Sulfonium salt monomer, polymer, chemically amplified resist composition, and pattern forming method

Abstract

In photolithography using high energy rays, a sulfonium salt-type monomer used in a chemical amplification resist composition having excellent solvent solubility, high sensitivity, high contrast, and excellent lithography performance such as LWR, CDU, EL, and DOF, a polymer comprising repeating units derived from said sulfonium salt-type monomer, a chemical amplification resist composition comprising said polymer, and a method for forming a pattern using said chemical amplification resist composition are provided. Sulfonium salt type monomer represented by the following formula (A). (In the formula, Z- is a fluoroalkanesulfonate anion having a polymerizable group.)

Description

Technology Field

[0001] The present invention relates to a sulfonium salt-type monomer, a polymer, a chemical amplification resist composition, 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. In particular, the expansion of the flash memory market and the increase in memory capacity are driving this miniaturization. As for cutting-edge miniaturization technology, mass production of 65 nm node devices using ArF lithography is underway, and preparations for mass production of 45 nm node devices using next-generation ArF immersion lithography are in progress. For next-generation 32 nm node devices, immersion lithography using an ultra-high NA lens combining a liquid with a higher refractive index than water, a high refractive index lens, and a high refractive index resist film, extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm, and double exposure (double patterning lithography) of ArF lithography are candidates and are currently under review.

[0003] As miniaturization progresses and approaches the diffraction limit, optical contrast decreases. Due to this decrease in optical contrast, in positive-type resist films, a decline in the resolution of hole and trench patterns, as well as a decrease in focus margin, occurs.

[0004] With the miniaturization of patterns, line width roughness (LWR) and hole pattern dimensional uniformity (CDU) are becoming problematic. The effects of localization or aggregation of base polymers or acid generators, as well as the influence of acid diffusion, have been pointed out. Furthermore, LWR tends to increase with the thinning of the resist film, and the degradation of LWR caused by thinning accompanying miniaturization is becoming a serious issue.

[0005] In resist compositions for EUV lithography, it is necessary to simultaneously achieve high sensitivity, high resolution, and low LWR. Shortening the acid diffusion distance reduces LWR but lowers sensitivity. For example, lowering the post-exposure baking (PEB) temperature reduces LWR but lowers sensitivity. Increasing the amount of added quencher also reduces LWR but lowers sensitivity. It is necessary to overcome the trade-off relationship between sensitivity and LWR.

[0006] To suppress acid diffusion, a resist compound containing repeating units derived from onium salts of sulfonic acids having polymerizable unsaturated bonds has been proposed (Patent Document 1). These so-called polymer-linked acid generators are characterized by very short acid diffusion because polymeric sulfonic acids are generated upon exposure. Additionally, sensitivity can be improved by increasing the proportion of the acid generator. In the case of additive acid generators, increasing the amount added also leads to high sensitivity, but in this case, the acid diffusion distance also increases. Since acid diffuses non-uniformly, increased acid diffusion leads to the deterioration of the LWR or CDU. It can be said that polymeric acid generators possess high capability in terms of the balance of sensitivity, LWR, and CDU.

[0007] Since iodine atoms have a very high absorption rate of EUV with a wavelength of 13.5 nm, the effect of secondary electron generation from iodine atoms during exposure has been confirmed and is receiving attention in EUV lithography. Patent Document 2 describes a photoacid generator in which iodine atoms are introduced into an anion, and Patent Documents 3 and 4 describe a photoacid generator containing a polymerizable group in which iodine atoms are introduced into anion. Although some improvement in lithography performance has been confirmed by this, iodine atoms do not have high solubility in organic solvents, so there is a concern about precipitation in the solvent.

[0008] Patent documents 5 and 6 describe a photoacid generator in which a pentafluorosulfanyl group (-SF5 group) is introduced into a cation. Patent document 7 describes a photoacid generator in which a trifluoromethoxy group (-OCF3 group) is introduced. Additionally, patent document 8 describes a photoacid generator derived from a sulfonium cation having a fluorine atom, a trifluoromethoxy group, and an acid-unstable group. Although the improvement of lithography performance has progressed to some extent through these, there is still room for improvement, and the development of a resist material effective for forming even finer patterns is desired. Prior art literature

[0009] Japanese Patent No. 4425776 Japanese Patent No. 6720926 Japanese Patent No. 6973274 Japanese Patent Publication No. 2024-43941 International Publication No. 2023 / 223624 International Publication No. 2024 / 128017 Japanese Patent Publication No. 2022-59112 Japanese Patent Publication No. 2023-169812 The problem to be solved

[0010] In acid-catalyzed chemical amplification resist compositions, there is a desire to develop a resist composition capable of further increasing sensitivity and improving lithography performance such as LWR, CDU, exposure margin (EL), and depth of focus (DOF).

[0011] The present invention has been made in consideration of the above circumstances, and aims to provide a sulfonium salt-type monomer used in a chemical amplification resist composition that has excellent solvent solubility, high sensitivity, high contrast, and excellent lithography performance such as LWR, CDU, EL, and DOF, particularly in photolithography using high energy rays such as KrF excimer laser light, ArF excimer laser light, electron beam (EB), and EUV; a polymer comprising repeating units derived from said sulfonium salt-type monomer; a chemical amplification resist composition comprising said polymer; and a method for forming a pattern using said chemical amplification resist composition. means of solving the problem

[0012] The inventors, having conducted repeated examinations to achieve the above objective, discovered that by using a polymer comprising repeating units derived from a sulfonium salt-type monomer comprising a sulfonium cation having an acid instability group having a pentafluorosulfanyl group and a tertiary / secondary ether structure, a tertiary / secondary carbonate structure, or an acetal structure, and a fluorosulfonic acid anion having a polymerizable group as a polymer-linked acid-generating agent, a chemical amplification resist composition with high sensitivity, improved lithography performance such as LWR, CDU, EL, and DOF, high contrast, and high resolution is obtained, and thus completed the present invention.

[0013] That is, the present invention provides the following sulfonium salt-type monomer, polymer, chemical amplification resist composition, and pattern forming method.

[0014] 1. A sulfonium salt-type monomer represented by the following formula (A).

[0015]

[0016] (In the equation, n1 is 0 or 1. n2 is 0, 1 or 2. n3 is 0, 1 or 2. n4 is 0, 1 or 2. Provided that when n1 is 0, 0 ≤ n2 + n3 + n4 ≤ 5, and when n1 is 1, 0 ≤ n2 + n3 + n4 ≤ 7. n5 is 0 or 1. n6 is 0, 1 or 2. n7 is 0, 1 or 2. n8 is 0, 1 or 2. Provided that when n5 is 0, 0 ≤ n6 + n7 + n8 ≤ 5, and when n5 is 1, 0 ≤ n6 + n7 + n8 ≤ 7. n9 is 0 or 1. n10 is 0, 1 or 2. n11 is 0, 1 or 2. n12 is 0, 1 or 2. However, when n9 is 0, 0 ≤ n10 + n11 + n12 ≤ 5, and when n9 is 1, 0 ≤ n10 + n11 + n12 ≤ 7. Also, 1 ≤ n2 + n6 + n10 ≤ 6, and 1 ≤ n3 + n7 + n11 ≤ 6.

[0017] R 1 , R 2 and R 3 Each is independently a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom. When n4 is 2, each R 1 They may be identical or different, and 2 R 1 These may bond with each other to form a ring with the carbon atom to which they bond. When n8 is 2, each R 2 They may be the same or different, and 2 R 2 They may bond with each other to form a ring together with the carbon atom to which they bond. When n12 is 2, each R 3 They may be identical or different, and 2 R 3 These may combine with each other to form a ring together with the carbon atoms they bond with.

[0018] R AL1 , R AL2 and R AL3 Each is an independent acid instability phase. When n3 is 2, each R AL1 They may be the same or different. When n7 is 2, each R AL2 They may be the same or different. When n11 is 2, each R AL3 They may be the same or different.

[0019] At least one -SF5 group, -OR AL1 , -OR AL2 or -OR AL3 It is bonded to the carbon atom adjacent to the carbon atom that is bonding.

[0020] Also, S + Two of the three aromatic rings bonded to it may bond with each other to form a ring together with the sulfur atom to which they bond.

[0021] Z - is a fluoroalkanesulfonic acid anion having a polymerizable group.

[0022] 2. A sulfonium salt-type monomer of 1 represented by the following formula (A1).

[0023]

[0024] (among the food, n2 to n4, n6 to n8, n10 to n12, R AL1 to R AL3 , R 1 to R 3 and Z - is the same as above.)

[0025] 3. A sulfonium salt-type monomer of type 1 or 2, wherein the acid unstable group is represented by the following formula (AL-1) or (AL-2).

[0026]

[0027] (In the formula, m1 and m2 are each independently 0 or 1.

[0028] RL1 and R L2 is, each independently, a hydrocarbyl group having 1 to 12 carbon atoms. R L3 It is silver, a hydrogen atom, or a hydrocarbyl group having 1 to 12 carbon atoms. R L1 , R L2 and R L3 A portion of the -CH2- of the hydrocarbyl group represented by may be substituted with -O- or -S-, and if the said hydrocarbyl group includes an aromatic ring, some or all of the hydrogen atoms of said aromatic ring may be substituted with a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms that may include a halogen atom, or an alkoxy group having 1 to 4 carbon atoms that may include a halogen atom. In addition, R L1 and R L2 a. They may bond with each other to form a ring together with the carbon atom to which they bond, and some of the -CH2- groups of the ring may be substituted with -O- or -S-. However, R L3 In the case of this hydrogen atom, R L1 and R L2 They combine with each other to form a ring containing multiple bonds with the carbon atoms they bond to.

[0029] R L4 and R L5 is, each independently, a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. R L6 Silver is a hydrocarbyl group having 1 to 20 carbon atoms, and a portion of the -CH2- of the said hydrocarbyl group may be substituted with -O- or -S-. In addition, R L5 and R L6 These, combining with each other, the carbon atoms and L that bond to them A It may form a complex group having 3 to 20 carbon atoms together with, and part of the -CH2- of the said complex group may be substituted with -O- or -S-.

[0030] L Ais -O- or -S-.

[0031] * indicates bonding loss with adjacent -O-.)

[0032] 4. Z - a, a sulfonium salt-type monomer of any one of 1 to 3 which is an anion represented by the following formula (Z1).

[0033]

[0034] (In the formula, k is 0, 1, 2, or 3.

[0035] R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0036] Z 1 Each independently, a phenylene group, naphthylene group, or *-C(=O)-OZ that may have a single bond or a substituent 11 -is. Z 11 The aliphatic hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the aliphatic hydrocarbylene group may include a halogen atom, a hydroxyl group, an ether bond, an ester bond, or a lactone ring.

[0037] Z 2 is a single bond, ether bond, ester bond, amide bond, sulfonic acid ester bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0038] Z 3 Silver, each independently, single bond, ***-Z 31 -C(=O)-O-, ***-C(=O)-N(H)-Z 31 - or ***-OZ 31 -is. Z 31 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms.

[0039] Z 4 is, each independently, single bond, ****-Z 41-C(=O)-O-, ****-C(=O)-N(H)-Z 41 - or ****-OZ 41 -is. Z 41 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms.

[0040] * indicates bond loss with carbon atoms in the main chain. *** is Z 2 Indicates the bonding hand with. **** is Z 3 It represents the bonding hand with.

[0041] L 1 It is a single bond, ether bond, ester bond, carbonyl group, sulfonic acid ester bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0042] Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms.

[0043] Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms.

[0044] 5. Z - a, a sulfonium salt-type monomer of any one of 1 to 3 which is an anion represented by the following formula (Z2).

[0045]

[0046] (In the equation, m1 is 0 or 1. m2 is 0, 1, 2, 3 or 4. m3 is 0, 1, 2 or 3. m4 is 0 or 1. m5 is 0, 1, 2, 3 or 4. m6 is 0, 1, 2 or 3. m7 is 0 or 1. m8 is 1, 2, 3 or 4. m9 is 0, 1, 2 or 3. m10 is 0, 1, 2, 3 or 4. m11 is 0 or 1. m12 is 0 or 1. Provided that when m1 is 0, 0 ≤ m2 + m3 + m12 ≤ 4, and when m1 is 1, 0 ≤ m2 + m3 + m12 ≤ 6. When m4 is 0, 0 ≤ m5 + m6 ≤ 4, and When m4 is 1, 0 ≤ m5 + m6 ≤ 6. When m7 is 0, 0 ≤ m8 + m9 ≤ 5, and when m7 is 1, 0 ≤ m8 + m9 ≤ 7. Also, 1 ≤ m2 + m5 + m8 ≤ 4.

[0047] R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0048] R 11 , R 12 and R 13 Each is independently a halogen atom other than an iodine atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. When m3 is 2 or 3, each R 11 They may be identical or different, and 2 R 11 These may bond with each other to form a ring with the carbon atom to which they bond. When m6 is 2 or 3, each R 12 They may be the same or different, and 2 R 12They may bond with each other to form a ring with the carbon atom to which they bond. When m9 is 2 or 3, each R 13 They may be identical or different, and 2 R 13 These may combine with each other to form a ring together with the carbon atoms they bond with.

[0049] L A , L B , L C , L D and L E Each is independently a single bond, an ether bond, an ester bond, a sulfonic acid ester bond, an amide bond, a sulfonic acid amide bond, a carbonate bond, or a carbamate bond.

[0050] X L1 and X L2 Each is a hydrocarbylene group having 1 to 40 carbon atoms, which may independently contain a single bond or a heteroatom.

[0051] Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms.

[0052] Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms.

[0053] However, there are no cases where m11 and m12 become 0 simultaneously, and L A , L B , L C , L D , X L1 and X L2 There is no case where a single bond is formed at the same time.

[0054] 6. A monomer-type photoacid generator comprising a sulfonium salt-type monomer of any one of 1 to 5.

[0055] 7. A polymer comprising repeating units derived from a monomeric photoacid generator of 6.

[0056] 8. Additionally, a polymer of 7 comprising at least one selected from a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (a2), and a repeating unit represented by the following formula (a3).

[0057]

[0058] (during food, R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0059] X 1 Silver, single bond, phenylene group, naphthylene group, *-C(=O)-OX 11 - or *-C(=O)-N(H)-X 11 - and, the corresponding phenylene group or naphthylene group may be substituted with a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbyl group having 1 to 10 carbon atoms that may include a fluorine atom, a saturated hydrocarbyloxy group having 1 to 10 carbon atoms that may include a fluorine atom, or a halogen atom. X 11 The silver is a saturated hydrocarbylene group, a phenylene group, or a naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may include a hydroxyl group, an ether bond, an ester bond, or a lactone ring.

[0060] X 2 is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-.

[0061] * indicates the bond loss with carbon atoms in the main chain.

[0062] R 21It is silver, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a pentafluorosulfanyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. When a1 is 2, 3, or 4, each R 21 They may be the same or different.

[0063] AL 1 and AL 2 Each is, independently, an acid instability phase.

[0064] a1 is 0, 1, 2, 3, or 4.)

[0065]

[0066] (In the equation, b1 is 0 or 1. b2 is 0, 1, 2 or 3 when b1 is 0, and 0, 1, 2, 3, 4 or 5 when b1 is 1.

[0067] R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0068] X 3 It is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-. * indicates a bond loss with a carbon atom in the main chain.

[0069] X 4 is a single bond, an aliphatic hydrocarbylene group having 1 to 4 carbon atoms, a carbonyl group, a sulfonyl group, or a group obtained by combining these.

[0070] X 5 and X 6 Each is independently an oxygen atom or a sulfur atom. However, X 4 and X6 It is bonded to adjacent carbon atoms of the aromatic ring.

[0071] R 22 and R 23 It is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a hydrogen atom or a heteroatom. Also, R 22 and R 23 These may combine with each other to form a ring together with the carbon atoms they bond with.

[0072] R 24 ...is a halogen atom, a hydroxyl group, a cyano group, a nitro group, a pentafluorosulfanyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom, or -N(R 24A )(R 24B ) is. R 24A and R 24B Each is independently a hydrogen atom or a hydrocarbyl group having 1 to 6 carbon atoms. When b2 is 2 or more, each R 24 They may be identical or different, and multiple R 24 They may combine with each other to form a ring together with the carbon atom of the aromatic ring to which they are bonded.

[0073] 9. Additionally, a polymer of 7 or 8 comprising at least one selected from a repeating unit represented by the following formula (b1) and a repeating unit represented by the following formula (b2).

[0074]

[0075] (during food, R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0076] Y1 It is a single bond or *-C(=O)-O-. * indicates a bond loss with a carbon atom in the main chain.

[0077] R 31 It is a group having 1 to 20 carbon atoms comprising at least one structure selected from hydroxyl groups other than phenolic hydroxyl groups, cyano groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, lactone rings, sulfone rings, and carboxylic acid anhydrides (-C(=O)-OC(=O)-).

[0078] R 32 is a halogen atom, a carboxyl group, a nitro group, a cyano group, a pentafluorosulfanyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. When c2 is 2, 3, or 4, each R 32 They may be the same or different.

[0079] c1 is 1, 2, 3, or 4. c2 is 0, 1, 2, 3, or 4. Provided that 1 ≤ c1 + c2 ≤ 5.

[0080] 10. A chemical amplification resist composition comprising a base polymer comprising (A) a polymer of any one of 7 to 9.

[0081] 11. Additionally, (B) a chemical amplification resist composition of 10 comprising an organic solvent.

[0082] 12. Additionally, (C) a chemical amplification resist composition of 10 or 11 comprising a quencher.

[0083] 13. Additionally, (D) a chemical amplification resist composition of any one of 10 to 12 comprising a photoacid generator.

[0084] 14. Additionally, (E) a chemical amplification resist composition of any one of 10 to 13 comprising a surfactant.

[0085] 15. A pattern forming method comprising: a process of forming a resist film on a substrate using a chemical amplification resist composition of any one of 10 to 14; a process of exposing the resist film to high-energy rays; and a process of developing the exposed resist film using a developer.

[0086] 16. A pattern forming method of 15 in which the high-energy line is KrF excimer laser light, ArF excimer laser light, EB, or EUV with a wavelength of 3 to 15 nm. Effects of the invention

[0087] When a pattern is formed using a chemical amplification resist composition comprising a polymer containing repeating units that function as photoacid generators derived from the sulfonium salt-type monomer of the present invention, a resist pattern with high contrast, good sensitivity, and excellent lithography performance such as LWR, CDU, EL, and DOF can be formed. Specific details for implementing the invention

[0088] The present invention will be described in detail below. In addition, in the following description, depending on the structure represented by the chemical formula, an asymmetric carbon may be present, and enantiomers or diastereomers may be present; however, in such cases, the isomers are represented by a single formula. The isomers may be used as a single type or as a mixture of two or more types.

[0089] [Sulfonium salt type monomer]

[0090] The sulfonium salt-type monomer of the present invention is represented by the following formula (A).

[0091]

[0092] In formula (A), n1 is 0 or 1. When n1 is 0, it is a benzene ring, and when n1 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable for n1 to be a benzene ring of 0. n2 is 0, 1, or 2. n3 is 0, 1, or 2. n4 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable for n4 to be 0 or 1. However, when n1 is 0, 0 ≤ n2 + n3 + n4 ≤ 5, and when n1 is 1, 0 ≤ n2 + n3 + n4 ≤ 7.

[0093] In formula (A), n5 is 0 or 1. When n5 is 0, it is a benzene ring, and when n5 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable for n5 to be a benzene ring of 0. n6 is 0, 1, or 2. n7 is 0, 1, or 2. n8 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable for n8 to be 0 or 1. However, when n5 is 0, 0 ≤ n6 + n7 + n8 ≤ 5, and when n5 is 1, 0 ≤ n6 + n7 + n8 ≤ 7.

[0094] In formula (A), n9 is 0 or 1. When n9 is 0, it is a benzene ring, and when n9 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable for n9 to be a benzene ring of 0. n10 is 0, 1, or 2. n11 is 0, 1, or 2. n12 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable for n12 to be 0 or 1. However, when n9 is 0, 0 ≤ n10 + n11 + n12 ≤ 5, and when n9 is 1, 0 ≤ n10 + n11 + n12 ≤ 7.

[0095] In formula (A), 1≤n2+n6+n10≤6, but preferably 1≤n2+n6+n10≤3, and more preferably 1≤n2+n6+n10≤2. Also, 1≤n3+n7+n11≤6, but preferably 1≤n3+n7+n11≤3, and more preferably 1≤n3+n7+n11≤2.

[0096] In Equation (A), R 1 , R 2 and R 3Each is independently a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom. Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The hydrocarbyl portion of the hydrocarbyl group, the hydrocarbyloxy group, and the hydrocarbylthio group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include: an alkyl group having 1 to 20 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 n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, etc.; a cyclic saturated hydrocarbyl group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, an adamantyl group, etc. Examples include alkenyl groups having 2 to 20 carbon atoms, such as vinyl groups, 1-propenyl groups, 2-propenyl groups, butenyl groups, and hexenyl groups; cyclic unsaturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclohexenyl groups; aryl groups having 6 to 20 carbon atoms, such as phenyl groups and naphthyl groups; aralkyl groups having 7 to 20 carbon atoms, such as benzyl groups, 1-phenylethyl groups, and 2-phenylethyl groups; and groups obtained by combining these. Among these, preferably, it is an aryl group.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 cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, 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.

[0097] When n4 is 2, each R 1 They may be identical or different. Also, when n4 is 2, the 2 R 1 These may combine with each other to form a ring together with the carbon atom to which they are bonded. As for the ring, a 5 to 8-membered ring is preferred. When n8 is 2, each R 2 They may be identical or different. Also, when n8 is 2, the 2 R 2 a, they may bond with each other to form a ring together with the carbon atom to which they bond. As the ring, a 5 to 8-membered ring is preferred. When n12 is 2, each R 3 They may be identical or different. Also, when n12 is 2, the 2 R 3 These may combine with each other to form a ring together with the carbon atom to which they are bonded. As for the ring, a 5 to 8-membered ring is preferred.

[0098] In Equation (A), R AL1 , R AL2 and R AL3 Each is an independent acid instability phase. When n3 is 2, each R AL1 They may be the same or different. When n7 is 2, each R AL2They may be the same or different. When n11 is 2, each R AL3 They may be the same or different.

[0099] The above acid instability group is preferably represented by the following formula (AL-1) or (AL-2).

[0100]

[0101] (In the formula, * indicates a joining hand.)

[0102] Among equations (AL-1) and (AL-2), m1 and m2 are, independently, 0 or 1.

[0103] In formula (AL-1), R L1 and R L2 is, each independently, a hydrocarbyl group having 1 to 12 carbon atoms. R L3 It is silver, a hydrogen atom, or a hydrocarbyl group having 1 to 12 carbon atoms. R L1 , R L2 and R L3 A portion of the -CH2- of the hydrocarbyl group represented by may be substituted with -O- or -S-, and if the hydrocarbyl group includes an aromatic ring, some or all of the hydrogen atoms of the aromatic ring may be substituted with a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms that may include a halogen atom, or an alkoxy group having 1 to 4 carbon atoms that may include a halogen atom. R L1 , R L2 and R L3 The hydrocarbyl group having 1 to 12 carbon atoms, represented by, may be saturated or unsaturated, and may be straight, branched, or cyclic. As a specific example, R 1 , R 2 and R 3 Among the hydrocarbyl groups represented by , those having 1 to 12 carbon atoms can be cited. In addition, R L1 and R L2a. They may bond with each other to form a ring together with the carbon atom to which they bond, and some of the -CH2- groups of the ring may be substituted with -O- or -S-. However, R L3 In the case of this hydrogen atom, R L1 and R L2 They combine with each other to form a ring containing multiple bonds with the carbon atoms they bond to.

[0104] In formula (AL-2), R L4 and R L5 is, each independently, a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. R L4 and R L5 The hydrocarbyl group having 1 to 10 carbon atoms represented by may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include R 1 , R 2 and R 3 Among the hydrocarbyl groups represented by , those having 1 to 10 carbon atoms can be cited. R L6 Silver is a hydrocarbyl group having 1 to 20 carbon atoms, and a portion of the -CH2- of the said hydrocarbyl group may be substituted with -O- or -S-. In addition, R L5 and R L6 These, combining with each other, the carbon atoms and L that bond to them A It may form a complex cyclic group having 3 to 20 carbon atoms together with, and part of the -CH2- of the said complex cyclic group may be substituted with -O- or -S-. R L6 The hydrocarbyl group having 1 to 20 carbon atoms represented by may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include R 1 , R 2 and R 3 Examples of hydrocarbilic groups indicated as such can be cited as those exemplified.

[0105] In formula (AL-2), L A is -O- or -S-.

[0106] Specific examples of the acid instability group represented by formula (AL-1) include those shown below, but are not limited thereto. Additionally, in the following formulas, * indicates a bond loss with an adjacent -O-.

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129] Specific examples of the acid instability group represented by formula (AL-2) include those shown below, but are not limited thereto. Additionally, in the following formulas, * indicates a bond loss with an adjacent -O-.

[0130]

[0131]

[0132] In Equation (A), at least one -SF5 group is -OR AL1 , -OR AL2 or -OR AL3 It is bonded to a carbon atom adjacent to the carbon atom it is bonding to. -SF5 group and -OR AL1 , -OR AL2 or -OR AL3 By being bonded to adjacent carbon atoms, -R AL1 , -R AL2 or -R AL3 After this deprotection, the acidity of the phenols is improved, and the dissolution contrast is improved.

[0133] Also, S + Two of the three aromatic rings bonded to may bond with each other to form a ring together with the sulfur atom to which they bond. In this case, specific examples of the structure of the ring include those represented by the following formula.

[0134]

[0135] (In the formula, the dashed line is a connecting hand.)

[0136] As for the sulfonium salt represented by formula (A), it is preferable that it be represented by the following formula (A1).

[0137]

[0138] (among the food, n2 to n4, n6 to n8, n10 to n12, R AL1 to R AL3 and R1 to R 3 is the same as above. Z - (This will be discussed later.)

[0139] Specific examples of the cation of the sulfonium salt represented by formula (A) include those shown below, but are not limited to these. In addition, in the following formula, Me is a methyl group.

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[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]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

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[0289]

[0290]

[0291]

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[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

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[0309]

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[0311]

[0312]

[0313]

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[0315]

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[0325]

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[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

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[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

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[0370]

[0371]

[0372]

[0373]

[0374]

[0375]

[0376]

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[0380]

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[0384]

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[0441]

[0442]

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[0450]

[0451]

[0452]

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[0459]

[0460]

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[0470]

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[0473]

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[0475]

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[0478]

[0479]

[0480]

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[0482]

[0483]

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[0487]

[0488]

[0489]

[0490]

[0491]

[0492]

[0493]

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[0497]

[0498]

[0499]

[0500]

[0501]

[0502]

[0503] Among equations (A) and (A1), Z - is a fluoroalkanesulfonic acid anion having a polymerizable group. As for the fluoroalkanesulfonic acid anion, it is preferable to represent it by the following formula (Z1).

[0504]

[0505] In equation (Z1), k is 0, 1, 2, or 3, but 1 is preferred.

[0506] In equation (Z1), R A is, each independently, a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z 1 Each independently, a phenylene group, naphthylene group, or *-C(=O)-OZ that may have a single bond or a substituent 11 -is. Z 11 Silver is an aliphatic hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the aliphatic hydrocarbylene group may include a halogen atom, a hydroxyl group, an ether bond, an ester bond, or a lactone ring. Z 2 is a single bond, ether bond, ester bond, amide bond, sulfonic acid ester bond, sulfonamide bond, carbonate bond, or carbamate bond. Z 3Silver, each independently, single bond, ***-Z 31 -C(=O)-O-, ***-C(=O)-N(H)-Z 31 - or ***-OZ 31 -is. Z 31 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms. Z 4 is, each independently, single bond, ****-Z 41 -C(=O)-O-, ****-C(=O)-N(H)-Z 41 - or ****-OZ 41 -is. Z 41 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms. * indicates a loss of bonding with a carbon atom in the main chain. *** is Z 2 Indicates the bonding hand with. **** is Z 3 It represents the bonding hand with.

[0507] Z 11 The aliphatic hydrocarbylene group represented by may be linear, branched, or cyclic, and specific examples thereof include a methanediyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a propane-2,2-diyl group, a butane-1,1-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a 1,1-dimethylethane-1,2-diyl group, a pentane-1,5-diyl group, a 2-methylbutane-1,2-diyl group, and a hexane-1,6-diyl group; Examples include cycloalkanedyl groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanedyl; groups obtained by combining these.

[0508] Z 31 and Z 41The hydrocarbylene group, which may contain a heteroatom represented by, may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof are shown below, but are not limited to these.

[0509]

[0510] (In the formula, dashed lines indicate joint loss.)

[0511] In equation (Z1), L 1 The bonds are single bonds, ether bonds, ester bonds, carbonyl groups, sulfonic acid ester bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. Among these, from a synthetic perspective, ether bonds, ester bonds, and carbonyl groups are preferred, and ester bonds and carbonyl groups are more preferred.

[0512] In Equation (Z1), Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. Among these, Rf 1 and Rf 2 As such, in order to increase the acid strength of the generated acid, it is desirable that all of them be fluorine atoms.

[0513] In Equation (Z1), Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. Among these, for improved solvent solubility, Rf 3 and Rf 4 It is preferable that at least one of them is a trifluoromethyl group.

[0514] Z - As for the fluoroalkanesulfonic acid anion represented by, it is also preferable to represent it with the following formula (Z2).

[0515]

[0516] In formula (Z2), m1 is 0 or 1. When m1 is 0, it is a benzene ring, and when m1 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable that m1 is a benzene ring of 0. m2 is 0, 1, 2, 3, or 4. From the perspective of raw material procurement, it is preferable that m2 is 0, 1, 2, or 3, more preferable that it is 0, 1, or 2, and even more preferable that it is 0 or 1. m3 is 0, 1, 2, or 3.

[0517] In formula (Z2), m4 is 0 or 1. When m4 is 0, it is a benzene ring, and when m4 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable for m4 to be a benzene ring of 0. m5 is 0, 1, 2, 3, or 4. From the perspective of raw material procurement, it is preferable for m5 to be 0, 1, 2, or 3, and more preferable for m5 to be 0, 1, or 2. m6 is 0, 1, 2, or 3.

[0518] In formula (Z2), m7 is 0 or 1. When m7 is 0, it is a benzene ring, and when m7 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable for m7 to be a benzene ring of 0. m8 is 1, 2, 3, or 4. From the perspective of raw material procurement, it is preferable for m8 to be 1, 2, or 3, and more preferable for it to be 1 or 2. m9 is 0, 1, 2, or 3.

[0519] In formula (Z2), m10 is 0, 1, 2, 3, or 4, but is preferably 0, 1, 2, or 3, more preferably 1, 2, or 3, and even more preferably 1. m11 is 0 or 1. m12 is 0 or 1.

[0520] When m1 is 0, 0≤m2+m3+m12≤4, and when m1 is 1, 0≤m2+m3+m12≤6. Also, when m4 is 0, 0≤m5+m6≤4, and when m4 is 1, 0≤m5+m6≤6. Also, when m7 is 0, 0≤m8+m9≤5, and when m7 is 1, 0≤m8+m9≤7. Furthermore, regarding the number of iodine atoms in the anion, as the number of iodine atoms increases, absorption, particularly for EUV, increases, but solvent solubility becomes insufficient, and there is a risk of precipitation in the resist composition, so it is preferable that 1≤m2+m5+m8≤4.

[0521] In equation (Z2), R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R A As for, it is preferable that it be a hydrogen atom or a methyl group, and more preferable that it be a hydrogen atom.

[0522] In equation (Z2), R 11The above is silver, a halogen atom other than an iodine atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. As for the halogen atom other than the iodine atom, it is preferable that it be a fluorine atom, a chlorine atom, or a bromine atom, and more preferable that it be a fluorine atom. The hydrocarbyl portion of the above hydrocarbyl group, and the hydrocarbyloxy group, hydrocarbylthio group, and hydrocarbyloxycarbonyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include: an alkyl group having 1 to 20 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 n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, etc.; a cyclic saturated hydrocarbyl group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, an adamantyl group, etc. Examples include alkenyl groups having 2 to 20 carbon atoms, such as vinyl groups, 1-propenyl groups, 2-propenyl groups, butenyl groups, and hexenyl groups; cyclic unsaturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclohexenyl groups; aryl groups having 6 to 20 carbon atoms, such as phenyl groups and naphthyl groups; aralkyl groups having 7 to 20 carbon atoms, such as benzyl groups, 1-phenylethyl groups, and 2-phenylethyl groups; and groups obtained by combining these.In addition, some or all of the hydrogen atoms of the above 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 above 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 cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, 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. When m3 is 2 or 3, each R. 11 They may be the same or different.

[0523] Also, when m3 is 2 or 3, 2 R 11 These may combine with each other to form a ring together with the carbon atom to which they are bonded. Specific examples of the ring formed at this time include a cyclopropane ring, a cyclobutane ring, a cyclophenane ring, a cyclohexane ring, a norbornane ring, an adamantane ring, etc. In addition, some or all of the hydrogen atoms in the ring may be substituted with a group containing heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and some of the -CH2- in the ring may be substituted with a group containing heteroatoms such as an oxygen atom, a sulfur atom, or 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 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.

[0524] In equation (Z2), R 12...is a halogen atom other than an iodine atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. Specific examples of the halogen atom other than the iodine atom include a fluorine atom, a chlorine atom, a bromine atom, etc. The hydrocarbyl portion of the hydrocarbyl group, and the hydrocarbyl group of the hydrocarbyloxyoxy group, hydrocarbylthio group, and hydrocarbyloxycarbonyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include R 11 Examples of hydrocarbyl groups represented by may be given, but are not limited to 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 cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, 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. When m6 is 2 or 3, each R 12 They may be the same or different.

[0525] Also, when m6 is 2 or 3, 2 R 12 a. They may combine with each other to form a ring together with the carbon atom to which they are bonded. As for the ring, a 5 to 8-membered ring is preferred.

[0526] In equation (Z2), R 13 It is silver, a halogen atom other than an iodine atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. Specific examples of the halogen atom other than the iodine atom include a fluorine atom, a chlorine atom, a bromine atom, etc. The hydrocarbyl portion of the hydrocarbyl group, and the hydrocarbyl group of the hydrocarbyloxy group, hydrocarbylthio group, and hydrocarbyloxycarbonyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include R 11 Examples of hydrocarbyl groups represented by may include those similar to those exemplified, but are not limited to these. 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 cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, 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. When m9 is 2 or 3, each R 13 They may be the same or different.

[0527] Also, when m9 is 2 or 3, 2 R 13These may combine with each other to form a ring together with the carbon atom to which they are bonded. As for the ring, a 5 to 8-membered ring is preferred.

[0528] In equation (Z2), L A , L B , L C , L D and L E Each is independently a single bond, an ether bond, an ester bond, a sulfonic acid ester bond, an amide bond, a sulfonate amide bond, a carbonate bond, or a carbamate bond. Among these, L A As such, it is preferable that it be a single bond, an ether bond, an ester bond, or a sulfonic acid ester bond, and more preferable that it be an ether bond, an ester bond, or a sulfonic acid ester bond. L B As such, it is preferable that it be a single bond, an ether bond, an ester bond, an amide bond, a sulfonate amide bond, or a sulfonic acid ester bond, and more preferable that it be an ester bond or a sulfonic acid ester bond. L C As such, it is preferable that it be a single bond, an ether bond, an ester bond, an amide bond, or a sulfonic acid ester bond, and more preferable that it be a single bond, an ether bond, or an ester bond. L D As such, it is preferable that it be a single bond, an ether bond, an ester bond, an amide bond, or a sulfonic acid ester bond, and more preferable that it be a single bond, an ether bond, or an ester bond. L E As such, it is preferable that it be a single bond, an ether bond, an ester bond, or a sulfonic acid ester bond, and more preferable that it be a single bond, an ether bond, or an ester bond.

[0529] When m12 is 1, L A and L BIt is preferable that the fluorosulfonic acid anion structure be bonded to an adjacent carbon atom of the aromatic ring. In this case, since the substituent comprising the fluorosulfonic acid anion structure and the substituent comprising the aromatic ring substituted with an iodine atom are located in spatially closer positions, it is expected that the sensitivity will be higher.

[0530] In equation (Z2), X L1 and X L2 Each is a hydrocarbylene group having 1 to 40 carbon atoms, which may independently contain a single bond or a heteroatom. The hydrocarbylene group may be straight, branched, or cyclic, and specific examples thereof include an alkanedyl group, a cyclic saturated hydrocarbylene group, an arylene group, etc. Specific examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0531] X L1 and X L2 Specific examples of hydrocarbylene groups having 1 to 40 carbon atoms that may include a heteroatom represented by are shown below, but are not limited thereto. In addition, in the following formulas, * represents L A and L C , or L B and L D It is a combined hand with.

[0532]

[0533]

[0534]

[0535]

[0536] Among these, X L -0 to X L -22, X L -29 to X L -34 and X L -47 to X L -61 is desirable.

[0537] However, in Equation (Z2), there is no case where m11 and m12 become 0 simultaneously, and L A , L B , L C , L D , X L1 and X L2 There is no case where a single bond is formed at the same time.

[0538] In equation (Z2), Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. As for the fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms, a trifluoromethyl group is preferred. Rf 1 and Rf 2 As for that, it is more preferable that it be a fluorine atom.

[0539] In equation (Z2), Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. As for the fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms, a trifluoromethyl group is preferred.

[0540] In Equation (Z2), -[C(Rf 3 )(Rf 4 )] m10 -C(Rf 1 )(Rf 2 )-SO3 - Specific examples of the substructure represented by are preferably shown below, but are not limited thereto. In addition, in the following formulas, * is L E It represents the bonding loss with.

[0541]

[0542] Among these, acids 1 to 7 are preferred, and acids 1 to 3, acid 6, and acid 7 are more preferred.

[0543] Z -Specific examples of the anion represented by are those shown below, but are not limited thereto. In addition, among the following formulas, R A and Rf 4 is the same as above, and Me is a methyl group. In addition, the bonding positions of various substituents on the aromatic ring may be interchanged.

[0544]

[0545]

[0546]

[0547]

[0548]

[0549]

[0550]

[0551]

[0552]

[0553]

[0554]

[0555]

[0556]

[0557]

[0558]

[0559]

[0560]

[0561]

[0562]

[0563]

[0564]

[0565]

[0566]

[0567]

[0568]

[0569]

[0570]

[0571]

[0572]

[0573]

[0574]

[0575]

[0576]

[0577]

[0578]

[0579]

[0580]

[0581]

[0582]

[0583]

[0584]

[0585]

[0586]

[0587]

[0588]

[0589]

[0590]

[0591]

[0592]

[0593]

[0594]

[0595]

[0596]

[0597]

[0598]

[0599]

[0600]

[0601]

[0602]

[0603]

[0604]

[0605]

[0606]

[0607]

[0608]

[0609]

[0610]

[0611]

[0612]

[0613]

[0614]

[0615]

[0616]

[0617]

[0618]

[0619]

[0620]

[0621]

[0622]

[0623]

[0624]

[0625]

[0626]

[0627]

[0628]

[0629]

[0630]

[0631]

[0632]

[0633]

[0634]

[0635]

[0636]

[0637]

[0638]

[0639]

[0640]

[0641]

[0642]

[0643]

[0644]

[0645]

[0646]

[0647]

[0648]

[0649]

[0650]

[0651]

[0652]

[0653]

[0654]

[0655]

[0656]

[0657]

[0658]

[0659]

[0660]

[0661]

[0662]

[0663]

[0664]

[0665]

[0666]

[0667]

[0668]

[0669]

[0670]

[0671]

[0672]

[0673]

[0674]

[0675]

[0676]

[0677]

[0678]

[0679]

[0680]

[0681]

[0682]

[0683]

[0684]

[0685] Z -Other specific examples of anions represented by

[0043] to

[0044] of International Publication No. 2024 / 176672, paragraphs

[0067] to

[0070] of International Publication No. 2024 / 176701, paragraphs

[0057] to

[0058] of International Publication No. 2024 / 190386, paragraphs

[0020] to

[0023] of Japanese Patent Publication No. 2024-103465, paragraphs

[0067] to

[0070] of Japanese Patent Publication No. 2024-120703, and paragraphs

[0075] to

[0084] of Japanese Patent No. 7520258.

[0686] Specific examples of the sulfonium salt-type monomer of the present invention include any combination of the aforementioned anion and cation.

[0687] The sulfonium salt-type monomer of the present invention can be synthesized by known methods. For example, it can be converted into a target sulfonium salt by performing a salt exchange reaction using the salt having the sulfonium cation and the salt having the anion synthesized by known methods. Salt exchange with the corresponding anion can be easily performed by known methods, and for example, Japanese Patent Publication No. 2007-145797 may be referenced. Furthermore, the above manufacturing method is merely an example, and the method for manufacturing the sulfonium salt of the present invention is not limited thereto.

[0688] Structural features of the sulfonium salt-type monomer of the present invention include a fluorosulfonic acid anion structure having a polymerizable group, and an acid instability group having a pentafluorosulfanyl group and a tertiary / secondary ether structure, a tertiary / secondary carbonate structure, or an acetal structure bonded to the aromatic ring of the sulfonium cation. Since the anion of the sulfonium salt-type monomer of the present invention has a polymerizable group, the polymer of the present invention obtained using it becomes an anion-bound acid-generating agent in which the anion side is bonded to the polymer main chain. That is, since acid is generated bonded to the polymer main chain, the diffusion of the generated acid can be suppressed. Furthermore, polymerizable groups including structures such as styrene or vinylnaphthalene are particularly preferred because they have greater rigidity than polymerizable groups such as methacrylic acid esters, and the glass transition temperature (Tg) of the polymer is improved. It is thought that through the interaction of aromatic rings within or between polymers (π-π stacking effect), the polymers are regularly arranged, and resistance to pattern collapse against the developer is exhibited even during the formation of fine patterns. Furthermore, excellent etching resistance is exhibited during the etching process after the formation of fine patterns by having aromatic rings directly linked to the main chain. Additionally, it is desirable to have iodine atoms among the anions. Regarding iodine atoms, particularly in EUV lithography at a wavelength of 13.5 nm, secondary electrons are generated from iodine atoms during exposure because the absorption of EUV by iodine atoms is very large. Meanwhile, the pentafluorosulfanyl group bonded to the aromatic ring of the sulfonium cation is known as a strong electron-withdrawing group. From this, it is thought that the energy level of the LUMO in frontier orbital theory is lowered. Therefore, it becomes easier to receive secondary electrons generated from iodine atoms in the anion, which promotes the decomposition of cations and efficiently generates acid.Acid instability groups having a tertiary / secondary ether structure, a tertiary / secondary carbonate structure, or an acetal structure substituted on the aromatic ring of a sulfonium cation undergo a deprotection reaction by acid generated by exposure to light, and produce corresponding phenols. As the structure changes from lipophilic to hydrophilic, the contrast between the exposed and unexposed areas is improved. In addition, a pentafluorosulfanyl group is bonded to a carbon atom adjacent to the carbon atom to which the generated phenolic hydroxyl group is bonded, and the acidity of the phenols is enhanced by the electron-withdrawing properties of the pentafluorosulfanyl group. When the exposed area where the deprotection reaction has taken place is developed with an alkaline developer, the phenols with enhanced acidity have improved solubility in the alkaline developer, thereby suppressing development residues. Furthermore, by suppressing swelling caused by the alkaline developer, the destruction of the resist pattern can be suppressed. Due to these synergistic effects, sensitivity is increased, and the degradation of resolution caused by acid diffusion blurring can be prevented, thereby making it possible to improve the lithography performance of LWR, CDU, etc. Therefore, the polymer of the present invention is particularly suitable as a material for a chemically amplified positive type resist composition.

[0689] [Polymer]

[0690] The polymer of the present invention comprises a repeating unit (hereinafter also referred to as repeating unit A) derived from a sulfonium salt-type monomer represented by formula (A).

[0691] The above polymer may include a repeating unit represented by the following formula (a1) (hereinafter also referred to as repeating unit a1) or a repeating unit represented by the following formula (a2) (hereinafter also referred to as repeating unit a2).

[0692]

[0693] Among equations (a1) and (a2), R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0694] In equation (a1), X 1 Silver, single bond, phenylene group, naphthylene group, *-C(=O)-OX 11 - or *-C(=O)-N(H)-X 11 - and, the corresponding phenylene group or naphthylene group may be substituted with a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbyl group having 1 to 10 carbon atoms that may include a fluorine atom, a saturated hydrocarbyloxy group having 1 to 10 carbon atoms that may include a fluorine atom, or a halogen atom. X 11 It is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may include a hydroxyl group, an ether bond, an ester bond, or a lactone ring. * indicates a bond loss with a carbon atom of the main chain.

[0695] In equation (a2), X 2 is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-. * indicates a bond loss with a carbon atom in the main chain. R 21 It is silver, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a pentafluorosulfanyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. a1 is 0, 1, 2, 3, or 4, and preferably 0 or 1. When a1 is 2, 3, or 4, each R 21 They may be the same or different.

[0696] Among equations (a1) and (a2), AL 1 and AL 2Each is an acid instability group independently. Specific examples of the above acid instability groups include those described in Japanese Patent Publication No. 2013-80033 or Japanese Patent Publication No. 2013-83821.

[0697] Typically, specific examples of the above acid instability group include those represented by the following formulas (AL-3) to (AL-5).

[0698]

[0699] (In the food, * is a connecting hand.)

[0700] Among equations (AL-3) and (AL-4), R L11 and R L12 Each is independently a hydrocarbyl group having 1 to 40 carbon atoms and may contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. As for the hydrocarbyl group, it is preferable that it has 1 to 20 carbon atoms.

[0701] In formula (AL-3), a2 is an integer from 0 to 10, and 1, 2, 3, 4, or 5 is preferred.

[0702] In formula (AL-4), R L13 and R L14 Each is independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and may contain heteroatoms such as oxygen, sulfur, nitrogen, or fluorine atoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. In addition, R L12 , R L13 and R L14Any two of them may combine with each other to form a ring having 3 to 20 carbon atoms together with the carbon atom or the carbon atom and oxygen atom to which they are bonded. As for the ring, a ring having 4 to 16 carbon atoms is preferred, and a ring is particularly preferred.

[0703] In formula (AL-5), R L15 , R L16 and R L17 Each is independently a hydrocarbyl group having 1 to 20 carbon atoms, and may contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. In addition, R L15 , R L16 and R L17 Any two of them may combine with each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. As for the ring, a ring having 4 to 16 carbon atoms is preferred, and a ring is particularly preferred.

[0704] Other specific examples of the above acid instability group include those described in paragraphs

[0064] to

[0068] of Japanese Patent Publication No. 2023-123222 and those described in paragraphs

[0013] to

[0014] of Japanese Patent Publication No. 7492842. These utilize the generation of conjugated olefins or acrylic acid ester derivatives after the acid deliquency reaction as the driving force for the reaction process.

[0705] Specific examples of the repeating unit a1 are those shown below, but are not limited thereto. In addition, among the following formulas, R A and AL 1 It is the same as above.

[0706]

[0707]

[0708]

[0709]

[0710]

[0711] Specific examples of the repeating unit a2 are those shown below, but are not limited thereto. In addition, among the following formulas, R A and AL 2 It is the same as above.

[0712]

[0713]

[0714]

[0715] The above polymer may include a repeating unit represented by the following formula (a3) ​​(hereinafter also referred to as repeating unit a3).

[0716]

[0717] In formula (a3), b1 is 0 or 1. When b1 is 0, it is a benzene ring, and when b1 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable that b1 is a benzene ring of 0. b2 is 0, 1, 2, or 3 when b1 is 0, and 0, 1, 2, 3, 4, or 5 when b1 is 1. From the perspective of raw material procurement, it is preferable that b2 is 0, 1, 2, or 3, and more preferable that it is 0, 1, or 2.

[0718] In equation (a3), R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R A As for, it is preferable that it be a hydrogen atom or a methyl group, and more preferable that it be a hydrogen atom.

[0719] In equation (a3), X 3The bond is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-. * indicates a bond with a carbon atom in the main chain. Among these, a single bond, *-C(=O)-O- is preferred, and a single bond is more preferred.

[0720] In equation (a3), X 4 The group is a single bond, an aliphatic hydrocarbylene group having 1 to 4 carbon atoms, a carbonyl group, a sulfonyl group, or a combination thereof. Among these, from the perspective of raw material procurement, it is preferable that it be a single bond, a carbonyl group, or a sulfonyl group, and from the perspective of the polar group generated after the reaction, it is more preferable that it be a single bond or a carbonyl group.

[0721] In equation (a3), X 5 and X 6 Each is independently an oxygen atom or a sulfur atom. However, X 4 and X 6 It is bonded to an adjacent carbon atom of the aromatic ring. X 5 and X 6 They may be identical or different, but in terms of reactivity, X 5 and X 6 It is desirable that all of them be oxygen atoms.

[0722] In equation (a3), R 22 and R 23Each 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 linear, branched, or cyclic. Specific examples include alkyl groups having 1 to 20 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group; Examples include cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, cyclopropylmethyl groups, 4-methylcyclohexyl groups, cyclohexylmethyl groups, norbornyl groups, adamantyl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl groups, 1-propenyl groups, 2-propenyl groups, butenyl groups, and hexenyl groups; cyclic unsaturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclohexenyl groups; aryl groups having 6 to 20 carbon atoms, such as phenyl groups and naphthyl groups; aralkyl groups having 7 to 20 carbon atoms, such as benzyl groups, 1-phenylethyl groups, and 2-phenylethyl 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 cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, 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.

[0723] Also, R 22 and R 23The atoms may combine with each other to form a ring together with the carbon atoms to which they are bonded. Specific examples of the ring formed at this time include a cyclopropane ring, a cyclobutane ring, a cyclophenane ring, a cyclohexane ring, a norbornane ring, an adamantane ring, etc. In addition, some or all of the hydrogen atoms in the ring may be substituted with a group containing heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and some of the -CH2- in the ring may be substituted with a group containing heteroatoms such as an oxygen atom, a sulfur atom, or 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 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.

[0724] In equation (a3), R 24 ...is a halogen atom, a hydroxyl group, a cyano group, a nitro group, a pentafluorosulfanyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom, or -N(R 24A )(R 24B ) is. R 24A and R 24BEach is independently a hydrogen atom or a hydrocarbyl group having 1 to 6 carbon atoms. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom or an iodine atom. The hydrocarbyl portion of the hydrocarbyl group, and the hydrocarbyl portion of the hydrocarbyloxy group, hydrocarbyloxycarbonyl group, and hydrocarbylthio group, may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include R 22 and R 23 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 cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, 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. When b2 is 2 or more, each R 24 They may be the same or different.

[0725] Also, when b2 is 2 or greater, multiple R 24a. They may combine with each other to form a ring together with the carbon atom of the aromatic ring to which they are combined. Specific examples of the ring formed at this time include a cyclopropane ring, a cyclobutane ring, a cyclophenane ring, a cyclohexane ring, a norbornane ring, an adamantane ring, etc. In addition, some or all of the hydrogen atoms in the ring may be substituted with a group containing heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and some of the -CH2- in the ring may be substituted with a group containing heteroatoms such as an oxygen atom, a sulfur atom, or 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 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.

[0726] Specific examples of the repeating unit a3 are those shown below, but are not limited thereto. In addition, among the following formulas, R A is the same as above, and Me is a methyl group. In addition, the bonding positions of various substituents on the aromatic ring may be interchanged.

[0727]

[0728]

[0729]

[0730]

[0731]

[0732]

[0733]

[0734]

[0735]

[0736]

[0737]

[0738]

[0739]

[0740]

[0741]

[0742]

[0743]

[0744]

[0745]

[0746]

[0747]

[0748]

[0749]

[0750]

[0751]

[0752]

[0753]

[0754]

[0755]

[0756]

[0757]

[0758]

[0759]

[0760]

[0761]

[0762]

[0763]

[0764]

[0765]

[0766]

[0767]

[0768]

[0769]

[0770]

[0771]

[0772]

[0773]

[0774]

[0775]

[0776]

[0777] The above base polymer may include a repeating unit represented by the following formula (b1) (hereinafter also referred to as repeating unit b1) or a repeating unit represented by the following formula (b2) (hereinafter also referred to as repeating unit b2).

[0778]

[0779] Among equations (b1) and (b2), R A Each is, independently, a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Y 1 It is a single bond or *-C(=O)-O-. * indicates a bond loss with a carbon atom in the main chain. R 31It is a group having 1 to 20 carbon atoms comprising at least one structure selected from silver, hydrogen atoms, or hydroxyl groups other than phenolic hydroxyl groups, cyano groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, lactone rings, sulfone rings, and carboxylic acid anhydrides (-C(=O)-OC(=O)-). 32 is a halogen atom, a carboxyl group, a nitro group, a cyano group, a pentafluorosulfanyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. When c2 is 2, 3, or 4, each R 32 c1 and c2 may be the same or different. c1 is 1, 2, 3, or 4. c2 is 0, 1, 2, 3, or 4. Provided that 1 ≤ c1 + c2 ≤ 5.

[0780] Specific examples of the repeating unit b1 are those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0781]

[0782]

[0783]

[0784]

[0785]

[0786]

[0787]

[0788]

[0789]

[0790]

[0791]

[0792]

[0793]

[0794]

[0795]

[0796]

[0797] Specific examples of the repeating unit b2 are those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0798]

[0799]

[0800]

[0801]

[0802]

[0803] As for the repeating unit b1 or b2, in ArF lithography, it is particularly desirable to have a lactone ring as a polar group, and in KrF lithography, EB lithography and EUV lithography, it is desirable to have a phenol group.

[0804] The above polymer may include a repeating unit (hereinafter also referred to as repeating unit c) having a structure in which a hydroxyl group is protected by an acid unstable group. As for the repeating unit c, it is not particularly limited as long as it has one or more structures in which a hydroxyl group is protected and the protecting group is decomposed by the action of an acid to form a hydroxyl group, but it is preferred to be represented by the following formula (c1).

[0805]

[0806] In equation (c1), R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 41 It is a (d+1) valence hydrocarbon group having 1 to 30 carbon atoms that may contain heteroatoms. R 42 is the acid instability phase. d is 1, 2, 3, or 4.

[0807] In equation (c1), R 42 The acid instability group denoted by must be one that deprotects upon the action of the acid and generates a hydroxyl group. R 42 The structure is not particularly limited, but an acetal structure, a ketal structure, a hydrocarbyloxycarbonyl group, a hydrocarbyloxymethyl group represented by the following formula (c2) are preferred, and in particular, a hydrocarbyloxymethyl group represented by the following formula (c2) is preferred.

[0808]

[0809] (In the formula, * indicates a bond. R 43 It is a hydrocarbyl group having 1 to 15 carbon atoms.)

[0810] R 42 Specific examples of the acid instability group represented by (c2), the hydrocarbyloxymethyl group represented by formula (c2), and the repeating unit c include those exemplified in the description of the repeating unit c in Japanese Patent Publication No. 2020-111564.

[0811] The above 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 to these.

[0812]

[0813] The above polymer may include repeating unit e derived from indan, vinylpyridine, or vinylcarbazole.

[0814] In the polymer of the present invention, the content ratio of repeating units A, a1, a2, a3, b1, b2, c, d, and e is preferably 0 <A≤0.4, 0≤a1≤0.8, 0≤a2≤0.8, 0≤a3≤0.6, 0<a1+a2+a3≤0.8, 0≤b1≤0.6, 0≤b2≤0.6, 0≤c≤0.5, 0≤d≤0.3 및 0≤e≤0.3이고, 보다 바람직하게는 0<A≤0.3, 0≤a1≤0.7, 0≤a2≤0.7, 0≤a3≤0.5, 0<a1+a2+a3≤0.7, 0≤b1≤0.5, 0≤b2≤0.5, 0≤c≤0.3, 0≤d≤0.3 및 0≤e≤0.3이다. 단, A+a1+a2+a3+b1+b2+c+d+e≤1.0이다.

[0815] The weight average molecular weight (Mw) of the above polymer is preferably 1,000 to 500,000, and more preferably 3,000 to 100,000. When Mw is in this range, sufficient etching resistance is obtained, and there is no concern about a decrease in resolution due to the inability to secure a difference in dissolution rate before and after exposure. In addition, in the present invention, Mw is a polystyrene equivalent measurement value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as a solvent.

[0816] Since the molecular weight distribution (Mw / Mn) of the above polymer tends to have a greater influence as the pattern rule becomes finer, in order to obtain a resist composition suitable for use with fine pattern dimensions, it is preferable that the Mw / Mn be narrowly dispersed to 1.0 to 2.0. If it is within the above range, there is less low molecular weight or high molecular weight polymer, so there is no risk of foreign matter being visible on the pattern or the shape of the pattern deteriorating after exposure.

[0817] As a method for synthesizing the above polymer, for example, a method may be used in which a monomer imparting the aforementioned repeating unit is heated in an organic solvent with the addition of a radical polymerization initiator and polymerized.

[0818] Specific examples of organic solvents used during polymerization include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), etc. Specific examples of the polymerization initiator include 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, lauroyl peroxide, etc. The amount of these initiators added is preferably 0.01 to 25 mol% with respect to the total amount of monomers to be polymerized. The reaction temperature is preferably 50 to 150°C, and more preferably 60 to 100°C. The reaction time is preferably 2 to 24 hours, and more preferably 2 to 12 hours from the perspective of production efficiency.

[0819] The polymerization initiator may be added to the monomer solution and supplied to the reactor, or the initiator solution may be prepared separately from the monomer solution and supplied to the reactor independently. From the perspective of quality control, it is preferable to prepare and dropwise add the monomer solution and the initiator solution independently, as there is a possibility that the polymerization reaction may proceed due to radicals generated from the initiator during the waiting time, thereby forming the superpolymer itself. The acid unstable group may be used as is upon introduction into the monomer, or it may be protected or partially protected after polymerization. Additionally, known chain transfer agents such as dodecyl mercaptan or 2-mercaptoethanol may be used in combination to adjust the molecular weight. In this case, the amount of these chain transfer agents added is preferably 0.01 to 20 mol% relative to the total amount of monomers to be polymerized.

[0820] In the case of 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.

[0821] When copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, hydroxystyrene or hydroxyvinylnaphthalene and other monomers may be heated polymerized in an organic solvent with the addition of a radical polymerization initiator, but acetoxystyrene or acetoxyvinylnaphthalene may be used to deprotect the acetoxy groups by alkali hydrolysis after polymerization to obtain polyhydroxystyrene or hydroxypolyvinylnaphthalene.

[0822] Specific examples of the base during alkaline hydrolysis include water ammonia, triethylamine, etc. 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.

[0823] In addition, the amount of each monomer in the above monomer solution can be appropriately set, for example, to a desirable content ratio of the repeating unit described above.

[0824] The polymer obtained by the above manufacturing method may be treated as a final product by the reaction solution obtained by the polymerization reaction, or as a final product by the powder obtained through a purification process such as a reprecipitation method in which the polymer solution is added to a solvent and a powder is obtained. However, from the perspective of work efficiency and quality stabilization, it is preferable to treat the polymer solution obtained by the purification process, dissolved in a solvent, as a final product.

[0825] Specific examples of solvents used at that time include ketones such as cyclohexanone and methyl-2-n-pentyl ketone, 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, and 1-ethoxy-2-propanol; and ethers such as propylene glycol monomethyl ether (PGME), 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 PGMEA, 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; lactones such as GBL; alcohols such as diacetone alcohol (DAA); high-boiling point alcohol-based solvents such as diethylene glycol, propylene glycol, glycerin, 1,4-butanediol, and 1,3-butanediol; and mixed solvents thereof.

[0826] Among the above polymer solution, the concentration of the polymer is preferably 0.01 to 30 mass%, and more preferably 0.1 to 20 mass%.

[0827] It is preferable to filter the above reaction solution or polymer solution. By filtering, foreign substances or gels that may cause defects can be removed, which is effective in terms of quality stabilization.

[0828] The material of the filter used for the above filter filtration may be a fluorocarbon-based, cellulose-based, nylon-based, polyester-based, or hydrocarbon-based material; however, for the filtration process of the resist composition, a filter formed from a fluorocarbon-based material called so-called Teflon (registered trademark), a hydrocarbon-based material such as polyethylene or polypropylene, or nylon is preferred. The pore diameter of the filter can be appropriately selected to match the target cleanliness, but is preferably 100 nm or less, and more preferably 20 nm or less. In addition, these filters may be used individually or in combination with multiple filters. The filtration method may involve passing the solution only once, but it is more preferable to circulate the solution and perform filtration multiple times. The filtration process may be performed in any sequence or number of times during the polymer manufacturing process, but it is preferable to filter the reaction solution after the polymerization reaction, the polymer solution, or both.

[0829] [Chemical Amplification Resist Composition]

[0830] [(A) Base Polymer]

[0831] The chemical amplification resist composition of the present invention comprises, as component (A), a base polymer comprising the aforementioned polymer.

[0832] The above polymer may be used as a single type, or two or more types with different composition ratios, Mw and / or Mw / Mn may be used in combination. In addition, (A) the base polymer may include, in addition to the above polymer, a hydrogenated ring-opening metathesis polymer, and regarding this, the one described in Japanese Patent Publication No. 2003-66612 may be used.

[0833] [(B) Organic solvents]

[0834] The chemical amplification resist composition of the present invention may include an organic solvent as component (B). The organic solvent (B) 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 such organic solvents include ketones such as cyclopentanone, cyclohexanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; keto alcohols such as DAA; and ethers such as PGME, 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 PGMEA, 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; lactones such as GBL; and mixed solvents of these.

[0835] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, ethyl lactate, DAA, and mixtures thereof are preferred, as they have particularly excellent solubility of the base polymer of component (A).

[0836] In the chemical amplification resist composition of the present invention, the content of (B) organic solvent is preferably 200 to 7000 parts by mass and more preferably 400 to 5000 parts by mass with respect to 80 parts by mass of (A) base polymer. (B) organic solvent may be used as a single type or as a mixture of two or more types.

[0837] [(C) Quencher]

[0838] The chemical amplification resist composition of the present invention may include a quencher as component (C). Furthermore, in the present invention, a quencher is a material for preventing diffusion to unexposed areas and forming a desired pattern by trapping a strong acid generated from a photoacid generator in the chemical amplification resist composition. Furthermore, a strong acid refers to an acid having sufficient acidity to cause a deprotection reaction of an acid unstable group.

[0839] (C) Specific examples of quenchers include onium salts represented by the following formulas (1) or (2).

[0840]

[0841] In Equation (1), R q1 It is a hydrocarbyl group having 1 to 40 carbon atoms that may contain silver, hydrogen atoms, or heteroatoms, except that the hydrogen atom bonded to the carbon atom at the α-position of the sulfo group is substituted with a fluorine atom or a fluoroalkyl group. In Formula (2), R q2 It is a hydrocarbyl group having 1 to 40 carbon atoms that may include hydrogen atoms or heteroatoms.

[0842] R q1 A hydrocarbyl group having 1 to 40 carbon atoms represented by, specifically, an alkyl group having 1 to 40 carbon atoms such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, tert-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group; a cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, norbornyl group, tricyclo[5.2.1.0 2,6Examples include cyclic saturated hydrocarbyl groups having 3 to 40 carbon atoms, such as decyl groups and adamantyl groups; and aryl groups having 6 to 40 carbon atoms, such as phenyl groups, naphthyl groups, and anthracenyl groups. Additionally, 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, and 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, and nitrogen atoms, and as a result, may include hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, lactone rings, sulfone rings, carboxylic acid anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0843] R q2 As a hydrocarbyl group represented by, specifically, R q1 In addition to the substituents exemplified as specific examples, fluorinated saturated hydrocarbyl groups such as trifluoromethyl groups and trifluoroethyl groups, or fluorinated aryl groups such as pentafluorophenyl groups and 4-trifluoromethylphenyl groups may also be cited.

[0844] Specific examples of the anion of the onium salt represented by formula (1) include those shown below, but are not limited to these.

[0845]

[0846]

[0847]

[0848]

[0849]

[0850] Specific examples of the anion of the onium salt represented by formula (2) include those shown below, but are not limited to these.

[0851]

[0852]

[0853]

[0854]

[0855]

[0856] Among equations (1) and (2), Mq + is an onium cation. Examples of the above onium cation include sulfonium cations, iodonium cations, ammonium cations, etc. Specific examples of the above sulfonium cation include those exemplified as specific examples of cations of sulfonium salt-type monomers represented by formula (A), those described in paragraphs

[0102] to

[0125] of Japanese Patent Publication No. 2024-3744, those described in paragraphs

[0044] to

[0049] of International Publication No. 2024 / 128017, and those described in paragraphs

[0035] to

[0046] of Patent Publication No. 7491173, but are not limited to these.

[0857] In addition, as the above sulfonium cation, a sulfonium cation represented by the following formula (sulfo-1) is also preferred.

[0858]

[0859] In formula (sulfo-1), e1 is 0 or 1. When e1 is 0, it is a benzene ring, and when e1 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable that e1 be a benzene ring with 0. e2 is 0 or 1. When e2 is 0, it is a benzene ring, and when e2 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable that e2 be a benzene ring with 0. e3 is 0 or 1. When e3 is 0, it is a benzene ring, and when e3 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable that e3 be a benzene ring with 0.

[0860] In formula (sulfo-1), e4 is 0, 1, 2, 3, or 4. As the number of iodine atoms in the cation structure increases, absorption of EUV, in particular, increases, but solvent solubility becomes insufficient, and there is a risk of precipitation in the resist composition; therefore, it is preferable that e4 be 0, 1, 2, or 3, and more preferable that it be 0, 1, or 2.

[0861] In formula (sulfo-1), e5 is 0, 1, 2, 3, or 4. From the perspective of raw material procurement, e5 is preferably 0, 1, 2, or 3, and more preferably 0, 1, or 2. e6 is 0, 1, 2, 3, 4, 5, or 6. From the perspective of raw material procurement, e6 is preferably 0, 1, 2, or 3, and more preferably 0, 1, or 2. e7 is 0, 1, 2, 3, 4, 5, or 6. From the perspective of raw material procurement, e7 is preferably 0, 1, 2, or 3, and more preferably 0, 1, or 2.

[0862] In formula (sulfo-1), e8 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable that e8 be 0 or 1. e9 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable that e9 be 0 or 1. e10 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable that e10 be 0 or 1.

[0863] In formula (sulfo-1), e11 is 0 or 1. When e11 is 0, it is a benzene ring, and when e11 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable for e11 to be a benzene ring of 0.

[0864] In formula (sulfo-1), e12 is 0, 1, 2, 3, or 4. As the number of iodine atoms in the cation structure increases, absorption of EUV, in particular, increases, but solvent solubility becomes insufficient, and there is a risk of precipitation in the resist composition; therefore, it is preferable that e12 be 0, 1, 2, or 3, and more preferable that it be 0, 1, or 2.

[0865] In formula (sulfo-1), e13 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable that e13 is 0 or 1. e14 is 0, 1, or 2. From the perspective of synthesis, it is preferable that e14 is 0 or 1.

[0866] However, when e1 is 0, 0 ≤ e6 + e9 ≤ 4, and when e1 is 1, 0 ≤ e6 + e9 ≤ 6. When e2 is 0, 0 ≤ e7 + e10 ≤ 4, and when e2 is 1, 0 ≤ e7 + e10 ≤ 6. When e3 is 0, 1 ≤ e4 + e5 + e8 + e14 ≤ 4, and when e3 is 1, 1 ≤ e4 + e5 + e8 + e14 ≤ 6. When e11 is 0, 0 ≤ e12 + e13 ≤ 4, and when e11 is 1, 0 ≤ e12 + e13 ≤ 6. Also, e4 + e12 ≥ 1.

[0867] Among formulas (sulfo-1), R F1 to R F3 Each is independently a fluorine atom, a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbyloxy group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbylthio group having 1 to 6 carbon atoms. Among these, it is preferred that it is a trifluoromethyl group, a trifluoromethoxy group, or a trifluorothiomethoxy group. When e5 is 2, 3, or 4, each R F1 may be the same or different. When e6 is 2, 3, 4, 5, or 6, each R F2 may be the same or different. When e7 is 2, 3, 4, 5, or 6, each R F3 They may be the same or different.

[0868] Among formulas (sulfo-1), R q11 to R q14 is a hydrocarbyl group having 1 to 20 carbon atoms that may contain a halogen atom other than an iodine atom and a fluorine atom, a nitro group, a cyano group, or a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom. The hydrocarbyl portion of the hydrocarbyl group, and the hydrocarbyl portion of the hydrocarbyloxy group and the hydrocarbylthio group, may be saturated or unsaturated, and may be linear, branched, or cyclic. As a specific example, in the explanation of formula (A), R 1 to R 3 Examples of hydrocarbyl groups represented as such can be given as those exemplified. In addition, some or all of the hydrogen atoms of the hydrocarbyl portion of the hydrocarbyl group, hydrocarbyloxy group, and hydrocarbylthio 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 cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, 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.

[0869] Also, when e8 is 2, 2 R q11 They may be identical or different, and 2 R q11 These may bond with each other to form a ring with the carbon atom to which they bond. When e9 is 2, 2 R q12 They may be the same or different, and 2 R q12They may bond with each other to form a ring with the carbon atom to which they bond. When e10 is 2, 2 R q13 They may be identical or different, and 2 R q13 These may bond with each other to form a ring with the carbon atom they bond to. When e13 is 2, 2 R q14 They may be the same or different, and 2 R q14 They may combine with each other to form a ring together with the carbon atom to which they are bonded. Specific examples of the ring formed at this time include a cyclopropane ring, a cyclobutane ring, a cyclophenane ring, a cyclohexane ring, a norbornane ring, an adamantane ring, etc. In addition, some or all of the hydrogen atoms in the ring may be substituted with a group containing heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and some of the -CH2- in the ring may be substituted with a group containing heteroatoms such as an oxygen atom, a sulfur atom, or 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 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.

[0870] In addition, S in the sulfonium cation represented by the formula (sulfo-1) + Direction rings that directly bind to each other combine with S + A ring may be formed together with. In this case, specific examples of the structure of the ring include those represented by the following formula.

[0871]

[0872] (In the formula, the dashed line is a connecting hand.)

[0873] Among the formula (sulfo-1), L F and L GEach is independently a single bond, ether bond, ester bond, amide bond, sulfonic acid ester bond, sulfonate amide bond, carbonate bond, or carbamate bond. Among these, L F As such, it is preferable that it be a single bond, an ether bond, an ester bond, or a sulfonic acid ester bond, and more preferable that it be an ester bond or a sulfonic acid ester bond. L G As such, it is preferable that it be a single bond, an ether bond, or an ester bond, and more preferable that it be a single bond.

[0874] Among formulas (sulfo-1), X L3 It is a hydrocarbylene group having 1 to 40 carbon atoms that may include a single bond or a heteroatom. The hydrocarbylene group may be linear, branched, or cyclic, and specific examples thereof include an alkanedyl group, a cyclic saturated hydrocarbylene group, an arylene group, etc. Specific examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, etc. X L3 Specific examples of hydrocarbylene groups having 1 to 40 carbon atoms that may include a heteroatom represented by , are X in the explanation of formula (Z2). L1 and X L2 X exemplified as a specific example of a hydrocarbylene group having 1 to 40 carbon atoms that may include a heteroatom represented by . L -0 to X L One example is -61. Among these, X L3 As for, X L -0 to X L -22, X L -29 to X L -34 and X L -47 to X L -61 is desirable.

[0875] As for the sulfonium cation represented by the formula (sulfo-1), it is preferable to represent it by the following formula (sulfo-1-1).

[0876]

[0877] (among the food, e4 to e10, e12 to e14, R F1 to R F3 , R q11 to R q14 , L F , L G and X L3 is the same as above.)

[0878] As for the sulfonium cation represented by the formula (sulfo-1-1), it is preferable to represent it by the following formula (sulfo-1-2).

[0879]

[0880] (among the food, e4 to e10, R F1 to R F3 and R q11 to R q13 is the same as above.)

[0881] Specific examples of the sulfonium cation represented by the formula (sulfo-1) include those shown below, but are not limited to these. In addition, in the following formula, Me is a methyl group.

[0882]

[0883]

[0884]

[0885]

[0886]

[0887]

[0888]

[0889]

[0890]

[0891]

[0892]

[0893]

[0894]

[0895]

[0896]

[0897]

[0898]

[0899]

[0900]

[0901]

[0902]

[0903]

[0904]

[0905]

[0906]

[0907]

[0908]

[0909]

[0910] Specific examples of the above iodine cations include those described in paragraph

[0181] of Japanese Patent Publication No. 2024-259, but are not limited to these.

[0911] Specific examples of the above ammonium cation include those represented by the following formula (am-1).

[0912]

[0913] In the equation (am-1), R q21 to R q24is a hydrocarbyl group having 1 to 40 carbon atoms that may each independently contain a heteroatom. Also, R q21 and R q22 a, they may combine with each other to form a ring together with the nitrogen atom to which they combine. As a specific example of the above hydrocarbyl group, R in the explanation of formula (A) 1 to R 3 Examples of hydrocarbilic groups indicated as such can be cited as those exemplified.

[0914] Specific examples of the ammonium cation represented by formula (am-1) include those shown below, but are not limited to these.

[0915]

[0916] Specific examples of the onium salts represented by formula (1) or (2) include any combination of the aforementioned anions and cations. Furthermore, these onium salts are easily prepared by an ion exchange reaction using known organic chemical methods. For ion exchange reactions, for example, Japanese Patent Publication No. 2007-145797 may be referenced.

[0917] The onium salt represented by formula (1) or (2) acts as a quencher in the chemical amplification resist composition of the present invention. This is because each counter anion of the onium salt is a conjugate base of a weak acid. The term "weak acid" here refers to an acidity that cannot deprotect the acid unstable group of the acid unstable group-containing unit used in the base polymer. The onium salt represented by formula (1) or (2) functions as a quencher when used in combination with an onium salt-type photoacid generator having a conjugate base of a strong acid, such as sulfonic acid with the α-position fluorinated, as a counter anion. That is, when a mixture of an onium salt that generates a strong acid, such as a sulfonic acid with an α-position fluorinated, and an onium salt that generates a weak acid, such as a non-fluorinated sulfonic acid or carboxylic acid, is used, when the strong acid generated from the photoacid generator by high-energy ray irradiation collides with the onium salt containing an unreacted weak acid anion, the weak acid is released through salt exchange and an onium salt containing a strong acid anion is generated. In this process, since the strong acid is exchanged for a weak acid with lower catalytic activity, the acid is seemingly eliminated, and the control of acid diffusion can be achieved.

[0918] In addition, (C) as a quencher, an onium salt having a sulfonium cation and a phenoxide anion site within the same molecule as described in Japanese Patent Publication No. 6848776, additionally an onium salt having a sulfonium cation and a carboxylate anion site within the same molecule as described in Japanese Patent Publication No. 6583136 and Japanese Patent Publication No. 2020-200311, and an onium salt having an iodonium cation and a carboxylate anion site within the same molecule as described in Japanese Patent Publication No. 6274755 may be used.

[0919] Here, when the acid-generating agent that produces a strong acid is an onium salt, as mentioned above, the strong acid generated by high-energy irradiation can be exchanged for a weak acid, but on the other hand, it is thought that the weak acid generated by high-energy irradiation cannot collide with the unreacted strong acid-generating onium salt to perform salt exchange. This is due to the phenomenon that onium cations are more likely to form ion pairs with anions that are stronger acids.

[0920] When the chemical amplification resist composition of the present invention includes an onium salt represented by formula (1) or (2) as (C) quencher, the content thereof is preferably 0.1 to 20 parts by mass with respect to 80 parts by mass of (A) base polymer, and more preferably 0.1 to 10 parts by mass. It is desirable that the content of the onium salt type quencher be within the above range because the resolution is good and there is no significant decrease in sensitivity. The onium salt represented by formula (1) or (2) may be used as a single type or in combination of two or more types.

[0921] The chemical amplification resist composition of the present invention may include (C) a nitrogen-containing compound as a quencher. Specific examples of the nitrogen-containing compound include primary, secondary, or tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Publication No. 2008-111103, particularly amine compounds having a hydroxyl group, an ether bond, an ester bond, a lactone ring, a cyano group, or a sulfonic acid ester bond. Additionally, compounds in which a primary or secondary amine is protected by a carbamate group as described in Japanese Patent Publication No. 3790649 may also be included.

[0922] In addition, a sulfonium sulfonate salt having a nitrogen-containing substituent may be used as a nitrogen-containing compound. Such a compound functions as a so-called photodisintegrating base, which functions as a quencher in the unexposed area and loses its quenching ability in the exposed area through neutralization with its own generated acid. By using a photodisintegrating base, the contrast between the exposed area and the unexposed area can be further enhanced. As for photodisintegrating bases, reference may be made to, for example, Japanese Patent Publication No. 2009-109595 and Japanese Patent Publication No. 2012-46501.

[0923] When the chemical amplification resist composition of the present invention includes a nitrogen-containing compound as (C) quencher, the content thereof is preferably 0.001 to 12 parts by mass and more preferably 0.01 to 8 parts by mass with respect to 80 parts by mass of (A) base polymer. The nitrogen-containing compound may be used alone or in combination of two or more types.

[0924] [(D) Mining Agent]

[0925] The chemical amplification resist composition of the present invention may include a photoacid generator as component (D). The photoacid generator is not particularly limited as long as it is a compound that generates acid upon irradiation with high energy rays. Suitable photoacid generators may be those represented by the following formulas (3) or (4).

[0926]

[0927] In Equation (3), R 101 to R 105 is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a halogen atom or a heteroatom. Also, R 101 , R 102 and R 103 Any two of them may combine with each other to form a ring together with the sulfur atom to which they are bonded. As a specific example of the above hydrocarbyl group, R in the explanation of formula (A)1 to R 3 Examples of hydrocarbilic groups indicated as such can be cited as those exemplified.

[0928] Specific examples of the cation of the sulfonium salt represented by Formula (3) include those exemplified as specific examples of the cation of the sulfonium salt-type monomer represented by Formula (A), those described in paragraphs

[0102] to

[0125] of Japanese Patent Publication No. 2024-3744, those described in paragraphs

[0044] to

[0049] of International Publication No. 2024 / 128017, those described in paragraphs

[0035] to

[0046] of Patent No. 7491173, and those exemplified as specific examples of the sulfonium cation represented by Formula (Sulpho-1), but are not limited thereto. Specific examples of the cation of the iodonium salt represented by Formula (4) include those described in paragraph

[0181] of Japanese Patent Publication No. 2024-259, but are not limited thereto.

[0929] Among equations (3) and (4), Xa - is an anion of a strong acid. Examples of the anions of the strong acid include those represented by any of the following formulas (Xa-1) to (Xa-4).

[0930]

[0931] In equation (Xa-1), R fa is a hydrocarbyl group having 1 to 60 carbon atoms that 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 (Xa-1-1) described below. fa1 One can cite the same as the example given as the hydrocarbyl group indicated by .

[0932] As for the anion represented by formula (Xa-1), it is preferable to represent it by the following formula (Xa-1-1).

[0933]

[0934] In equation (Xa-1-1), Q 1 and Q 2 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms, but for improved solvent solubility, it is preferable that at least one is a trifluoromethyl group. m is 0, 1, 2, 3, or 4, but is particularly preferable to be 1. R fa1 The hydrocarbyl group has 1 to 40 carbon atoms and 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 from the perspective of obtaining high resolution in fine pattern formation.

[0935] In equation (Xa-1-1), R fa1The hydrocarbyl group having 1 to 40 carbon atoms represented by may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples include an alkyl group having 1 to 40 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, 2-ethylhexyl group, nonyl group, undecyl group, tridecyl group, pentadecyl group, heptadecyl group, icosyl group; Cyclic saturated hydrocarbyl groups having 3 to 40 carbon atoms, such as cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl; unsaturated aliphatic hydrocarbyl groups having 2 to 40 carbon atoms, such as 2-propenyl and 3-cyclohexenyl; aryl groups having 6 to 40 carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, and 9-fluorenyl; and aralkyl groups having 7 to 40 carbon atoms, such as benzyl and diphenylmethyl. Examples include 9,10-ethano-9,10-dihydroanthryl group, 6,13-ethano-6,13-dihydropentaxenyl group, and other aromatic ring-containing polycyclic hydrocarbyl groups having 7 to 40 carbon atoms; hydrocarbyl groups having 17 to 40 carbon atoms having a steroid backbone; and groups obtained by combining these.

[0936] 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.

[0937] In equation (Xa-1-1), L a1 The bonds are single bonds, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, or carbamate bonds, but from a synthetic perspective, ether bonds or ester bonds are preferred, and ester bonds are more preferred.

[0938] Specific examples of the anion represented by formula (Xa-1) include those shown below, but are not limited thereto. In addition, among the following formulas, Q 1 ...is the same as above, and Ac is an acetyl group.

[0939]

[0940]

[0941]

[0942]

[0943]

[0944]

[0945]

[0946]

[0947]

[0948]

[0949]

[0950]

[0951] In equation (Xa-2), R fb1 and R fb2 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 (Xa-1-1). 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 a, combining with each other, the group that combines these (-CF2-SO2-N - It may form a ring with -SO2-CF2-), and in this case, R fb1 and R fb2 As for the groups obtained by combining with each other, a fluorinated ethylene group or a fluorinated propylene group is preferred.

[0952] In equation (Xa-3), R fc1 , R fc2 and R fc3Each 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 (Xa-1-1). 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 a, combining with each other, the group that combines these (-CF2-SO2-C - It may form a ring with -SO2-CF2-), and in this case, R fc1 and R fc2 As for the groups obtained by combining with each other, a fluorinated ethylene group or a fluorinated propylene group is preferred.

[0953] In equation (Xa-4), 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 (Xa-1-1). fa1Examples of hydrocarbyl groups represented by [ ] can be given as those exemplified. 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.

[0954] Specific examples of anions represented by formula (Xa-4) include those shown below, but are not limited to these.

[0955]

[0956]

[0957] Examples of the above-mentioned non-nucleophilic counterions include anions having an aromatic ring substituted with an iodine atom or a bromine atom. Specific examples of such anions include those represented by the following formula (Xa-5).

[0958]

[0959] In equation (Xa-5), x is 1, 2, or 3. y is 1, 2, 3, 4, or 5.

[0960] z is 0, 1, 2, or 3, provided that 1 ≤ y + z ≤ 5. y is preferably 1, 2, or 3, and more preferably 2 or 3. z is preferably 0, 1, or 2.

[0961] In equation (Xa-5), X BIis an iodine atom or a bromine atom. When x and / or y are 2 or greater, each X BI They may be the same or different.

[0962] In equation (Xa-5), L 11 The group may be a single bond, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a carbamate bond, or a saturated hydrocarbylene group having 1 to 6 carbon atoms, and a portion of the -CH2- of the hydrocarbylene group may be substituted by an ether bond or an ester bond. The saturated hydrocarbylene group may be straight, branched, or cyclic.

[0963] In equation (Xa-5), L 12 When x is 1, it is a hydrocarbylene group having 1 to 20 carbon atoms that may contain a single bond or a heteroatom, and when x is 2 or 3, it is a hydrocarbon group having 1 to 20 carbon atoms that may contain a heteroatom.

[0964] L 12 The hydrocarbylene group having 1 to 20 carbon atoms, represented by [the radical], may be saturated or unsaturated and may be linear, branched, or cyclic. Specific examples include an alkane diyl group having 1 to 20 carbon atoms, such as 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; Cyclopentanediyl, cyclohexanediyl, norbornandiyl, adamantandiyl, tricyclo[5.2.1.0 2,6Examples include cyclic saturated hydrocarbylene groups having 3 to 20 carbon atoms, such as decandyl groups; unsaturated aliphatic hydrocarbylene groups having 2 to 20 carbon atoms, such as vinylene groups and propene-1,3-diyl groups; arylene groups having 6 to 20 carbon atoms, such as phenylene groups, naphthylene groups and anthracendiyl groups; aromatic ring-containing polycyclic hydrocarbylene groups having 7 to 20 carbon atoms, such as 9,10-ethano-9,10-dihydroanthracendiyl groups and 6,13-ethano-6,13-dihydropentacene groups; and groups obtained by combining these. 12 The (x+1) hydrocarbon group having 1 to 20 carbon atoms represented by may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include a group obtained by removing one or two additional hydrogen atoms from the aforementioned specific example of a hydrocarbylene group having 1 to 20 carbon atoms.

[0965] In addition, some or all of the hydrogen atoms of the hydrocarbon group (x+1) may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and some of the -CH2- of the hydrocarbon group (x+1) may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, etc., and as a result, may include a hydroxyl group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, 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.

[0966] In equation (Xa-5), L 13 It is a single bond, ether bond, ester bond, sulfonic acid ester bond, carbonate bond, or carbamate bond.

[0967] In equation (Xa-5), R feis, hydroxyl group, carboxyl group, fluorine atom, chlorine atom, bromine atom, amino group, hydrocarbyl group having 1 to 20 carbon atoms, hydrocarbyloxy group having 1 to 20 carbon atoms, hydrocarbylthio group having 1 to 20 carbon atoms, hydrocarbylcarbonyl group having 2 to 20 carbon atoms, hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms, hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms, or hydrocarbylsulfonyloxy group having 1 to 20 carbon atoms, -N(R feA )(R feB ), -N(R feC )-C(=O)-R feD or -N(R feC )-C(=O)-OR feD And, the corresponding hydrocarbyl group, hydrocarbyloxy group, hydrocarbylthio group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group, hydrocarbylcarbonyloxy group, and hydrocarbylsulfonyloxy group may include at least one selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, an amino group, an ester bond, and an ether bond. R feA and R feB is, each independently, a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. R feC is 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. feD...is an aliphatic hydrocarbyl group having 1 to 16 carbon atoms, an aryl group having 6 to 12 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 x and / or z is 2 or more, each R fe They may be the same or different.

[0968] Among these, R fe As, hydroxyl group, -N(R feC )-C(=O)-R feD , -N(R feC )-C(=O)-OR feD Fluorine atoms, chlorine atoms, bromine atoms, methyl groups, methoxy groups, etc. are preferred.

[0969] In Equation (Xa-5), Rf 11 to Rf 14 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 11 and Rf 12 They may combine to form a carbonyl group. In particular, Rf 13 and Rf 14 It is desirable that all of them are fluorine atoms.

[0970] Specific examples of the anion represented by formula (Xa-5) include those shown below, but are not limited thereto. In addition, among the following formulas, X BI It is the same as above.

[0971]

[0972]

[0973]

[0974]

[0975]

[0976]

[0977]

[0978]

[0979]

[0980]

[0981]

[0982]

[0983]

[0984]

[0985]

[0986]

[0987]

[0988]

[0989]

[0990]

[0991]

[0992]

[0993]

[0994]

[0995] Shah -Other examples of anions represented by are paragraphs

[0076] and

[0106] of International Publication No. 2023 / 157455, paragraph

[0111] of International Publication No. 2024 / 24801, paragraphs

[0253] to

[0256] of International Publication No. 2024 / 43121, paragraphs

[0044] to

[0045] of International Publication No. 2024 / 57751, paragraphs

[0205] to

[0220] of International Publication No. 2024 / 122423, paragraphs

[0170] to

[0178] of Japanese Patent Publication No. 2023-123183, paragraphs

[0026] to

[0028] of Japanese Patent Publication No. 2024-62406, and paragraph

[0024] of Japanese Patent Publication No. 2024-62407.

[0022] to

[0025] , Paragraphs

[0026] to

[0028] of Japanese Patent Publication No. 2024-62408, Paragraphs

[0028] to

[0030] of Japanese Patent Publication No. 2024-68156, Paragraphs

[0026] to

[0028] of Japanese Patent Publication No. 2024-68157, Paragraphs

[0028] to

[0030] of Japanese Patent Publication No. 2024-68158, Paragraphs

[0028] to

[0030] of Japanese Patent Publication No. 2024-68159, Paragraphs

[0028] to

[0030] of Japanese Patent Publication No. 2024-72280, Paragraphs

[0031] to

[0033] of Japanese Patent Publication No. 2024-72281, Paragraphs

[0023] to

[0025] of Japanese Patent Publication No. 2024-72281, Japan Paragraphs

[0026] to

[0029] of Patent Publication No. 2024-77618, Paragraphs

[0020] to

[0021] of Japanese Patent Publication No. 2024-77619, Paragraphs

[0140] to

[0143] of Japanese Patent Publication No. 2024-80672, Paragraphs

[0023] to

[0025] of Japanese Patent Publication No. 2024-83303, Paragraphs

[0028] to

[0031] of Japanese Patent Publication No. 2024-83304, Paragraphs

[0030] to

[0033] of Japanese Patent Publication No. 2024-99500Paragraphs

[0028] to

[0030] of Japanese Patent Publication No. 2024-99502, Paragraphs

[0030] to

[0032] of Japanese Patent Publication No. 2024-101557, Paragraphs

[0025] to

[0027] of Japanese Patent Publication No. 2024-102842, Paragraphs

[0033] to

[0035] of Japanese Patent Publication No. 2024-102843, Paragraphs

[0021] to

[0022] of Japanese Patent Publication No. 2024-127832, Paragraphs

[0169] to

[0172] of Japanese Patent Publication No. 2024-144354, Paragraphs

[0178] to

[0181] of Japanese Patent Publication No. 2024-144356, Japanese Patent Publication Examples include paragraphs

[0040] to

[0143] of Japanese Patent Publication No. 2024-160436, paragraphs

[0157] to

[0158] of Japanese Patent Publication No. 7247732, paragraphs

[0227] to

[0238] of Japanese Patent Publication No. 7446352, paragraphs

[0253] to

[0256] of Japanese Patent Publication No. 7466597, and paragraphs

[0309] to

[0312] of Japanese Patent Publication No. 7466782.

[0996] As the above-mentioned non-nucleophilic counterion, a fluorobenzenesulfonic acid anion bonded to an aromatic group containing an iodine atom as described in Japanese Patent Publication No. 6648726, an anion having a mechanism that decomposes by acid as described in International Publication No. 2021 / 200056 or Japanese Patent Publication No. 2021-70692, an anion having a cyclic ether group as described in Japanese Patent Publication No. 2018-180525 or Japanese Patent Publication No. 2021-35935, or an anion as described in Japanese Patent Publication No. 2018-92159 may be used.

[0997] As the above-mentioned non-nucleophilic counterion, additionally, anion of a bulky benzenesulfonic acid derivative not containing a fluorine atom as described in Japanese Patent Publication No. 2006-276759, Japanese Patent Publication No. 2015-117200, Japanese Patent Publication No. 2016-65016 and Japanese Patent Publication No. 2019-202974 and Japanese Patent Publication No. 2024-104830, or a benzenesulfonic acid anion or an alkylsulfonic acid anion not containing a fluorine atom bonded to an aromatic group containing an iodine atom as described in Japanese Patent Publication No. 6645464. In addition, anions described in

[0229] to

[0231] of Japanese Patent Publication No. 2024-77330 and

[0033] to

[0093] of Japanese Patent Publication No. 2024-140135 may also be used.

[0998] As the above non-nucleophilic counterion, additionally, the anion of a bissulfonic acid described in Japanese Patent Publication No. 2015-206932, the anion of a sulfonamide or sulfonimide in which one side is a sulfonic acid and the other side is different from this described in International Publication No. 2020 / 158366, and the anion of a carboxylic acid in which one side is a sulfonic acid and the other side is a carboxylic acid described in Japanese Patent Publication No. 2015-24989 may be used.

[0999] In addition, as a component of (D), it is also desirable to have it represented by the following formula (5).

[1000]

[1001] In Equation (5), R 201 and R 202 R is a hydrocarbyl group having 1 to 30 carbon atoms that may each independently contain a heteroatom. 203 It is a hydrocarbylene group having 1 to 30 carbon atoms that may contain heteroatoms. Also, R 201 , R 202 and R 203Any two of them may combine with each other to form a ring together with the sulfur atom to which they combine.

[1002] R 201 and R 202 The hydrocarbyl group having 1 to 30 carbon atoms represented by may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples include alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, n-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 cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, 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.

[1003] R 203The hydrocarbylene group having 1 to 30 carbon atoms 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; and 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, and tert-butylnaphthylene. 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 cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, 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.

[1004] In formula (5), L 21 It is a hydrocarbylene group having 1 to 20 carbon atoms that 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.

[1005] In equation (5), 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.

[1006] As for the oxidizing agent represented by formula (5), it is preferable to have it represented by the following formula (5').

[1007]

[1008] In equation (5'), L 21 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 It is a hydrocarbyl group having 1 to 20 carbon atoms, which may each 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 (Xa-1-1). fa1 Examples of hydrocarbyl groups represented by can be given as those exemplified. p and q are, independently, 0, 1, 2, 3, 4 or 5, and r is 0, 1, 2, 3 or 4.

[1009] Specific examples of the light-generating agent represented by formula (5) include those similar to the light-generating agent represented by formula (2) in Japanese Patent Publication No. 2017-26980.

[1010] Among the above-mentioned photoacid generators, those containing anion represented by formula (Xa-1-1) or (Xa-4) are particularly desirable because they have low acid diffusion and excellent solubility in solvents. Additionally, those represented by formula (5') are particularly desirable because they have very low acid diffusion.

[1011] When the chemical amplification resist composition of the present invention includes (D) a photoacid generator, the content thereof is preferably 0.1 to 40 parts by mass and more preferably 0.5 to 20 parts by mass with respect to 80 parts by mass of (A) base polymer. It is desirable that the amount of (D) photoacid generator added is within the above range because it provides good resolution and there is no risk of foreign matter occurring after development or peeling of the resist film. (D) The photoacid generator may be used as a single type or in combination of two or more types.

[1012] [(E) Surfactant]

[1013] The chemical amplification resist composition of the present invention may additionally include a surfactant as component (E). Preferably, (E) the surfactant is a surfactant that is insoluble or sparingly soluble in water and soluble in an alkaline developer, or a surfactant that is insoluble or sparingly soluble in water and an alkaline developer. As such a surfactant, reference may be made to those described in Japanese Patent Publication No. 2010-215608 or Japanese Patent Publication No. 2011-16746.

[1014] As surfactants that are insoluble or sparingly soluble in water and alkaline developing solutions, among the surfactants described in the above publication, FC-4430 (manufactured by 3M), Surflon (registered trademark) S-381 (manufactured by AGC Seimi Chemical Co., Ltd.), Olfin (registered trademark) E1004 (manufactured by Nissin Kagaku Kogyo Co., Ltd.), KH-20, KH-30 (manufactured by AGC Seimi Chemical Co., Ltd.), and oxetane ring-opening polymers represented by the following formula (surf-1) are preferred.

[1015]

[1016] Here, R, Rf, A, B, C, m, and n apply only to formula (surf-1), regardless of the description above. R is a 2 to 4-valent aliphatic group having 2 to 5 carbon atoms. Examples of the aliphatic groups include, for divalent groups, ethylene groups, 1,4-butylene groups, 1,2-propylene groups, 2,2-dimethyl-1,3-propylene groups, 1,5-pentylene groups, etc., and for trivalent or 4-valent groups, the following may be examples.

[1017]

[1018] (In the formulas, dashed lines are bonding hands and are substructures derived from glycerol, trimethylolethane, trimethylolpropane, and pentaerythritol, respectively.)

[1019] Among these, 1,4-butylene groups, 2,2-dimethyl-1,3-propylene groups, etc. are preferred.

[1020] Rf is a trifluoromethyl group or a pentafluoroethyl group, preferably a trifluoromethyl group. m is an integer from 0 to 3, n is an integer from 1 to 4, the sum of n and m is the valence of R, and is an integer from 2 to 4. A is 1. B is an integer from 2 to 25, preferably an integer from 4 to 20. C is an integer from 0 to 10, preferably 0 or 1. In addition, the arrangement of each constituent unit in formula (surf-1) is not specified, and they may be joined in a block or randomly. The preparation of a partially fluorinated oxetane ring-opening polymer-based surfactant is described in detail in U.S. Patent No. 5650483, etc.

[1021] A surfactant that is insoluble or sparingly soluble in water and soluble in an alkaline developer has the function of reducing water seepage or leaching by orienting it on the surface of the resist film when a resist protective film is not used in ArF immersion lithography. Therefore, it is useful for suppressing the leaching of water-soluble components from the resist film to reduce damage to the exposure device, and it is also useful because it becomes soluble during alkaline aqueous development after exposure or after exposure baking (PEB) and is unlikely to become a foreign substance that causes defects. Such a surfactant has the property of being insoluble or sparingly soluble in water and soluble in an alkaline developer, is a polymeric surfactant, is also called a hydrophobic resin, and is particularly desirable to have high water repellency and improved water activity.

[1022] Specific examples of such polymeric surfactants include at least one selected from the repeating unit represented by the following formula (6A) (hereinafter also referred to as repeating unit 6A), the repeating unit represented by the following formula (6B) (hereinafter also referred to as repeating unit 6B), the repeating unit represented by the following formula (6C) (hereinafter also referred to as repeating unit 6C), the repeating unit represented by the following formula (6D) (hereinafter also referred to as repeating unit 6D), and the repeating unit represented by (6E) (hereinafter also referred to as repeating unit 6E).

[1023]

[1024] Among formulas (6A) to (6E), R B is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. W 1 It is -CH2-, -CH2CH2-, -O-, or two separate -Hs. R s1 Each is independently a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. R s2 is a single bond, or a straight-chain or branched hydrocarbylene group having 1 to 5 carbon atoms. R s3 R is, each independently, a hydrogen atom, a hydrocarbyl group having 1 to 15 carbon atoms or a fluorinated hydrocarbyl group, or an acid instability group. s3 In the case of this hydrocarbyl group or fluorinated hydrocarbyl group, an ether bond or a carbonyl group may be interposed between the carbon-carbon bonds. R s4 is a (u+1) valence hydrocarbon group or a fluorinated hydrocarbon group having 1 to 20 carbon atoms. u is 1, 2, or 3. R s5 are, respectively, hydrogen atoms, or -C(=O)-OR sa It is a unit represented by . R sa is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms. R s6It is a hydrocarbyl group or a fluorinated hydrocarbyl group having 1 to 15 carbon atoms, and an ether bond or a carbonyl group may be interposed between the carbon-carbon bonds.

[1025] R s1 The hydrocarbyl group having 1 to 10 carbon atoms represented by is preferably a saturated hydrocarbyl group and may be straight, branched, or cyclic. Specific examples include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cyclic saturated hydrocarbyl groups having 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornyl groups. Among these, those having 1 to 6 carbon atoms are preferred.

[1026] R s2 The hydrocarbylene group represented by is preferably a saturated hydrocarbylene group and may be straight, branched, or cyclic. Specific examples include methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, etc.

[1027] R s3 or R s6 The hydrocarbyl group represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include saturated hydrocarbyl groups, aliphatic unsaturated hydrocarbyl groups such as alkenyl groups and alkynyl groups, but saturated hydrocarbyl groups are preferred. Specific examples of the above saturated hydrocarbyl group include R s1 In addition to the hydrocarbyl group represented by , examples include undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl groups. R s3 or R s6As a fluorinated hydrocarbyl group represented by, examples include a group in which some or all of the hydrogen atoms bonded to the carbon atoms of the aforementioned hydrocarbyl group are substituted with fluorine atoms. As previously mentioned, an ether bond or a carbonyl group may be interposed between these carbon-carbon bonds.

[1028] R s3 Specific examples of acid instability groups represented by the above-described formulas (AL-3) to (AL-5) include trialkylsilyl groups in which each alkyl group has 1 to 6 carbon atoms, and oxo-containing alkyl groups having 4 to 20 carbon atoms.

[1029] R s4 The (u+1) valence hydrocarbon group or fluorinated hydrocarbon group represented by may be straight-chain, branched, or cyclic, and specific examples thereof include a group obtained by additionally removing u hydrogen atoms from the aforementioned hydrocarbyl group or fluorinated hydrocarbyl group.

[1030] R sa The fluorinated hydrocarbyl group represented by is preferably saturated and may be straight, branched, or cyclic. Specific examples thereof include cases where some or all of the hydrogen atoms of the hydrocarbyl group are substituted with fluorine atoms, and specific examples thereof include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoro-1-propyl group, a 3,3,3-trifluoro-2-propyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,1,3,3,3-hexafluoroisopropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a 2,2,3,3,4,4,5,5-octafluoropentyl group, a 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl group, a 2-(perfluorobutyl)ethyl group, a 2-(perfluorohexyl)ethyl group, a 2-(perfluorooctyl)ethyl group, and a 2-(perfluorodecyl)ethyl group You can lift the back.

[1031] Specific examples of repeating units 6A to 6E may be those shown below, but are not limited thereto. In addition, among the following formulas, R B It is the same as above.

[1032]

[1033]

[1034]

[1035]

[1036]

[1037]

[1038] The above polymeric surfactant may additionally include repeating units other than repeating units 6A to 6E. Specific examples of other repeating units include repeating units obtained from methacrylic acid or α-trifluoromethylacrylic acid derivatives. Among the polymeric surfactant, the content of repeating units 6A to 6E is preferably 20 mol% or more of the total repeating units, more preferably 60 mol% or more, and even more preferably 100 mol%.

[1039] The Mw of the above polymeric surfactant is preferably 1,000 to 500,000, and more preferably 3,000 to 100,000. The Mw / Mn is preferably 1.0 to 2.0, and more preferably 1.0 to 1.6.

[1040] As a method for synthesizing the above polymeric surfactant, a monomer comprising an unsaturated bond that provides at least one repeating unit selected from 6A to 6E and, if necessary, other repeating units is heated in an organic solvent with the addition of a radical initiator and polymerized. Specific examples of organic solvents used during polymerization include toluene, benzene, THF, diethyl ether, dioxane, etc. Specific examples of polymerization initiators include AIBN, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, lauroyl peroxide, etc. The reaction temperature is preferably 50 to 100°C. The reaction time is preferably 4 to 24 hours. The acid instability group may be used as is introduced into the monomer, or may be protected or partially protected after polymerization.

[1041] When synthesizing the above polymeric surfactant, known chain transfer agents such as dodecyl mercaptan or 2-mercaptoethanol may be used to adjust the molecular weight. In that case, the amount of these chain transfer agents added is preferably 0.01 to 10 mol% with respect to the total moles of the monomers to be polymerized.

[1042] When the chemical amplification resist composition of the present invention includes (E) a surfactant, the content thereof is preferably 0.1 to 50 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 80 parts by mass of (A) base polymer. If the content of (E) surfactant is 0.1 parts by mass or more, the receding contact angle between the surface of the resist film and water is sufficiently improved, and if it is 50 parts by mass or less, the dissolution rate of the surface of the resist film with respect to the developer is low, so the height of the formed fine pattern is sufficiently maintained. (E) surfactant may be used as a single type or may be used in combination of two or more types.

[1043] [(F) Other components]

[1044] The chemical amplification resist composition of the present invention may include (F) other components, such as a compound that decomposes to generate acid when exposed to acid (acid-producing compound), an organic acid derivative, a fluorine-substituted alcohol, a compound having an Mw of 3000 or less that changes solubility in a developer solution due to the action of acid (dissolution inhibitor), etc. As for the acid-producing compound, reference may be made to the compounds described in Japanese Patent Publication No. 2009-269953 or Japanese Patent Publication No. 2010-215608. When the acid-producing compound is included, the content thereof is preferably 0 to 5 parts by mass with respect to (A) 80 parts by mass of base polymer, and more preferably 0 to 3 parts by mass. If the content is too high, it is difficult to control acid diffusion, and deterioration of resolution and pattern shape may occur. As for the above organic acid derivative, fluorine-substituted alcohol, and solubility inhibitor, reference may be made to the compounds described in Japanese Patent Publication No. 2009-269953 or Japanese Patent Publication No. 2010-215608.

[1045] [Pattern Formation Method]

[1046] The pattern forming method of the present invention comprises a process of forming a resist film on a substrate using the aforementioned chemically amplified resist composition, a process of exposing the resist film to high-energy rays, and a process of developing the exposed resist film using a developer.

[1047] As the above substrate, for example, a substrate for manufacturing integrated circuits (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.) or a substrate for manufacturing mask circuits (Cr, CrO, CrON, MoSi2, SiO2, etc.) may be used.

[1048] A resist film can be formed by applying the chemical amplification resist composition onto a substrate such that the film thickness is preferably 0.05 to 2 μm by a method such as spin coating, for example, and pre-baking it on a hot plate, preferably at 60 to 150°C for 1 to 10 minutes, more preferably at 80 to 140°C for 1 to 5 minutes.

[1049] Examples of high-energy rays used for exposing the resist film include KrF excimer laser light, ArF excimer laser light, EB, and EUV with a wavelength of 3 to 15 nm. When using KrF excimer laser light, ArF excimer laser light, or EUV, exposure can be performed by using a mask to form a desired pattern and irradiating so that the exposure amount is preferably 1 to 200 mJ / cm², more preferably 10 to 100 mJ / cm². When using EB, exposure is performed either by using a mask to form a desired pattern or directly so that the exposure amount is preferably 1 to 300 μC / cm², more preferably 10 to 200 μC / cm².

[1050] In addition, in addition to the conventional exposure method, it is also possible to use an immersion method in which a liquid with a refractive index of 1.0 or higher is interposed between the resist film and the projection lens. In that case, it is also possible to use a protective film that is insoluble in water.

[1051] The above-mentioned water-insoluble protective film is used to prevent leaching from the resist film and to increase the water-repellent properties of the film surface, and is broadly classified into two types. One is an organic solvent peeling type that requires peeling before alkaline aqueous solution development by an organic solvent that does not dissolve the resist film, and the other is an alkaline aqueous solution soluble type that is soluble in the alkaline developer and removes the protective film along with the removal of the resist film-soluble portion. The latter is particularly preferably a material in which a polymer having 1,1,1,3,3,3-hexafluoro-2-propanol residues that is insoluble in water and soluble in the alkaline developer is used as the base, and which is dissolved in an alcohol-based solvent having 4 or more carbon atoms, an ether-based solvent having 8 to 12 carbon atoms, or a mixture of these solvents. The aforementioned water-insoluble and alkaline developer-soluble surfactant may also be a material in which it is dissolved in an alcohol-based solvent having 4 or more carbon atoms, an ether-based solvent having 8 to 12 carbon atoms, or a mixture of these solvents.

[1052] After exposure, PEB may be performed. PEB can be performed, for example, by heating on a hot plate at 60 to 150°C for 1 to 5 minutes, more preferably at 80 to 140°C for 1 to 3 minutes.

[1053] The development is carried out by using a developer solution of an alkaline aqueous solution, such as tetramethylammonium hydroxide (TMAH), preferably 0.1 to 5 mass%, more preferably 2 to 3 mass%, preferably for 0.1 to 3 minutes, more preferably for 0.5 to 2 minutes, by conventional methods such as the dip method, puddle method, and spray method, so that the exposed portion is dissolved and a desired pattern is formed on the substrate.

[1054] In addition, after forming the resist film, extraction of acid-generating agents from the film surface or washing away of particles may be performed by rinsing with water, or a rinse may be performed to remove water remaining on the film after exposure.

[1055] Additionally, a pattern may be formed by a double patterning method. Examples of double patterning methods include a trench method in which a 1:3 trench pattern underlay is processed by a first exposure and etching, and a 1:3 trench pattern is formed by a second exposure with offset to form a 1:1 pattern, and a line method in which a first underlay of a 1:3 isolated residual pattern is processed by a first exposure and etching, and a second underlay is processed by a second exposure with offset to form a 1:3 isolated residual pattern under the first underlay to form a 1:1 pattern with half the pitch.

[1056] In the pattern forming method of the present invention, a negative tone development method may be used in which an organic solvent is used instead of the alkaline aqueous solution as a developer to dissolve the unexposed area.

[1057] In the above organic solvent development, as a developer, 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, Pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, etc., may be used. These organic solvents may be used individually or in a mixture of two or more types.

[1058] [Example]

[1059] The present invention will be specifically described below by presenting synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In addition, the apparatus used is as follows.

[1060] · MALDI TOF-MS: S3000 manufactured by Nihon Denshi Co., Ltd.

[1061] [1] Synthesis of sulfonium salt-type monomers

[1062] [Example 1-1] Synthesis of Monomer PAG-1

[1063] (1) Synthesis of intermediate In-1

[1064]

[1065] Grignard reagent was prepared according to a conventional method using chlorobenzene (67.5 g), metallic magnesium (14.6 g), and THF (400 g) under a nitrogen atmosphere. Subsequently, the reaction mixture was cooled to 10°C or lower, and a solution containing compound SM-1 (90.9 g) and THF (90 g) was added. Additionally, trimethylsilyl chloride (65.2 g) was added dropwise at a temperature of 20°C or lower. After adding, the mixture was aged for 3 hours at a temperature of 20°C or lower. After aging, a saturated aqueous ammonium chloride solution (500 g) was added dropwise to stop the reaction. Subsequently, methylene chloride (500 g) was added to separate the organic layer, the mixture was washed with water, and then concentrated under reduced pressure to remove the solvent by distillation. By purifying the residue by silica gel column chromatography, 89.3 g of intermediate In-1 was obtained as a colorless oily substance (yield 81%).

[1066] (2) Synthesis of monomer PAG-1

[1067]

[1068] Under a nitrogen atmosphere, intermediate In-1 (55.1g), intermediate In-2 (84.9g), methylene chloride (300g), and water (150g) were added and stirred at room temperature for 30 minutes. The organic layer was aliquoted, washed with water, and then concentrated under reduced pressure. By purifying the residue by silica gel column chromatography, 115.3g of monomer PAG-1 was obtained as an oil phase (yield 95%).

[1069] The results of the PAG-1 TOF-MS are shown below.

[1070] MALDI TOF-MS: POSITIVE M + 515(C 26 H 28 F5OS2 + (Significant)

[1071] NEGATIVE M - 699(C 17 H 11 F2I2O8S2 - (Significant)

[1072] [Examples 1-2 to 1-9] Synthesis of Monomers PAG-2 to PAG-9

[1073] Sulfonium salt-type monomers PAG-2 to PAG-9, as described below, were synthesized through various organic synthesis reactions with corresponding raw materials.

[1074]

[1075]

[1076] [Comparative Examples 1-1 to 1-6] Synthesis of Comparative Monomers PAG-A to PAG-F

[1077] Comparative sulfonium salt-type monomers PAG-A to PAG-F, shown below, were synthesized by using corresponding raw materials and various organic synthesis reactions.

[1078]

[1079] [2] Synthesis of base polymer

[1080] Among the monomers used in the synthesis of the base polymer, those other than PAG-1 to PAG-9 and PAG-A to PAG-F are as follows.

[1081]

[1082]

[1083]

[1084] [Example 2-1] Synthesis of Polymer P-1

[1085] Under a nitrogen atmosphere, monomer a1-1 (36.1g), monomer b1-1 (10.6g), monomer PAG-1 (53.5g), V-601 (manufactured by Wako Junyaku Kogyo Co., Ltd.) 3.38g and 140g of MEK were placed in a flask to prepare a monomer-polymerization initiator solution. 46g of MEK was placed in a separate flask under a nitrogen atmosphere and heated to 80°C while stirring, after which the monomer-polymerization initiator solution was added dropwise over 4 hours. After the addition was finished, stirring was continued for 2 hours while maintaining the temperature of the polymerization solution at 80°C, and then cooled to room temperature. The obtained polymerization solution was added dropwise to 3000g of vigorously stirred hexane, and the precipitated polymer was separated by filtration. In addition, the obtained polymer was washed twice with 600 g of hexane and vacuum dried at 50°C for 20 hours to obtain a white powdery polymer P-1 (quantity 97.1 g, yield 97%). The Mw of polymer P-1 was 9200, and the Mw / Mn ratio was 1.54. In addition, Mw is a polystyrene equivalent measurement value by GPC using DMF as a solvent.

[1086]

[1087] [Examples 2-2 to 2-26, Comparative Examples 2-1 to 2-18] Synthesis of Polymers P-2 to P-26, CP-1 to CP-18

[1088] The polymers shown in Tables 1 and 2 were prepared in the same manner as in Example 2-1, except that the type and mixing ratio of each monomer were changed.

[1089]

[1090]

[1091] [3] Preparation of a chemical amplification resist composition

[1092] [Examples 3-1 to 3-26, Comparative Examples 3-1 to 3-18]

[1093] A chemical amplification resist composition (R-1 to R-26, CR-1 to CR-18) was prepared by dissolving a base polymer (P-1 to P-26) containing the sulfonium salt-type monomer (PAG-1 to PAG-9) of the present invention, a base polymer (CP-1 to CP-18) containing the sulfonium salt-type monomer (PAG-A to PAG-F) of comparison, a photoacid generator (PAG-X to PAG-Z), and a quencher (Q-1 to Q-4) in a solvent containing 0.01 mass% of surfactant A (Omnova Co.) in the compositions shown in Tables 3 and 4 below, and by filtering the said solution with a 0.2 μm Teflon (registered trademark) type filter.

[1094]

[1095]

[1096] In Tables 3 and 4, the solvent, the light acid generators PAG-X, PAG-Y, PAG-Z, the quenchers Q-1 to Q-4, and the surfactant A are as follows.

[1097] · Solvent: PGMEA (propylene glycol monomethyl ether acetate)

[1098] EL (ethyl lactate)

[1099] DAA (diacetone alcohol)

[1100] · Oxide generators: PAG-X, PAG-Y, PAG-Z

[1101]

[1102] · Quencher: Q-1 to Q-4

[1103]

[1104] · Surfactant A: 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane·tetrahydrofuran·2,2-dimethyl-1,3-propanediol copolymer (Omnovasage)

[1105]

[1106] a: (b+b'):(c+c')=1:4 to 7:0.01 to 1 (molar ratio)

[1107] Mw=1500

[1108] [4] EUV lithography evaluation (1)

[1109] [Examples 4-1 to 4-26, Comparative Examples 4-1 to 4-18]

[1110] Each chemical amplification resist composition (R-1 to R-26, CR-1 to CR-18) shown in Tables 3 and 4 was spin-coated onto a Si substrate formed with a silicon-containing spin-on hard mask SHB-A940 (silicon content of 43 mass%) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd. to a film thickness of 20 nm, and pre-baked at 100°C for 60 seconds using a hot plate to produce a resist film with a film thickness of 50 nm. With respect to the above resist film, an LS pattern with wafer dimensions of 18 nm and a pitch of 36 nm was exposed using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9 / 0.6, dipole illumination) while varying the exposure amount and focus (exposure amount pitch: 1 mJ / cm², focus pitch: 0.020 μm), and after exposure, PEB was performed for 60 seconds at the temperatures shown in Tables 5 and 6. Subsequently, puddle development was performed for 30 seconds with a 2.38 mass% aqueous TMAH solution, rinsed with a surfactant-containing rinse material, and spin-dried to obtain a positive pattern.

[1111] The obtained LS pattern was observed using a Hitachi High-Tech Corporation measuring SEM (CG6300), and sensitivity, EL, LWR, DOF, and collapse limit were evaluated according to the following methods. In addition, the developed defects of the obtained LS pattern were evaluated. The results are shown in Tables 5 and 6.

[1112] [Sensitivity Evaluation]

[1113] The optimal exposure dose Eop (mJ / cm²) for obtaining an LS pattern with a line width of 18 nm and a pitch of 36 nm was determined and defined as sensitivity. The smaller this value, the higher the sensitivity.

[1114] [EL Evaluation]

[1115] EL (unit: %) was calculated from the exposure amount formed within the range of ±10% (16.2 to 19.8 nm) of the 18 nm space width in the above LS pattern using the following formula. The larger this value, the better the performance.

[1116] EL(%)=(|E1-E2| / Eop)×100

[1117] E1: Optimal exposure amount for imparting an LS pattern with a line width of 16.2 nm and a pitch of 36 nm

[1118] E2: Optimal exposure amount for imparting an LS pattern with a line width of 19.8 nm and a pitch of 36 nm

[1119] Eop: Optimal exposure amount for imparting an LS pattern with a line width of 18 nm and a pitch of 36 nm

[1120] [LWR Evaluation]

[1121] The LS pattern obtained by investigation with Eop was measured at 10 points along the long side of the line, and the value of three times the standard deviation (σ) (3σ) from the result was calculated as LWR. The smaller this value, the smaller the roughness and the more uniform the line width pattern is obtained.

[1122] [DOF Evaluation]

[1123] As a DOF evaluation, a focus range formed within ±10% (16.2 to 19.8 nm) of the 18 nm dimension in the above LS pattern was determined. The larger this value, the wider the depth of focus.

[1124] [Assessment of Line Pattern Breakdown Limit]

[1125] The line dimensions of each exposure amount at the optimal focus of the above LS pattern were measured at 10 points along the long side. The thinnest line dimension obtained without collapse was called the collapse limit dimension. The smaller this value, the better the collapse limit.

[1126] [Survey of Phenomenon Defects]

[1127] An LS pattern with a line width of 18 nm and a pitch of 36 nm formed with the above optimal exposure amount was used with a defect inspection device KLA2360 (product name) manufactured by KLA Tenkors. The pixel size of the defect inspection device was set to 0.16 μm and the threshold to 20. Defects (number / cm²) extracted from the difference generated by pixel-level overlap with a comparison image were detected, and the number of defects per unit area (number / cm²) was calculated. Subsequently, developed defects were classified and extracted from all defects by performing a defect review, and the number of developed defects per unit area (number / cm²) was calculated. Values ​​less than 0.5 were designated as A, values ​​0.5 or more but less than 1.0 as B, values ​​1.0 or more but less than 5.0 as C, and values ​​5.0 or more as D. A smaller value indicates better performance.

[1128]

[1129]

[1130] From the results shown in Tables 5 and 6, it was found that the chemical amplification resist composition comprising a polymer containing a sulfonium salt-type monomer of the present invention exhibits good sensitivity and excellent EL, LWR, and DOF. Furthermore, it was confirmed that the breakdown limit value is small and that the pattern is resistant to breakdown even during fine pattern formation. Additionally, it was confirmed that development defects are suppressed. Therefore, it was found that the chemical amplification resist composition of the present invention is suitable as a material for EUV lithography.

[1131] [5] EUV lithography evaluation (2)

[1132] [Examples 5-1 to 5-26, Comparative Examples 5-1 to 5-18]

[1133] Each chemical amplification resist composition (R-1 to R-26, CR-1 to CR-18) shown in Tables 3 and 4 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 105°C for 60 seconds using a hot plate to produce a resist film with a film thickness of 50 nm. The above resist film was exposed using an ASML EUV scanner NXE3400 (NA0.33, σ0.9 / 0.6, quadruple illumination, wafer dimensions, pitch 46 nm, mask of a hole pattern with +20% bias), and PEB was performed for 60 seconds at the temperatures listed in Tables 7 and 8 using a hot plate, and development was performed for 30 seconds with a 2.38 mass% TMAH aqueous solution to form a hole pattern with dimensions of 23 nm.

[1134] Using a measuring SEM (CG6300) manufactured by Hitachi High-Tech Corp., the exposure amount at which the hole dimensions are formed to 23 nm was measured and this was defined as sensitivity. Additionally, the dimensions of 50 holes at this time were measured, and the value of three times the standard deviation (σ) calculated from the result (3σ) was defined as CDU. The results are shown in Tables 7 and 8.

[1135]

[1136]

[1137] From the results shown in Tables 7 and 8, it was confirmed that the chemical amplification resist composition comprising a polymer containing repeating units derived from the sulfonium salt-type monomer of the present invention has good sensitivity and excellent CDU.

Claims

Claim 1 A sulfonium salt-type monomer represented by the following formula (A). (In the equation, n1 is 0 or 1. n2 is 0, 1 or 2. n3 is 0, 1 or 2. n4 is 0, 1 or 2. Provided that when n1 is 0, 0 ≤ n2 + n3 + n4 ≤ 5, and when n1 is 1, 0 ≤ n2 + n3 + n4 ≤ 7. n5 is 0 or 1. n6 is 0, 1 or 2. n7 is 0, 1 or 2. n8 is 0, 1 or 2. Provided that when n5 is 0, 0 ≤ n6 + n7 + n8 ≤ 5, and when n5 is 1, 0 ≤ n6 + n7 + n8 ≤ 7. n9 is 0 or 1. n10 is 0, 1 or 2. n11 is 0, 1 or 2. n12 is 0, 1 or 2. However, when n9 is 0, 0 ≤ n10 + n11 + n12 ≤ 5, and when n9 is 1, 0 ≤ n10 + n11 + n12 ≤ 7. Also, 1 ≤ n2 + n6 + n10 ≤ 6, and 1 ≤ n3 + n7 + n11 ≤ 6.R 1 , R 2 and R 3 Each is independently a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom. When n4 is 2, each R 1 They may be identical or different, and 2 R 1 These may bond with each other to form a ring with the carbon atom to which they bond. When n8 is 2, each R 2 They may be the same or different, and 2 R 2 They may bond with each other to form a ring together with the carbon atom to which they bond. When n12 is 2, each R 3 They may be identical or different, and 2 R 3 These may combine with each other to form a ring together with the carbon atoms they bond to. AL1 , R AL2 and R AL3 Each is an independent acid instability phase. When n3 is 2, each R AL1 They may be the same or different. When n7 is 2, each R AL2 They may be the same or different. When n11 is 2, each R AL3 They may be identical or different. At least one -SF5 unit, -OR AL1 , -OR AL2 or -OR AL3 It is bonded to the carbon atom adjacent to the carbon atom that is bonding. Also, S + Two of the three aromatic rings bonded to may bond with each other to form a ring together with the sulfur atom to which they bond. - is a fluoroalkanesulfonic acid anion having a polymerizable group. Claim 2 In claim 1, a sulfonium salt-type monomer represented by the following formula (A1). (among the food, n2 to n4, n6 to n8, n10 to n12, R AL1 to R AL3 , R 1 to R 3 and Z - is the same as above.) Claim 3 In claim 1, the above acid unstable group is a sulfonium salt-type monomer represented by the following formula (AL-1) or (AL-2). (In the equation, m1 and m2 are each independently 0 or 1.R L1 and R L2 is, each independently, a hydrocarbyl group having 1 to 12 carbon atoms. R L3 It is silver, a hydrogen atom, or a hydrocarbyl group having 1 to 12 carbon atoms. R L1 , R L2 and R L3 A portion of the -CH2- of the hydrocarbyl group represented by may be substituted with -O- or -S-, and if the said hydrocarbyl group includes an aromatic ring, some or all of the hydrogen atoms of said aromatic ring may be substituted with a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms that may include a halogen atom, or an alkoxy group having 1 to 4 carbon atoms that may include a halogen atom. In addition, R L1 and R L2 a. They may bond with each other to form a ring together with the carbon atom to which they bond, and some of the -CH2- groups of the ring may be substituted with -O- or -S-. However, R L3 In the case of this hydrogen atom, R L1 and R L2 They bond with each other to form a ring containing multiple bonds with the carbon atoms they bond to. L4 and R L5 is, each independently, a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. R L6 Silver is a hydrocarbyl group having 1 to 20 carbon atoms, and a portion of the -CH2- of the said hydrocarbyl group may be substituted with -O- or -S-. In addition, R L5 and R L6 These, combining with each other, the carbon atoms and L that bond to them A It may form a complex group having 3 to 20 carbon atoms together with, and part of the -CH2- of the said complex group may be substituted with -O- or -S-. A is -O- or -S-. * indicates a bond loss with an adjacent -O-.) Claim 4 In paragraph 1, Z - a, a sulfonium salt-type monomer, which is an anion represented by the following formula (Z1). (In the equation, k is 0, 1, 2, or 3.R A Z are, independently, a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 Each independently, a phenylene group, naphthylene group, or *-C(=O)-OZ that may have a single bond or a substituent 11 -is. Z 11 Silver is an aliphatic hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the aliphatic hydrocarbylene group may include a halogen atom, a hydroxyl group, an ether bond, an ester bond, or a lactone ring. 2 is a single bond, ether bond, ester bond, amide bond, sulfonic acid ester bond, sulfonamide bond, carbonate bond, or carbamate bond. 3 Silver, each independently, single bond, ***-Z 31 -C(=O)-O-, ***-C(=O)-N(H)-Z 31 - or ***-OZ 31 -is. Z 31 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms. 4 is, each independently, single bond, ****-Z 41 -C(=O)-O-, ****-C(=O)-N(H)-Z 41 - or ****-OZ 41 -is. Z 41 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms. * indicates a bond loss with a carbon atom in the main chain. *** is Z 2 Indicates the bonding hand with. **** is Z 3 Represents the bonding loss with.L 1 It is a single bond, ether bond, ester bond, carbonyl group, sulfonic acid ester bond, sulfonamide bond, carbonate bond, or carbamate bond. Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. Claim 5 In paragraph 1, Z - a, a sulfonium salt-type monomer, which is an anion represented by the following formula (Z2). (In the equation, m1 is 0 or 1. m2 is 0, 1, 2, 3 or 4. m3 is 0, 1, 2 or 3. m4 is 0 or 1. m5 is 0, 1, 2, 3 or 4. m6 is 0, 1, 2 or 3. m7 is 0 or 1. m8 is 1, 2, 3 or 4. m9 is 0, 1, 2 or 3. m10 is 0, 1, 2, 3 or 4. m11 is 0 or 1. m12 is 0 or 1. Provided that when m1 is 0, 0 ≤ m2 + m3 + m12 ≤ 4, and when m1 is 1, 0 ≤ m2 + m3 + m12 ≤ 6. When m4 is 0, 0 ≤ m5 + m6 ≤ 4, and When m4 is 1, 0 ≤ m5 + m6 ≤ 6. When m7 is 0, 0 ≤ m8 + m9 ≤ 5, and when m7 is 1, 0 ≤ m8 + m9 ≤ 7. Also, 1 ≤ m2 + m5 + m8 ≤ 4.R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 11 , R 12 and R 13 Each is independently a halogen atom other than an iodine atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. When m3 is 2 or 3, each R 11 They may be identical or different, and 2 R 11 These may bond with each other to form a ring with the carbon atom to which they bond. When m6 is 2 or 3, each R 12 They may be the same or different, and 2 R 12 They may bond with each other to form a ring with the carbon atom to which they bond. When m9 is 2 or 3, each R 13 They may be identical or different, and 2 R 13 These may combine with each other to form a ring together with the carbon atoms they bond to. A , L B , L C , L D and L E Each is, independently, a single bond, an ether bond, an ester bond, a sulfonic acid ester bond, an amide bond, a sulfonate amide bond, a carbonate bond, or a carbamate bond. L1 and X L2 Rf is a hydrocarbylene group having 1 to 40 carbon atoms, which may each independently contain a single bond or a heteroatom. 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. provided that m11 and m12 are never simultaneously 0, and L A , L B , L C , L D , X L1 and X L2 There is no case where a single bond is formed at the same time. Claim 6 A monomer-type photovoltaic agent comprising a sulfonium salt-type monomer described in any one of paragraphs 1 to 5. Claim 7 A polymer comprising repeating units derived from the monomer-type photoacid generator described in paragraph 6. Claim 8 In claim 7, additionally, a polymer comprising at least one selected from a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (a2), and a repeating unit represented by the following formula (a3). (during food, R A Each is, independently, a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 Silver, single bond, phenylene group, naphthylene group, *-C(=O)-OX 11 - or *-C(=O)-N(H)-X 11 - and, the corresponding phenylene group or naphthylene group may be substituted with a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbyl group having 1 to 10 carbon atoms that may include a fluorine atom, a saturated hydrocarbyloxy group having 1 to 10 carbon atoms that may include a fluorine atom, or a halogen atom. X 11 Silver is a saturated hydrocarbylene group, a phenylene group, or a naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may include a hydroxyl group, an ether bond, an ester bond, or a lactone ring. 2 is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-. * indicates a bond loss with a carbon atom in the main chain. R 21 It is silver, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a pentafluorosulfanyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. When a1 is 2, 3, or 4, each R 21 They may be the same or different.AL 1 and AL 2 are, each independently, acid instability groups. a1 is 0, 1, 2, 3, or 4.) (In the expression, b1 is 0 or 1. b2 is 0, 1, 2 or 3 when b1 is 0, and 0, 1, 2, 3, 4 or 5 when b1 is 1.R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 3 It is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-. * indicates a bond loss with a carbon atom in the main chain. 4 is a single bond, an aliphatic hydrocarbylene group having 1 to 4 carbon atoms, a carbonyl group, a sulfonyl group, or a group obtained by a combination thereof. 5 and X 6 Each is independently an oxygen atom or a sulfur atom. However, X 4 and X 6 It is bonded to an adjacent carbon atom of the aromatic ring. 22 and R 23 It is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a hydrogen atom or a heteroatom. Also, R 22 and R 23 These may combine with each other to form a ring together with the carbon atoms to which they bond. 24 ...is a halogen atom, a hydroxyl group, a cyano group, a nitro group, a pentafluorosulfanyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom, or -N(R 24A )(R 24B ) is. R 24A and R 24B Each is independently a hydrogen atom or a hydrocarbyl group having 1 to 6 carbon atoms. When b2 is 2 or more, each R 24 They may be identical or different, and multiple R 24 They may combine with each other to form a ring together with the carbon atom of the aromatic ring to which they are bonded. Claim 9 In claim 7, additionally, a polymer comprising at least one selected from a repeating unit represented by the following formula (b1) and a repeating unit represented by the following formula (b2). (during food, R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It is a single bond or *-C(=O)-O-. * indicates a bond loss with a carbon atom in the main chain.R 31 It is a group having 1 to 20 carbon atoms comprising at least one structure selected from silver, hydrogen atoms, or hydroxyl groups other than phenolic hydroxyl groups, cyano groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, lactone rings, sulfone rings, and carboxylic acid anhydrides (-C(=O)-OC(=O)-). 32 is a halogen atom, a carboxyl group, a nitro group, a cyano group, a pentafluorosulfanyl group, a hydrocarbyl group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms that may contain a heteroatom. When c2 is 2, 3, or 4, each R 32 c1 and c2 may be the same or different. c1 is 1, 2, 3, or 4. c2 is 0, 1, 2, 3, or 4. Provided that 1 ≤ c1 + c2 ≤ 5. Claim 10 A chemical amplification resist composition comprising a base polymer comprising the polymer (A) described in claim 7. Claim 11 In item 10, additionally, (B) a chemical amplification resist composition comprising an organic solvent. Claim 12 In claim 10, additionally, (C) a chemical amplification resist composition comprising a quencher. Claim 13 In item 10, additionally, (D) a chemical amplification resist composition comprising a photoacid generator. Claim 14 In item 10, additionally, (E) a chemical amplification resist composition comprising a surfactant. Claim 15 A pattern forming method comprising: a process of forming a resist film on a substrate using a chemically amplified resist composition described in claim 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 16 A pattern forming method according to claim 15, 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.

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