 to 180°C, more preferably 80 to 170°C, and the baking time is preferably 10 to 300 seconds, and the excess shrinking agent is removed to shrink the hole pattern.

[0393] [Example]

[0394] The present invention will be specifically described below by presenting synthetic examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0395] The structures of quenchers Q-1 to Q-16 used in the resist material are shown below.

[0396]

[0397]

[0398] [Synthesization Example] Synthesis of base polymers (polymers P-1 to P-4)

[0399] Each monomer was combined and copolymerization was carried out in THF as a solvent, the mixture was placed in methanol, and the precipitated solid was washed with hexane, isolated, and dried to obtain base polymers (polymers P-1 to P-4) having the compositions shown below. The composition of the obtained base polymers is 1 Mw and Mw / Mn were confirmed by H-NMR and GPC (solvent: THF, standard: polystyrene).

[0400]

[0401] [Examples 1 to 19, Comparative Examples 1, 2] Preparation of Resist Material and Evaluation thereof

[0402] (1) Preparation of resist material

[0403] A resist material was prepared by dissolving each component in a solution with the composition shown in Table 1 and filtering it through a 0.2 μm size filter. The resist materials of Examples 1 to 18 and Comparative Example 1 are positive type, and the resist materials of Example 19 and Comparative Example 2 are negative type.

[0404] In Table 1, each component is as follows.

[0405] · Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

[0406] DAA (diacetone alcohol)

[0407] EL (ethyl lactate)

[0408] · Acid-generating agents: PAG-1, PAG-2

[0409]

[0410] · Comparative Quencher: cQ-1

[0411]

[0412] (2) EUV lithography evaluation

[0413] Each resist material shown in Table 1 was spin-coated onto a Si substrate formed with a film thickness of 20 nm using a silicon-containing spin-on hard mask SHB-A940 (silicon content of 43 mass%) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd., and pre-baked at 100°C for 60 seconds using a hot plate to produce a resist film with a film thickness of 60 nm. Next, the resist film was exposed using an ASML EUV scanner NXE3400 (NA0.33, σ0.9 / 0.6, quadruple illumination, wafer dimensions of pitch 44 nm, mask of a hole pattern with +20% bias), PEB was performed on a hot plate at the temperature listed in Table 1 for 60 seconds, and development was performed with a 2.38 mass% TMAH aqueous solution for 30 seconds, and a hole pattern with dimensions of 22 nm was obtained in Examples 1 to 18 and Comparative Example 1, and a dot pattern with dimensions of 22 nm was obtained in Example 19 and Comparative Example 2.

[0414] Using a measuring SEM (CG6300) manufactured by Hitachi High-Tech Corp., the exposure amount at which a hole or dot dimension is formed to 22 nm was measured and this was defined as sensitivity. In addition, the dimensions of 50 holes or dots at this time were measured, and the value of three times the standard deviation (σ) calculated from the result (3σ) was determined as the CDU. The results are shown in Table 1.

[0415]

[0416] From the results shown in Table 1, it was found that the resist material of the present invention containing the sulfonium salt of an iodinated phenolic compound has high sensitivity and improved CDU.

Claims

Claim 1 A resist material comprising one or more of: an acid-generating agent comprising a sulfonium salt of an iodinated phenolic compound; and a base polymer comprising at least one selected from a repeating unit represented by the following formula (f4) and a repeating unit represented by the following formula (f5), wherein the sulfonium salt is represented by the following formula (1). (In the equation, m is 2, 3, 4, or 5. n is 1, 2, 3, or 4. provided that 3≤m+n≤5.R 1 Each is independently a halogen atom other than an iodine atom, a nitro group, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms, or a hydrocarbylsulfonyloxy group having 1 to 20 carbon atoms, and said hydrocarbyloxy group, hydrocarbylcarbonyloxy group and hydrocarbylsulfonyloxy group may have at least one selected from a halogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom. 2 to R 4 Each is an aryl group having 6 to 20 carbon atoms that may independently contain a heteroatom. Also, R 2 and R 3 These may combine with each other to form a ring together with the sulfur atom to which they combine. (during food, R A Z is, independently, a hydrogen atom or a methyl group. 6 It is a single bond, a phenylene group, a naphthylene ring, an ester bond, or an amide bond. 7A Z is a single bond or a divalent organic group having 1 to 24 carbon atoms, and may have at least one selected from a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. 7B Z is a monovalent organic group having 1 to 10 carbon atoms and may have at least one selected from a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. 8 It is a single bond, ether bond, ester bond, thioether bond, or an alkanedyl group having 1 to 6 carbon atoms. 9 R is a trivalent organic group having 1 to 12 carbon atoms and may have at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom. 23 to R 25 is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a halogen atom or a heteroatom. Also, R 23 and R 24 a, they may combine with each other to form a ring together with the sulfur atom to which they combine. 26 Each is independently a saturated hydrocarbyl 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. The element R is a (j+2) aromatic hydrocarbon group having 6 to 10 carbon atoms. j is independently an integer from 0 to 5. Claim 2 A resist material according to claim 1, further comprising a base polymer comprising at least one selected from a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (a2). (during food, R A is, independently, a hydrogen atom or a methyl group. 1 A linker having 1 to 12 carbon atoms comprising at least one selected from a single bond, a phenylene group or a naphthylene group, or an ester bond, an ether bond, and a lactone ring, wherein the phenylene group, the naphthylene group, and the linker may have at least one selected from a halogen atom, a hydroxyl group, a saturated hydrocarbyloxy group having 1 to 8 carbon atoms, and a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms. 2 is a single bond, ester bond, or amide bond. 3 It is a single bond, an ether bond, or an ester bond. 11 and R 12 are, independently, acid instability groups. 13 It is silver, a hydroxyl group, a halogen atom, a trifluoromethyl group, a cyano group, or a saturated hydrocarbyl group having 1 to 6 carbon atoms. 14 is a single bond or an alkandyl group having 1 to 6 carbon atoms, and a portion of the -CH2- of the said alkandyl group may be substituted by an ether bond or an ester bond. a is 1 or 2. b is an integer from 0 to 4. provided that 1 ≤ a + b ≤ 5.) Claim 3 In paragraph 2, a resist material that is a chemically amplified positive type resist material. Claim 4 In claim 1, a resist material comprising, additionally, a base polymer that does not contain acid unstable groups. Claim 5 In paragraph 4, a resist material that is a chemically amplified negative type resist material. Claim 6 A resist material according to claim 1, further comprising a base polymer including at least one selected from a repeating unit represented by the following formula (f1), a repeating unit represented by the following formula (f2), and a repeating unit represented by the following formula (f3). (during food, R A Z is, independently, a hydrogen atom or a methyl group. 1 Silver, single bonds, 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 a combination thereof, or -OZ 11 -, -C(=O)-OZ 11 - or -C(=O)-NH-Z 11 -is. Z 11 It 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 a combination thereof, and may include a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 2 is a single bond or an ester bond. 3 Silver, single bond, -Z 31 -C(=O)-O-, -Z 31 -O- or -Z 31 -OC(=O)- is. Z 31 It is an aliphatic hydrocarbylene group having 1 to 12 carbon atoms, a phenylene group, or a group having 7 to 18 carbon atoms obtained by combining these, and may include a carbonyl group, an ester bond, an ether bond, an iodine atom, or a bromine atom. 4 is a methylene group, a 2,2,2-trifluoro-1,1-ethanediyl group, or a carbonyl group. 5 is, single bond, methylene group, ethylene group, phenylene group, fluorinated phenylene group, phenylene group substituted with trifluoromethyl group, -OZ 51 -, -C(=O)-OZ 51 - or -C(=O)-NH-Z 51 -is. Z 51 It is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may include a carbonyl group, an ester bond, an ether bond, a halogen atom, or a hydroxyl group. 21 to R 25 is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a halogen atom or a heteroatom. Also, R 23 and R 24 a, they may combine with each other to form a ring together with the sulfur atom to which they combine. - is a non-nucleophilic counterion.) Claim 7 A resist material according to claim 1, wherein the acid generating agent is an acid generating agent that generates a strong acid. Claim 8 A resist material according to claim 7, wherein the acid generating agent generates sulfonic acid, imidic acid, or methic acid. Claim 9 In paragraph 1, additionally, a resist material comprising an organic solvent. Claim 10 In claim 1, a resist material further comprising a surfactant. Claim 11 A pattern forming method comprising: a process of forming a resist film on a substrate using a resist material described in any one of claims 1 to 10; a process of exposing the resist film to high-energy rays; and a process of developing the exposed resist film using a developer. Claim 12 A pattern forming method according to claim 11, wherein the high-energy line is KrF excimer laser light, ArF excimer laser light, electron beam, or extreme ultraviolet light with a wavelength of 3 to 15 nm. Claim 13 delete Claim 14 delete

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