Chemically amplified positive resist composition and resist pattern forming process

Abstract

The objective of the present invention is to provide a chemically amplified positive type resist composition and a pattern forming method using the said chemically amplified resist composition, which, in photolithography using high energy rays, has excellent solvent solubility, high sensitivity, high contrast, and excellent lithography performance such as resolution and LER, while also suppressing development defects and having excellent etching resistance in fine pattern formation. (A) a base polymer comprising a repeating unit represented by the following formula (A1) and a polymer whose solubility in an alkaline aqueous solution is increased by the action of an acid, and (B) a photoacid generating agent comprising an onium salt represented by the following formula (B) a chemically amplified positive type resist composition. (In the formula, Z+ is an onium cation. ArAL is an acid instability-containing group represented by the following formula (AL). However, at least one ArAL is bonded to a carbon atom adjacent to the carbon atom to which -SO3- is bonded.)

Description

Technology Field

[0001] The present invention relates to a chemically amplified positive type resist composition and a method for forming a resist pattern. Background Technology

[0002] In recent years, with the increasing integration of integrated circuits, the formation of finer patterns is required, and chemically amplified resist compositions using only acid as a catalyst are used for processing patterns of 0.2 μm or less. High-energy rays such as ultraviolet, far-ultraviolet, and electron beams (EB) are used as exposure sources for this purpose, but EB lithography, which is particularly utilized as an ultrafine processing technology, has also become indispensable as a method for processing photomask blanks when producing photomasks for semiconductor manufacturing. As for the resist compositions used in such photolithography, there are positive types that dissolve the exposed area to form a pattern and negative types that leave the exposed area intact to form a pattern, and the one that is easier to use is selected depending on the shape of the required resist pattern.

[0003] Generally, for EB-based imaging, a method is employed in which, for positive type, areas other than the region where the resist film is to be preserved are sequentially irradiated with a fine-area EB without using a mask. For negative type, the region where the resist film is to be preserved is sequentially irradiated. Since this involves erasing the entire image of a finely partitioned area of ​​the processing surface, it takes longer than batch exposure using a photomask, and high sensitivity of the resist film is required to maintain throughput. Furthermore, because the imaging time is long, a difference between the initially and later-imprinted areas is likely to occur, and the stability of the exposed area over time in a vacuum is an important performance requirement. In addition, in the processing of photomask blanks, which are particularly important applications, there are surface materials that are prone to affecting the pattern shape of the chemical amplification resist film, such as chromium oxide and chromium compound films deposited on the photomask substrate. In order to maintain high resolution and the shape after etching, maintaining the pattern profile of the resist film as a rectangle regardless of the type of substrate is also one of the important performance requirements.

[0004] The control of the sensitivity and pattern profile of the aforementioned resist film has been improved in various ways depending on the selection or combination of materials used in the resist composition and process conditions. One such improvement involves the issue of acid diffusion, which has a significant impact on the resolution of chemically amplified resist films. In photomask processing, it is required that the shape of the resulting resist pattern not change depending on the time from exposure to heating (PEB), but a major cause of this time-dependent change is the diffusion of acid generated by the exposure. This problem of acid diffusion is not limited to photomask processing but is being extensively investigated as it has a significant impact on sensitivity and resolution in general resist compositions as well.

[0005] Patent documents 1 and 2 describe examples in which acid diffusion is suppressed and roughness is reduced by increasing the volume of the acid generated from an acid generator. However, since the suppression of acid diffusion in such acid generators is still insufficient, there was a desire to develop an acid generator with smaller diffusion.

[0006] In addition, Patent Document 3 describes an example of controlling acid diffusion by incorporating sulfonic acid generated by exposure into a resin used in a resist composition. This method of suppressing acid diffusion by introducing repeating units that generate acid by exposure into a base polymer is effective for obtaining a small pattern of line edge roughness (LER). However, depending on the structure or introduction rate of such repeating units, there have been cases where problems occurred with the solubility of the base polymer containing repeating units that generate acid by exposure in organic solvents.

[0007] However, polymers having a large amount of aromatic backbones with acidic side chains, such as polyhydroxystyrene, have been used as materials for resist compositions for KrF lithography, but they have not been used as materials for resist compositions for ArF lithography because they exhibit high absorption for light around a wavelength of 200 nm. However, they are important materials for resist compositions for EB lithography, which is a powerful technique for forming patterns smaller than the processing limit of ArF lithography, and for resist compositions for extreme ultraviolet (EUV) lithography, in that high etching resistance is obtained.

[0008] As base polymers for positive-type EB lithography resist compositions or EUV lithography resist compositions, materials are mainly used that use acid generated from a photoacid generator by irradiating high-energy rays as a catalyst to deprotect acid unstable groups (acid-degradable protecting groups) masking acidic functional groups of the phenol side chains of the base polymer, thereby making them solubilized in an alkaline developer. Tertiary alkyl groups, tert-butoxycarbonyl groups, and acetal groups have been mainly used as the acid unstable groups. Here, while there is an advantage that using a protecting group with relatively low activation energy required for deprotection, such as an acetal group, yields a high-sensitivity resist film, there was a problem in that if the suppression of acid diffusion is not sufficient, the deprotection reaction occurs even in unexposed parts of the resist film, leading to degradation of LER and a decrease in the dimensional uniformity (CDU) of the pattern line width.

[0009] In addition, when using a polymer having repeating units with acetal groups and a sulfonium salt that generates an acid with a low pKa and strong acid strength, such as the fluorinated alkanesulfonic acid described in Patent Document 4, there was a problem that a large pattern of LER was formed. That is, because the acid strength of the fluorinated alkanesulfonic acid is too high for the deprotection of acetal groups, which have relatively low activation energy required for deprotection, even if the diffusion of the acid is suppressed, the deprotection reaction proceeds due to the trace amount of acid diffused into the unexposed area.

[0010] Additionally, Patent Documents 5 and 6 propose a photoacid generator that generates non-fluorinated aromatic sulfonic acid having multiple bulky alkyl substituents, and Patent Document 7 proposes a photoacid generator with a triarylbenzenesulfonic acid anion structure. Patent Document 8 proposes a photoacid generator that generates non-fluorinated aromatic sulfonic acid by introducing an iodine-containing aromatic ring. Patent Document 9 proposes a photoacid generator that generates aromatic sulfonic acid by introducing a tertiary ester-type acid instability group. Although acid diffusion is reduced by increasing the molecular weight of the generated acid through multiple alkyl substituents, aromatic rings, or iodine atoms, the suppression of acid diffusion is not yet sufficient when the purpose is to form fine patterns, leaving room for further improvement.

[0011] With the recent progress in the miniaturization of resist patterns, the formation of particularly fine isolated patterns has become important. To improve the dissolution contrast between the exposed and unexposed regions, structural modifications are being made to the acid instability groups of the base polymer. Patent Document 10 describes a structure in which the hydroxyl groups of polyhydroxystyrene are protected by tertiary ethers or acetals, and additionally, fluorine atoms are introduced at positions adjacent to them. Patent Document 11 describes a structure in which the hydroxyl and carboxyl groups of vinyl salicylic acid are protected by cyclic acetals. Both are designed to increase the dissolution rate of the polymer after the deprotection reaction of the acid instability groups in the exposed region, and some degree of performance improvement has been confirmed. Prior art literature

[0012] Japanese Patent Publication No. 2009-053518 Japanese Patent Publication No. 2010-100604 Japanese Patent Publication No. 2011-22564 Japanese Patent No. 5083528 Japanese Patent No. 6248882 Japanese Patent No. 7067271 Japanese Patent No. 7032549 Japanese Patent Publication No. 2023-177038 Japanese Patent No. 7531671 Japanese Patent Publication No. 2025-000201 International Publication No. 2023 / 162837 The problem to be solved

[0013] In recent years, there has been a demand for resist compositions that are excellent not only in line and space (LS), iso-line (IL), and iso-space (IS), but also in hole pattern shape. In the acid generator described in Patent Document 5, which has a large volume of generated acid and suppresses acid diffusion, a pattern with good resolution and roughness was obtained, but there was a problem that corner rounding occurred in the hole pattern.

[0014] The present invention has been made in consideration of the above circumstances, and in particular, aims to provide a chemically amplified positive type resist composition and a pattern forming method using the said chemically amplified resist composition, which has excellent solvent solubility, high sensitivity, high contrast, and excellent lithography performance such as resolution and LER in photolithography using high-energy rays such as KrF excimer laser light, ArF excimer laser light, electron beam (EB), and EUV, while also suppressing development defects and having excellent etching resistance in fine pattern formation. means of solving the problem

[0015] As a result of repeated careful consideration to achieve the above objective, the inventors have found a polymer comprising repeating units having a cyclic acetal structure condensed in an aromatic ring and a photoacid generator that generates an arenesulfonic acid derivative, and -SO3 -α has 2, 3, or 4 aryl groups having ether-type acid instability groups on the aromatic ring to which it is bonded, and at least one aryl group having an ether-type acid instability group is -SO3 - It was discovered that when an onium salt having a structure in which a carbon atom adjacent to a carbon atom to which it is bonded is introduced into a resist composition as a photoacid generator, the acid generated therefrom has a suitable acidity and excessive diffusion of the acid is suppressed, thereby obtaining a resist pattern with good resolution, a low LER, and suppressed development defects, and additionally, a resist pattern with good rectangularity is obtained due to suitable dissolution inhibition, and thus the present invention was made.

[0016] That is, the present invention provides the following chemically amplified positive type resist composition and a method for forming a resist pattern.

[0017] 1. (A) A base polymer comprising a repeating unit represented by the following formula (A1) and a polymer whose solubility in an alkaline aqueous solution is increased by the action of an acid, and

[0018] (B) A photoacid generator comprising an onium salt represented by the following formula (B)

[0019] A chemically amplified positive type resist composition comprising

[0020]

[0021] (In the equation, a1 is 0 or 1. a2 is 0, 1, 2 or 3 when a1 is 0, and 0, 1, 2, 3, 4 or 5 when a1 is 1.

[0022] R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0023] X 1 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.

[0024] X2 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.

[0025] X 3 and X 4 is, each independently, an oxygen atom or a sulfur atom. However, X 2 and X 4 It is bonded to an adjacent carbon atom of the aromatic ring.

[0026] R 1 and R 2 is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a hydrogen atom or a heteroatom. Also, R 1 and R 2 a, they may combine with each other to form a ring together with the carbon atom to which they are bonded.

[0027] R 3 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 3A )(R 3B ) is. R 3A and R 3B Each is independently a hydrogen atom or a hydrocarbyl group having 1 to 6 carbon atoms. When a2 is 2 or more, each R 3 They may be identical or different from each other, and multiple R 3 These may combine with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded.

[0028]

[0029] [In the equation, n1 is 0 or 1. n2 is 0, 1, 2, 3 or 4. n3 is 2, 3 or 4. Provided that when n1 is 0, 2 ≤ n2 + n3 ≤ 5, and when n1 is 1, 2 ≤ n2 + n3 ≤ 7.

[0030] R 101 It is 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, a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 1 to 20 carbon atoms that may contain a heteroatom. When n2 is 2, 3, or 4, each R 101 They may be identical or different from each other, and multiple R 101 These may combine with each other to form a ring together with the carbon atoms they bond with.

[0031] Z + is an onium cation.

[0032] Ar AL is an acid instability group containing a group represented by the following formula (AL). provided that at least one Ar AL silver, -SO3 - It is bonded to the carbon atom adjacent to the carbon atom it is bonding to.

[0033]

[0034] (In the equation, n4 is 0 or 1. n5 is 0, 1, 2, 3 or 4. n6 is 0, 1, 2, 3 or 4. n7 is 1 or 2. Provided that when n4 is 0, 1 ≤ n5 + n6 + n7 ≤ 5, and when n4 is 1, 1 ≤ n5 + n6 + n7 ≤ 7.

[0035] R 102is a halogen atom other than a fluorine 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 n5 is 2, 3, or 4, each R 102 They may be identical or different from each other, and multiple R 102 They may combine with each other to form a ring together with the carbon atoms they bond with.

[0036] R F is 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, a fluorinated saturated hydrocarbylthio group having 1 to 6 carbon atoms, or a pentafluorosulfanyl group. When n6 is 2, 3, or 4, each R F They may be the same or different.

[0037] R L1 and R L2 is, each independently, a hydrocarbyl group having 1 to 12 carbon atoms. R L3 It is 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 or a multiple bond, some or all of the hydrogen atoms bonded to the carbon atoms constituting the said aromatic ring or multiple bond 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, RL1 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 cases where this cyclic structure, directional ring, and multiple bonds are not all included, R L1 and R L2 They bond with each other to form a ring together with the carbon atoms they bond to, and some of the -CH2- of the ring may be substituted with -O- or -S-.

[0038] * indicates a joining hand.)]

[0039] 2. X 3 and X 4 A chemically amplified positive type resist composition in which all atoms are oxygen atoms.

[0040] 3. X 2 A chemically amplified positive resist composition having 1 or 2 carbonyl groups.

[0041] 4. A chemically amplified positive type resist composition of any one of 1 to 3, wherein the above-mentioned photoacid generator is represented by the following formula (B1).

[0042]

[0043] (Eating, n1, n2, n3, n5, n6, n7, R 101 , R 102 , R F , R L1 to R L3 and Z + is the same as above.)

[0044] 5. A chemically amplified positive type resist composition of 4 in which the above-mentioned photoacid generator is represented by the following formula (B2).

[0045]

[0046] (Eating, n2, n3, n5, n6, n7, R 101 , R 102, R F , R L1 to R L3 and Z + is the same as above.)

[0047] 6. Z + A chemically amplified positive type resist composition of any one of 1 to 5, wherein the sulfonium cation represented by the following formula (Z-1) or the iodonium cation represented by the following formula (Z-2).

[0048]

[0049] (during food, R ct1 to R ct5 is a hydrocarbyl group having 1 to 30 carbon atoms, which may each independently contain a halogen atom or a heteroatom. Also, R ct1 and R ct2 a. They may combine with each other to form a ring together with the sulfur atom to which they combine.)

[0050] 7. Z + a. A chemically amplified positive type resist composition of any one of 1 to 5, which is a sulfonium cation represented by the following formula (Z-3).

[0051]

[0052] (In the equation, m1 is 0 or 1. m2 is 0 or 1. m3 is 0 or 1. m4 is 0, 1, 2, 3 or 4. m5 is 0, 1, 2, 3 or 4. m6 is 0, 1, 2, 3, 4, 5 or 6. m7 is 0, 1, 2, 3, 4, 5 or 6. m8 is 0, 1 or 2. m9 is 0, 1 or 2. m10 is 0, 1 or 2. m11 is 0 or 1. m12 is 0, 1, 2, 3 or 4. m13 is 0, 1 or 2. m14 is 0, 1 or 2. provided that when m1 is 0, 0 ≤ m6 + m9 ≤ 4, and m1 is When m2 is 1, 0 ≤ m6 + m9 ≤ 6. When m2 is 0, 0 ≤ m7 + m10 ≤ 4, and when m2 is 1, 0 ≤ m7 + m10 ≤ 6. When m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4, and when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6. When m11 is 0, 0 ≤ m12 + m13 ≤ 4, and when m11 is 1, 0 ≤ m12 + m13 ≤ 6. Also, m4 + m12 ≥ 1.

[0053] 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. When m5 is 2, 3, or 4, each R F1 They may be the same or different. When m6 is 2, 3, 4, 5, or 6, each R F2 may be the same or different. When m7 is 2, 3, 4, 5, or 6, each R F3 They may be the same or different.

[0054] R ct6 to R ct9is a halogen atom other than an iodine atom and a fluorine atom, a nitro group, a cyano 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 m8 is 2, 2 R ct6 They may be identical or different, and 2 R ct6 These may bond with each other to form a ring with the carbon atom they bond to. When m9 is 2, 2 R ct7 They may be identical or different, and 2 R ct7 These may bond with each other to form a ring with the carbon atom to which they bond. When m10 is 2, 2 R ct8 They may be identical or different, and 2 R ct8 These may bond with each other to form a ring with the carbon atom to which they bond. When m13 is 2, 2 R ct9 They may be the same or different, and 2 R ct9 They may combine with each other to form a ring together with the carbon atoms they bond with.

[0055] In addition, S in the sulfonium cation + Direction rings that directly bind to each other combine with S + It is also acceptable to form a ring with.

[0056] L A and L B Each is independently a single bond, ether bond, ester bond, amide bond, sulfonic acid ester bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0057] X L It is a hydrocarbylene group having 1 to 40 carbon atoms that may contain single bonds or heteroatoms.

[0058] 8. A chemically amplified positive type resist composition of any one of 1 to 7, wherein the polymer further comprises a repeating unit represented by the following formula (A2).

[0059]

[0060] (In the equation, b1 is 0, 1, or 2. b2 is 1, 2, or 3. b3 is an integer satisfying 0 ≤ b3 ≤ 5 + 2(b1) - b2.

[0061] R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0062] Y 1 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.

[0063] R 11 It is a saturated hydrocarbyl group having 1 to 6 carbon atoms that may be substituted with a halogen atom, a nitro group, a carboxyl group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms that may be substituted with a halogen atom, or a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen atom.

[0064] A 1 ...is a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and a portion of the -CH2- of the said saturated hydrocarbylene group may be substituted with -O-.)

[0065] 9. A chemical amplification positive type resist composition of any one of 1 to 8, wherein the polymer comprises at least one selected from a repeating unit represented by the following formula (A3), a repeating unit represented by the following formula (A4), and a repeating unit represented by the following formula (A5).

[0066]

[0067] (In the expression, c is 0, 1, 2, 3, 4, 5 or 6. d is 0, 1, 2, 3 or 4. e1 is 0 or 1. e2 is 0, 1 or 2. e3 is 0, 1, 2, 3, 4 or 5.

[0068] R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0069] R 21 and R 22 Each is independently a hydroxyl group, a halogen atom, a saturated hydrocarbyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, a saturated hydrocarbyloxy group having 1 to 8 carbon atoms that may be substituted with a halogen atom, or a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen atom.

[0070] R 23 The group is a saturated hydrocarbyl group having 1 to 20 carbon atoms, a saturated hydrocarbyloxy group having 1 to 20 carbon atoms, a saturated hydrocarbylcarbonyloxyoxy group having 2 to 20 carbon atoms, a saturated hydrocarbyloxyhydrocarbyl group having 2 to 20 carbon atoms, a saturated hydrocarbylthiohydrocarbyl group having 2 to 20 carbon atoms, a halogen atom, a nitro group, or a cyano group, and when e3 is 1 or 2, it may be a hydroxyl group.

[0071] A 2 is a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and a portion of the -CH2- of the said saturated hydrocarbylene group may be substituted with -O-.)

[0072] 10. A chemically amplified positive type resist composition of any one of 1 to 9, wherein the polymer further comprises at least one selected from a repeating unit represented by the following formula (A6-1) and a repeating unit represented by the following formula (A6-2).

[0073]

[0074] (In the equation, f1 is 0 or 1. f2 is 0, 1 or 2. f3 is an integer satisfying 0 ≤ f3 ≤ 5 + 2(f2) - f4. f4 is 1, 2 or 3. f5 is 0 or 1.

[0075] f11 is 0, 1, or 2. f12 is 0, 1, or 2. f13 is 0, 1, or 2. f14 is 0, 1, 2, 3, 4, or 5.

[0076] R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

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

[0078] A 4 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OA 41 -is. A 41 is an aliphatic hydrocarbylene group having 1 to 20 carbon atoms, or a phenylene group or a naphthylene group, which 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.

[0079] R 31 It is a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms that may be substituted with a halogen atom, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms that may be substituted with a halogen atom, or a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen atom.

[0080] R 32 and R 33 Each is a hydrocarbyl group having 1 to 10 carbon atoms that may independently contain a heteroatom, and R 32 and R 33These may combine with each other to form a ring together with the carbon atoms they bond with.

[0081] R 34 Each is independently a fluorine atom, a carbon-1 to carbon-5 fluorinated alkyl group, or a carbon-1 to carbon-5 fluorinated alkoxy group.

[0082] R 35 Each is a hydrocarbyl group having 1 to 10 carbon atoms that may independently contain a heteroatom.

[0083] X is an acid unstable group when f4 is 1, and a hydrogen atom or an acid unstable group when f4 is 2 or 3, but at least one is an acid unstable group.

[0084] 11. A chemical amplification positive type resist composition of any one of 1 to 10, wherein the polymer comprises at least one selected from a repeating unit represented by the following formula (A7), a repeating unit represented by the following formula (A8), a repeating unit represented by the following formula (A9), a repeating unit represented by the following formula (A10), and a repeating unit represented by the following formula (A11).

[0085]

[0087] (In the equation, g1 and g2 are each independently 0, 1, 2, or 3. h1 is 0 or 1. h2 is 0, 1, 2, 3, or 4. h3 is 0, 1, 2, 3, or 4. provided that when h1 is 0, 0 ≤ h2 + h3 ≤ 4, and when h1 is 1, 0 ≤ h2 + h3 ≤ 6.

[0088] R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0089] Z 1 It is a phenylene group that may have a single bond or a substituent.

[0090] Z 2 is a single bond, **-C(=O)-OZ21 -, **-C(=O)-N(H)-Z 21 - or **-OZ 21 -is. Z 21 It is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining these, and may include a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group.

[0091] Z 3 It is a single bond, ether bond, ester bond, sulfonic acid ester bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0092] Z 4 It is a single bond, or an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining these, and may include a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group.

[0093] Z 5 are, respectively, single bond, a phenylene group that may have a substituent, a naphthylene group that may have a substituent, *-C(=O)-OZ 51 - or *-C(=O)-N(R)-Z 51 -is. Z 51 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. R is a hydrocarbylene group having 1 to 10 carbon atoms that may include a hydrogen atom or a heteroatom.

[0094] Z 6 It is a single bond, ether bond, ester bond, sulfonic acid ester bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0095] Z 7Silver, each independently, single bond, ***-Z 71 -C(=O)-O-, ***-C(=O)-N(R)-Z 71 - or ***-OZ 71 -is. Z 71 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms. R is the same as above.

[0096] Z 8 Silver, each independently, single bond, ****-Z 81 -C(=O)-O-, ****-C(=O)-N(R)-Z 81 - or ****-OZ 81 -is. Z 81 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms. R is the same as above.

[0097] Z 9 is a single bond, methylene group, ethylene group, phenylene group, fluorinated phenylene group, phenylene group substituted with a trifluoromethyl group, *-C(=O)-OZ 91 -, *-C(=O)-N(R)-Z 91 - or *-OZ 91 -is. Z 91 is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may include a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. R is the same as above.

[0098] * indicates bond loss with carbon atoms in the main chain. ** is Z 1 Indicates the bonding loss with. *** is Z 6 Indicates the bond with. **** is Z 7 It represents the bonding hand with.

[0099] L 1 It is a single bond, ether bond, ester bond, carbonyl group, sulfonic acid ester bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0100] Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms.

[0101] 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.

[0102] Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. provided that all Rf 5 and Rf 6 There is no case where it becomes a hydrogen atom at the same time.

[0103] Rf 7 The fluorine atom, the C1 to C6 fluorinated alkyl group, and the C1 to C6 fluorinated alkoxy group are C1 to C6 fluorinated alkyl thio groups or pentafluorosulfanyl groups. When h2 is 2, 3, or 4, each Rf 7 They may be the same or different.

[0104] R 41 and R 42 is a hydrocarbyl group having 1 to 20 carbon atoms that may each independently contain a heteroatom. Also, R 41 and R 42 a, they may combine with each other to form a ring together with the sulfur atom to which they combine.

[0105] R 43 It is a hydrocarbyl group having 1 to 20 carbon atoms that may contain halogen atoms other than fluorine atoms or heteroatoms. When h3 is 2, 3, or 4, each R 43 They may be identical or different from each other, and multiple R 43 These may combine with each other to form a ring together with the carbon atoms they bond with.

[0106] M - is a non-nucleophilic counterion.

[0107] A + is an onium cation.)

[0108] 12. A chemically amplified positive type resist composition of any one of 1 to 11, wherein the content of repeating units having an aromatic ring backbone among the total repeating units of the polymer included in the base polymer is 60 mol% or more.

[0109] 13. Additionally, (C) a chemically amplified positive type resist composition of any one of 1 to 12 comprising an organic solvent.

[0110] 14. Additionally, (D) a chemically amplified positive type resist composition of any one of 1 to 13 comprising a quencher.

[0111] 15. A chemical amplification positive type resist composition of any one of 1 to 14 comprising a fluorine atom-containing polymer that additionally comprises at least one selected from the repeating unit represented by the following formula (E1), the repeating unit represented by the following formula (E2), the repeating unit represented by the following formula (E3), and the repeating unit represented by the following formula (E4), and additionally comprises at least one selected from the repeating unit represented by the following formula (E5) and the repeating unit represented by the following formula (E6).

[0112]

[0113] (In the equation, j1 is 1, 2, or 3. j2 is an integer satisfying 0 ≤ j2 ≤ 5 + 2(j3) - j1. j3 is 0 or 1. k is 1, 2, or 3.

[0114] R B Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0115] R C Each is independently a hydrogen atom or a methyl group.

[0116] R 301 , R 302 , R 304 and R 305 Each is independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 10 carbon atoms.

[0117] R 303 , R 306 , R 307 and R 308 Each independently is a hydrogen atom, a hydrocarbyl group having 1 to 15 carbon atoms, a fluorinated hydrocarbyl group having 1 to 15 carbon atoms, or an acid instability group, and R 303 , R 306 , R 307 and R 308 When this is a hydrocarbyl group or a fluorinated hydrocarbyl group, an ether bond or a carbonyl group may be interposed between the carbon-carbon bonds.

[0118] R 309 is a straight-chain or branched hydrocarbyl group having 1 to 5 carbon atoms, which may include a hydrogen atom or a group containing a heteroatom between carbon-carbon bonds. When j1 is 2 or 3, each R 309 They may be the same or different.

[0119] R 310 It is a straight-chain or branched hydrocarbyl group having 1 to 5 carbon atoms, wherein a group containing a heteroatom may be interposed between carbon-carbon bonds. When j2 is 2 or more, each R 210 They may be the same or different.

[0120] R 311 The silver is a saturated hydrocarbyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and a portion of the -CH2- of the saturated hydrocarbyl group may be substituted with an ester bond or an ether bond.

[0121] W 1It is a (k+1) hydrocarbon group having 1 to 20 carbon atoms or a (k+1) fluorinated hydrocarbon group having 1 to 20 carbon atoms.

[0122] W 2 is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-. * is a bond with a carbon atom in the main chain.

[0123] W 3 is a single bond, -O-, *-C(=O)-OW 31 -W 32 - or *-C(=O)-N(H)-W 31 -W 32 -is. W 31 It is a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms. W 32 is a single bond, ester bond, ether bond, or sulfonamide bond. * is a bond with a carbon atom of the main chain.)

[0124] 16. Additionally, a chemically amplified positive type resist composition of any one of 1 to 15 comprising a photoacid generating agent other than the onium salt represented by formula (B).

[0125] 17. A method for forming a resist pattern comprising: a process of forming a resist film on a substrate using a chemically amplified positive type resist composition of any one of 1 to 16; a process of irradiating a pattern onto the resist film using a high-energy beam; and a process of developing the resist film irradiated with the pattern using an alkaline developer.

[0126] 18. A method for forming a resist pattern of 17, wherein the high-energy line is an extreme ultraviolet or electron line with a wavelength of 3 to 15 nm.

[0127] 19. A method for forming a resist pattern of 17 or 18, wherein the outermost surface of the substrate comprises a material including chromium.

[0128] 20. A method for forming a resist pattern of any one of 17 to 19, wherein the substrate is a photomask blank. Effects of the invention

[0129] A chemically amplified positive type resist composition comprising an onium salt represented by formula (B) as a photoacid generator can impart a pattern with extremely high resolution, a small LER, and suppressed development defects in microfabrication technology, particularly EB lithography and EUV lithography. In addition, the onium salt represented by formula (B) is suitable as a material for a chemically amplified positive type resist composition because it can impart a pattern of good rectangularity by having appropriate dissolution inhibition properties. Specific details for implementing the invention

[0130] The present invention will be described in detail below. In addition, in the following description, an asymmetric carbon may be present in the structure represented by the chemical formula, and enantiomers or diastereomers may be present, but 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.

[0131] [Chemical Amplification Positive Type Resist Composition]

[0132] [(A) Base Polymer]

[0133] The chemically amplified positive type resist composition of the present invention comprises (A) a base polymer comprising a polymer whose solubility in an alkaline developer is increased by the action of an acid.

[0134] The above polymer includes a repeating unit represented by the following formula (A1) (hereinafter also referred to as repeating unit A1).

[0135]

[0136] In formula (A1), a1 is 0 or 1. When a1 is 0, it is a benzene ring, and when a1 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable for a1 to be a benzene ring of 0. a2 is 0, 1, 2, or 3 when a1 is 0, and 0, 1, 2, 3, 4, or 5 when a1 is 1. From the perspective of raw material procurement, it is preferable for a2 to be 0, 1, 2, or 3, and more preferable for it to be 0, 1, or 2.

[0137] In equation (A1), 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.

[0138] In Equation (A1), X 1 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.

[0139] In Equation (A1), X 2 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.

[0140] In Equation (A1), X 3 and X 4 is, each independently, an oxygen atom or a sulfur atom. However, X 2 and X 4 It is bonded to an adjacent carbon atom of the aromatic ring. X 3 and X 4 They may be identical or different, but in terms of reactivity, X 3 and X4 It is desirable that all of them are oxygen atoms.

[0141] In equation (A1), R 1 and R 2Each 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, 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.

[0142] Also, R 1 and R 2The 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.

[0143] In equation (A1), R 3 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 3A )(R 3B ) is. R 3A and R 3BEach 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. As a specific example, R 1 and R 2 Examples of hydrocarbyl groups represented by may be those similar to those exemplified. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a 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 a2 is 2 or more, each R 3 They may be the same or different.

[0144] Also, when a2 is 2 or greater, multiple R 3These 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.

[0145] Specific examples of the repeating unit A1 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.

[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] In the chemical amplification resist composition of the present invention, (A) as a structural feature of the base polymer, it may include a repeating unit A1 having a cyclic acetal structure condensed in an aromatic ring. The cyclic acetal structure condensed in an aromatic ring has good solvent solubility and also acts as an acid unstable group, so that a deprotection reaction proceeds under the action of an acid, generating two polar groups. This improves the contrast between the exposed area and the unexposed area. In addition, since the two polar groups generated are bonded to adjacent carbon atoms, the hydroxyl or carboxyl groups form hydrogen bonds with each other. This suppresses swelling caused by the alkaline developer during alkaline development and suppresses the collapse of the resist pattern in the unexposed area. The cyclic acetal structure condensed in an aromatic ring remaining in the unexposed area becomes a bicyclocyclic structure, thus exhibiting high resistance in the etching process. The polymer before exposure has high solvent solubility of the cyclic acetal structure contained in the repeating unit A1, so precipitation in the solvent is suppressed, and when developed with an alkaline developer after exposure, the polar group generated after deprotection of the acetal structure has high affinity for the alkaline developer, so the exposed area is effectively removed, thereby reducing the risk of development defects.

[0197] Among the total repeating units of the polymer, the content of repeating unit A1 is preferably 5 to 50 mol%, more preferably 10 to 45 mol%, and even more preferably 15 to 40 mol%. Repeating unit A1 may be used alone or in combination of two or more types.

[0198] The above polymer may additionally include a repeating unit represented by the following formula (A2) (hereinafter also referred to as repeating unit A2).

[0199]

[0200] In formula (A2), b1 is 0, 1, or 2, and when 0 it is a benzene skeleton, when 1 it is a naphthalene skeleton, and when 2 it is an anthracene skeleton. b2 is 1, 2, or 3. b3 is an integer satisfying 0 ≤ b3 ≤ 5 + 2(b1) - b2. When b1 is 0, preferably b2 is 0, 1, 2, or 3 and b3 is 1, 2, or 3, and when b1 is 1 or 2, preferably b2 is 0, 1, 2, 3, or 4 and b3 is 1, 2, or 3.

[0201] In equation (A2), R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0202] In Equation (A2), Y 1 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.

[0203] In equation (A2), R 11 The saturated hydrocarbyl group having 1 to 6 carbon atoms that may be substituted with a halogen atom, a nitro group, a carboxyl group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms that may be substituted with a halogen atom, or a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen atom. The saturated hydrocarbyl portion of the saturated hydrocarbyl group, the saturated hydrocarbyloxy group, and the saturated hydrocarbylcarbonyloxy group may be straight-chain, branched, or cyclic, and specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, and structural isomers thereof; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups; and groups obtained by combining these. If the number of carbon atoms is below the upper limit, solubility in alkaline developer is good. When b3 is 2 or greater, each R 11 They may be the same or different.

[0204] In equation (A2), A 1 The group may be a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and a portion of the -CH2- of the saturated hydrocarbylene group may be substituted with -O-. The saturated hydrocarbylene group may be straight-chain, branched, or cyclic, and specific examples thereof include an alkanediyl group having 1 to 10 carbon atoms such as a methylene 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, and structural isomers thereof; a cyclic saturated hydrocarbylene group having 3 to 10 carbon atoms such as a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group; or a group obtained by combining these. In the case where the above saturated hydrocarbillene group includes an ether bond, Y in formula (A2) 1 In the case of *-C(=O)-O- or *-C(=O)-N(H)-, -O- or -N(H)- may be placed at any location excluding the space between the carbon atom at the α position and the carbon atom at the β position. Also, Y 1 In the case of this single bond, the atom bonded to the main chain becomes an etheric oxygen atom, and a second etheric bond may be formed at any location other than between the carbon atom at the α position and the carbon atom at the β position with respect to the said etheric oxygen atom. Additionally, it is preferable that the number of carbon atoms in the saturated hydrocarbylene group be 10 or less, as this allows for sufficient solubility in an alkaline developer.

[0205] Y 1 and A 1 In the case where all of these are single bonds, that is, where the aromatic ring is directly bonded to the polymer's main chain (i.e., the linker (-Y 1 -A 1In the case where it does not have -), preferred examples of the repeating unit A2 include units derived from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene, 6-hydroxy-2-vinylnaphthalene, etc. Specifically, those shown below may be examples, but are not limited to these. In addition, among the following formulas, R A It is the same as above.

[0206]

[0207]

[0208]

[0209] Y 1 This *-C(=O)-O- or *-C(=O)-N(H)- (i.e., as a linker Y 1 -A 1 In the case of having -, preferred examples of the repeating unit A2 include those shown below, but are not limited thereto. Also, among the following formulas, R A It is the same as above.

[0210]

[0211]

[0212]

[0213]

[0214]

[0215] When the above polymer includes repeating unit A2, the content thereof is preferably 30 to 95 mol% of the total repeating units constituting the polymer, and more preferably 35 to 85 mol%. However, if the polymer described later includes at least one of the repeating unit represented by formula (A3), the repeating unit represented by formula (A4), and the repeating unit represented by formula (A5) which imparts high etching resistance, and the unit has a phenolic hydroxyl group as a substituent, it is preferable to add the ratio thereof to be within the above range. Repeating unit A2 may be used alone or in combination of two or more types.

[0216] The above polymer may include at least one selected from a repeating unit represented by the following formula (A3) (hereinafter also referred to as repeating unit A3), a repeating unit represented by the following formula (A4) (hereinafter also referred to as repeating unit A4), and a repeating unit represented by the following formula (A5) (hereinafter also referred to as repeating unit A5).

[0217]

[0218] In equations (A3) and (A4), c is 0, 1, 2, 3, 4, 5 or 6. d is 0, 1, 2, 3 or 4.

[0219] Among equations (A3) and (A4), R 21 and R 22 Each is independently a hydroxyl group, a halogen atom, a saturated hydrocarbyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, a saturated hydrocarbyloxy group having 1 to 8 carbon atoms that may be substituted with a halogen atom, or a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen atom. The above saturated hydrocarbyl group, saturated hydrocarbyloxy group, and saturated hydrocarbylcarbonyloxy group may be linear, branched, or cyclic. When c is 2, 3, 4, 5, or 6, each R 21They may be the same or different. When d is 2, 3, or 4, each R 22 They may be the same or different.

[0220] In formula (A5), e1 is 0 or 1. e2 is 0, 1 or 2. When e2 is 0, it is a benzene skeleton; when e2 is 1, it is a naphthalene skeleton; and when e2 is 2, it is an anthracene skeleton. e3 is 0, 1, 2, 3, 4 or 5. When e2 is 0, e3 is preferably 0, 1, 2 or 3, and when e2 is 1 or 2, e3 is preferably 0, 1, 2, 3 or 4.

[0221] In equation (A5), R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0222] In equation (A5), R 23 Silver, a saturated hydrocarbyl group having 1 to 20 carbon atoms, a saturated hydrocarbyloxy group having 1 to 20 carbon atoms, a saturated hydrocarbylcarbonyloxyoxy group having 2 to 20 carbon atoms, a saturated hydrocarbyloxyhydrocarbyl group having 2 to 20 carbon atoms, a saturated hydrocarbylthiohydrocarbyl group having 2 to 20 carbon atoms, a halogen atom, a nitro group, or a cyano group, and may be a hydroxyl group when e3 is 1 or 2. The above saturated hydrocarbyl group, saturated hydrocarbyloxyoxy group, saturated hydrocarbylcarbonyloxyoxyoxyoxycarbyl group, saturated hydrocarbyloxyhydrocarbyl group, and saturated hydrocarbylthiohydrocarbyl group may be straight-chain, branched, or cyclic. When e3 is 2, 3, 4, or 5, each R 23 They may be the same or different.

[0223] In equation (A5), A 2is a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and a portion of the -CH2- of the said saturated hydrocarbylene group may be substituted with -O-. The said saturated hydrocarbylene group may be straight-chain, branched, or cyclic, and as a specific example, A in formula (A2). 1 In the explanation, one can cite the same as the example given.

[0224] When at least one of the repeating units A3 to A5 is used as a constituent unit of the polymer, the effect of increasing etching resistance or EB irradiation resistance during pattern inspection is obtained by adding a ring structure to the main chain in addition to the etching resistance of the aromatic ring.

[0225] When the above polymer includes repeating units A3 to A5, the content thereof is preferably 5 mol% or more of the total repeating units of the polymer in order to obtain the effect of improving etching resistance. In addition, the content of repeating units A3 to A5 is preferably 25 mol% or less of the total repeating units constituting the polymer, and more preferably 20 mol% or less. It is preferable that the amount of non-functionalized units or functionalized units other than hydroxyl groups introduced is 25 mol% or less, as there is no risk of developing defects occurring. Repeating units A3 to A5 may be used as a single type or in combination of two or more types.

[0226] The above polymer is preferably composed of at least one selected from repeating unit A1, repeating unit A2, and repeating units A3 to A5, in that it offers excellent compatibility of high etching resistance and resolution. At this time, it is preferable that these repeating units comprise 60 mol% or more of the total repeating units of the polymer, more preferable that they comprise 70 mol% or more, even more preferable that they comprise 80 mol% or more, and even more preferable that they comprise 90 mol% or more.

[0227] The polymer may additionally include at least one selected from the repeating unit represented by the following formula (A6-1) and the repeating unit represented by the following formula (A6-2).

[0228]

[0229] In formula (A6-1), f1 is 0 or 1. f2 is 0, 1 or 2, and when 0 it is a benzene skeleton, when 1 it is naphthalene, and when 2 it is anthracene. f3 is an integer satisfying 0 ≤ f3 ≤ 5 + 2(f2) - f4. f4 is 1, 2 or 3. f5 is 0 or 1. When f2 is 0, preferably f3 is 0, 1, 2 or 3 and f4 is 1, 2 or 3, and when f2 is 1 or 2, preferably f3 is 0, 1, 2, 3 or 4 and f4 is 1, 2 or 3.

[0230] In Equation (A6-2), f11 is 0, 1, or 2. f12 is 0, 1, or 2. f13 is 0, 1, or 2. f14 is 0, 1, 2, 3, 4, or 5.

[0231] Among equations (A6-1) and (A6-2), R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0232] In Equation (A6-1), A 3The group is a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and a portion of the -CH2- of the saturated hydrocarbylene group may be substituted with -O-. The saturated hydrocarbylene group may be straight-chain, branched, or cyclic, and specific examples include alkanediyl groups having 1 to 10 carbon atoms such as methylene groups, ethane-1,2-diyl groups, propane-1,3-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, and structural isomers thereof; cyclic saturated hydrocarbylene groups having 3 to 10 carbon atoms such as cyclopropanediyl groups, cyclobutanediyl groups, cyclopentanediyl groups, and cyclohexanediyl groups; and groups obtained by combining these. In the case where the above-mentioned saturated hydrocarbylene group contains an ether bond, when f1 in formula (A6-1) is 1, it may be placed at any location other than between the carbon atom at the α position and the carbon atom at the β position with respect to the ester oxygen atom. Also, when f1 is 0, the atom bonded to the main chain becomes an ether oxygen atom, and a second ether bond may be placed at any location other than between the carbon atom at the α position and the carbon atom at the β position with respect to the ether oxygen atom. Additionally, it is preferable that the number of carbon atoms in the above-mentioned saturated hydrocarbylene group be 10 or less, as sufficient solubility in an alkaline developer can be obtained.

[0233] In Equation (A6-2), A 4 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OA 41 -is. A 41 is an aliphatic hydrocarbylene group having 1 to 20 carbon atoms, or a phenylene group or a naphthylene group, which 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.

[0234] In Equation (A6-1), R 31The saturates are a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms that may be substituted with a halogen atom, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms that may be substituted with a halogen atom, or a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen atom. The saturated hydrocarbyl portions of the saturated hydrocarbyl group, the saturated hydrocarbyloxy group, and the saturated hydrocarbylcarbonyloxy group may be straight-chain, branched, or cyclic, and specific examples thereof include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, and structural isomers thereof; cycloalkyl groups having 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups; and groups obtained by combining these. If the number of carbon atoms is below the upper limit, solubility in alkaline developer is good. When f3 is 2 or greater, each R 31 They may be the same or different.

[0235] In Equation (A6-2), R 32 and R 33 Each is a hydrocarbyl group having 1 to 10 carbon atoms that may independently contain a heteroatom, and R 32 and R 33 These may combine with each other to form a ring together with the carbon atoms they bond with.

[0236] In Equation (A6-2), R 34 Each is independently a fluorine atom, a C1 to C5 fluorinated alkyl group, or a C1 to C5 fluorinated alkoxy group. When f13 is 2, each R 34 They may be the same or different.

[0237] In Equation (A6-2), R 35 is a hydrocarbyl group having 1 to 10 carbon atoms that may each independently contain a heteroatom. When f14 is 2, 3, 4, or 5, each R35 They may be the same or different.

[0238] In formula (A6-1), when f4 is 1, X is an acid unstable group. When f4 is 2 or 3, X is, respectively, a hydrogen atom or an acid unstable group, but at least one is an acid unstable group. That is, the repeating unit A6-1 is such that at least one phenolic hydroxyl group bonded to the aromatic ring is protected by an acid unstable group, or a carboxyl group bonded to the aromatic ring is protected by an acid unstable group. As for the acid unstable group, any that is detached by acid and imparted an acidic group, which has been used in a number of known chemically amplified positive type resist compositions, can be used without particular limitation.

[0239] As the above acid instability group, for example, a tertiary saturated hydrocarbyl group may be used. In order to obtain the obtained monomer for polymerization by distillation, the tertiary saturated hydrocarbyl group is preferably one having 4 to 18 carbon atoms.

[0240] As for the saturated hydrocarbyl group bonded to the tertiary carbon atom of the above-mentioned tertiary saturated hydrocarbyl group, it is preferable that it has 1 to 15 carbon atoms. The above-mentioned saturated hydrocarbyl group having 1 to 15 carbon atoms may be straight-chain, branched, or cyclic, and may include oxygen-containing functional groups such as ether bonds or carbonyl groups between the carbon-carbon bonds. In addition, the saturated hydrocarbyl groups bonded to the tertiary carbon atom may bond with each other to form a ring together with the tertiary carbon atom to which they are bonded.

[0241] Specific examples of groups bonded to the above tertiary carbon atom include a methyl group, an ethyl group, a propyl group, an adamantyl group, a norbornyl group, a tetrahydrofuran-2-yl group, a 7-oxanorbornan-2-yl group, a cyclopentyl group, a 2-tetrahydrofuryl group, a tricyclo[5.2.1.0 2,6 ]decyl group, 8-ethyl-8-tricyclo[5.2.1.02,6 ]decyl group, 3-methyl-3-tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecyl group, tetracyclo[4.4.0.1 2,5 .1 7,10 Examples include the dodecyl group, 3-oxo-1-cyclohexyl group, etc.

[0242] As the above tertiary saturated hydrocarbyl group, the tert-butyl group, tert-pentyl group, 1-ethyl-1-methylpropyl group, 1,1-diethylpropyl group, 1,1,2-trimethylpropyl group, 1-adamantyl-1-methylethyl group, 1-methyl-1-(2-norbornyl)ethyl group, 1-methyl-1-(tetrahydrofuran-2-yl)ethyl group, 1-methyl-1-(7-oxanorbornan-2-yl)ethyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-propylcyclopentyl group, 1-cyclopentylcyclopentyl group, 1-cyclohexylcyclopentyl group, 1-(2-tetrahydrofuryl)cyclopentyl group, 1-(7-oxanorbornan-2-yl)cyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-cyclopentylcyclohexyl group, 1-cyclohexylcyclohexyl group, 2-methyl-2-norbornyl group, 2-ethyl-2-norbornyl group, 8-methyl-8-tricyclo[5.2.1.0 2,6 ]decyl group, 8-ethyl-8-tricyclo[5.2.1.0 2,6 ]decyl group, 3-methyl-3-tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecyl group, 3-ethyl-3-tetracyclo[4.4.0.1 2,5 .1 7,10 Examples include, but are not limited to, dodecyl groups, 2-methyl-2-adamantyl groups, 2-ethyl-2-adamantyl groups, 1-methyl-3-oxo-1-cyclohexyl groups, 1-methyl-1-(tetrahydrofuran-2-yl)ethyl groups, 5-hydroxy-2-methyl-2-adamantyl groups, and 5-hydroxy-2-ethyl-2-adamantyl groups.

[0243] In addition, as the above acid instability group, a group represented by the following formula (A6-1-1) may be used. The group represented by the formula (A6-1-1) is frequently used as an acid instability group and is a useful choice as an acid instability group that stably imparts a pattern in which the interface between the pattern and the substrate is relatively rectangular. When X is the group represented by the formula (A6-1-1), an acetal structure is formed.

[0244]

[0245] (In the formula, dashed lines indicate joint loss.)

[0246] In Equation (A6-1-1), R L11 It is a hydrogen atom, or a saturated hydrocarbyl group having 1 to 10 carbon atoms. The saturated hydrocarbyl group may be straight, branched, or cyclic.

[0247] R L11 It is appropriately selected depending on the design of the sensitivity of the decomposition group to acid. For example, if the design is such that it decomposes into a strong acid after securing relatively high stability, a group in which the carbon atom bonded to the hydrogen atom or the acetal carbon is a tertiary carbon atom is preferred. R bonded to the acetal carbon by the tertiary carbon atom. L11 Examples include, but are not limited to, tert-butyl groups, tert-pentyl groups, and 1-adamantyl groups. If the design aims for high sensitivity to pH changes using relatively high reactivity, straight-chain alkyl groups are preferred. Although it varies depending on the combination with the acid-generating agent or quencher incorporated into the resist composition, R L12 In the case where a relatively large saturated hydrocarbyl group is selected at the terminal and the change in solubility due to decomposition is designed to be significant, R L11 As such, it is preferable that the carbon atom bonded to the acetal carbon is a secondary carbon atom. R bonded to the acetal carbon by a secondary carbon atom L11Examples of such groups include isopropyl groups, sec-butyl groups, cyclopentyl groups, cyclohexyl groups, etc., but are not limited to these.

[0248] In Equation (A6-1-1), R L12 is a hydrocarbyl group having 1 to 30 carbon atoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. A portion of the -CH2- of the hydrocarbyl group may be substituted with heteroatoms such as oxygen or sulfur atoms, and as a result, may include ether bonds, sulfide bonds, etc. Specific examples of the hydrocarbyl group include saturated hydrocarbyl groups having 1 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, etc. In particular, to obtain higher resolution in fine pattern formation, R L12 It is preferable that is a hydrocarbyl group having 1 to 6 carbon atoms. L12 In the case where the group is a hydrocarbyl group having 1 to 6 carbon atoms, the alcohol produced after the deprotection reaction by acid is water-soluble, so it dissolves in the developer when forming a positive type pattern with an alkaline developer, thereby suppressing residual defects in the exposed area.

[0249] Preferable examples of the term represented by Equation (A6-1-1) include those shown below, but are not limited thereto. In addition, among the following equations, R L11 It is the same as above, and the dashed line indicates the connection loss.

[0250]

[0251]

[0252]

[0253] Preferable examples of the repeating unit A6-2 include those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0254]

[0255]

[0256] As other acid instability groups, a hydrogen atom of a phenolic hydroxyl group may be substituted with -CH2COO- (a tertiary saturated hydrocarbyl group). In this case, the same tertiary saturated hydrocarbyl group used for protecting the aforementioned phenolic hydroxyl group may be used as the tertiary saturated hydrocarbyl group.

[0257] When the above polymer comprises at least one selected from repeating units A6-1 and A6-2, the content thereof is preferably 5 to 30 mol% of the total repeating units of the polymer, and when repeating units A1, A3-1, and A3-2 are combined, it is preferably 10 to 60 mol% of the total repeating units of the polymer, more preferably 10 to 50 mol%, and even more preferably 10 to 40 mol%. Repeating units A6-1 and A6-2 may be used as a single type or in combination of two or more types.

[0258] The above polymer may include at least one selected from the following repeating unit represented by the following formula (A7) (hereinafter also referred to as repeating unit A7), the following repeating unit represented by the following formula (A8) (hereinafter also referred to as repeating unit A8), the following repeating unit represented by the following formula (A9) (hereinafter also referred to as repeating unit A9), the following repeating unit represented by the following formula (A10) (hereinafter also referred to as repeating unit A10), and the following repeating unit represented by the following formula (A11) (hereinafter also referred to as repeating unit A11).

[0259]

[0260] Among formulas (A7) to (A11), R A is, each independently, a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z 1is a phenylene group that may have a single bond or a substituent. Z 2 is a single bond, **-C(=O)-OZ 21 -, **-C(=O)-N(H)-Z 21 - or **-OZ 21 -is. Z 21 It is a divalent group obtained by combining 1 to 6 carbon atoms, an aliphatic hydrocarbylene group, a phenylene group, or a combination thereof, and may include a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 3 It is a single bond, ether bond, ester bond, sulfonic acid ester bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. Z 4 is a single bond, or an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by a combination thereof, and may include a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 5 are, respectively, single bond, a phenylene group that may have a substituent, a naphthylene group that may have a substituent, *-C(=O)-OZ 51 - or *-C(=O)-N(R)-Z 51 -is. Z 51 is an aliphatic hydrocarbylene group, a phenylene group, or a naphthylene group having 1 to 10 carbon atoms, and the aliphatic hydrocarbylene group may include a halogen atom, a hydroxyl group, an ether bond, an ester bond, or a lactone ring. R is a hydrocarbylene group having 1 to 10 carbon atoms that may include a hydrogen atom or a heteroatom. Z 6 It is a single bond, ether bond, ester bond, sulfonic acid ester bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. Z 7 Silver, each independently, single bond, ***-Z 71 -C(=O)-O-, ***-C(=O)-N(R)-Z 71- or ***-OZ 71 -is. Z 71 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms. R is the same as above. Z 8 Silver, each independently, single bond, ****-Z 81 -C(=O)-O-, ****-C(=O)-N(R)-Z 81 - or ****-OZ 81 -is. Z 81 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms. R is the same as above. Z 9 is a single bond, methylene group, ethylene group, phenylene group, fluorinated phenylene group, phenylene group substituted with a trifluoromethyl group, *-C(=O)-OZ 91 -, *-C(=O)-N(R)-Z 91 - or *-OZ 91 -is. Z 91 is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may include a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. R is the same as above. * indicates a loss of bond with a carbon atom of the main chain. ** is Z 1 Indicates the bonding loss with. *** is Z 6 Indicates the bond with. **** is Z 7 It represents the bonding hand with.

[0261] Z 21 , Z 51 and Z 91The aliphatic hydrocarbylene group represented by may be linear, branched, or cyclic, and specific examples 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.

[0262] Z 71 and Z 81 The hydrocarbylene group, which may contain a heteroatom represented by, may be saturated or unsaturated and may be straight, branched, or cyclic. Specific examples thereof are shown below, but are not limited to these.

[0263]

[0264] (In the formula, dashed lines indicate joint loss.)

[0265] In equation (A7), R 41 and R 42Each is a hydrocarbyl group having 1 to 20 carbon atoms, which may independently contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples 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, or a tert-butyl group; 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, or adamantyl group; and an alkenyl group having 2 to 20 carbon atoms, such as a vinyl group, a 1-propenyl group, a 2-propenyl group, a butenyl group, or a hexenyl group. Examples include cyclic unsaturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclohexanyl groups; aryl groups having 6 to 20 carbon atoms, such as phenyl groups, naphthyl groups, and thienyl 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, but aryl groups are preferred. 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 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.

[0266] Also, R 41 and R 42 a. They may combine with each other to form a ring together with the sulfur atom to which they combine. In this case, specific examples of the above ring include those represented by the following formula.

[0267]

[0268] (In the formula, the dashed line is Z 4 It is a combined hand with.)

[0269] Specific examples of the cation of the repeating unit A7 are those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280] In formula (A7), M -is a non-nucleophilic counterion. As the above non-nucleophilic counterion, halide ions, sulfonate anions, imidate anions, and methide anions are preferred. Specific examples of the above halide ions include chloride ions, bromide ions, etc. Specific examples of the above sulfonate anions (sulfonate ions) include fluoroalkylsulfonate ions such as trilate ions, 1,1,1-trifluoroethanesulfonate ions, and nonafluorobutanesulfonate ions; arylsulfonate ions such as tosylate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, and 1,2,3,4,5-pentafluorobenzenesulfonate ions; and alkylsulfonate ions such as mesylate ions and butanesulfonate ions. Specific examples of the above imidate anion (imide ion) include bis(trifluoromethylsulfonyl)imide ion, bis(perfluoroethylsulfonyl)imide ion, bis(perfluorobutylsulfonyl)imide ion, etc. Specific examples of the above methide anion (methide ion) include tris(trifluoromethylsulfonyl)methide ion, tris(perfluoroethylsulfonyl)methide ion, etc.

[0281] Other examples of the above-mentioned non-nucleophilic counter-ions include anions represented by any of the following formulas (A7-1) to (A7-4).

[0282]

[0283] In Equation (A7-1), R fa is a hydrocarbyl group having 1 to 40 carbon atoms that may 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 (A7-1-1) described below. fa1Examples of hydrocarbyl groups represented by [ ] can be given as examples. 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.

[0284] As for the anion represented by formula (A7-1), it is preferable to represent it by the following formula (A7-1-1).

[0285]

[0286] In Equation (A7-1-1), 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 It is a hydrocarbyl group having 1 to 40 carbon atoms that may include heteroatoms. As the heteroatom, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, etc. are preferred, and oxygen atoms are more preferred. As for the hydrocarbyl group, it is particularly preferred to have 6 to 30 carbon atoms from the viewpoint of obtaining high resolution in fine pattern formation.

[0287] In Equation (A7-1-1), 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.

[0288] 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.

[0289] In formula (A7-1-1), 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.

[0290] Specific examples of the anion represented by formula (A7-1) 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.

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303] In Equation (A7-2), 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 (A7-1-1). 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.

[0304] In Equation (A7-3), 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. Specific examples thereof include R in formula (A7-1-1). 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 groups that combine (-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.

[0305] In Equation (A7-4), 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 (A7-1-1). 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.

[0306] Specific examples of anions represented by formula (A7-4) include those shown below, but are not limited to these.

[0307]

[0308]

[0309] 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 (A7-5).

[0310]

[0311] In Equation (A7-5), x is 1, 2, or 3. y is 1, 2, 3, 4, or 5. 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.

[0312] In Equation (A7-5), X BI is an iodine atom or a bromine atom. When x and / or y are 2 or more, each X BIThey may be the same or different.

[0313] In formula (A7-5), L 11 The group is 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.

[0314] In formula (A7-5), 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.

[0315] 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.

[0316] 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.

[0317] In formula (A7-5), L 13 It is a single bond, ether bond, ester bond, sulfonic acid ester bond, carbonate bond, or carbamate bond.

[0318] In Equation (A7-5), R feis a hydroxyl group, a carboxyl group, a fluorine atom, a chlorine atom, a bromine atom, an amino group, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbylthio group having 1 to 20 carbon atoms, a hydrocarbylcarbonyl group having 2 to 20 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms, or a 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. feDis 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 are 2 or more, each R fe They may be the same or different.

[0319] 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.

[0320] In Equation (A7-5), 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.

[0321] Specific examples of the anion represented by formula (A7-5) include those shown below, but are not limited thereto. In addition, among the following formulas, X BI It is the same as above.

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346] M -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.

[0347] 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.

[0348] As the above 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, Japanese Patent Publication No. 2019-202974 and Japanese Patent Publication No. 2024-104830, or a benzenesulfonic acid anion not containing a fluorine atom bonded to an aromatic group containing an iodine atom as described in Japanese Patent Publication No. 6645464, may be used. In addition, anions described in paragraphs

[0229] to

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

[0033] to

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

[0349] As the above-mentioned non-nucleophilic counterion, additionally, a bissulfonic acid anion described in Japanese Patent Publication No. 2015-206932, a sulfonamide or sulfonimide anion described in International Publication No. 2020 / 158366 in which one side is a sulfonic acid and the other side is different from this, and a sulfonic acid anion described in Japanese Patent Publication No. 2015-24989 in which one side is a sulfonic acid and the other side is a carboxylic acid may be used.

[0350] Among formulas (A8) and (A9), g1 and g2 are each independently 0, 1, 2 or 3, but 1 is preferred.

[0351] In Equation (A10), h1 is 0 or 1. h2 is 0, 1, 2, 3 or 4. h3 is 0, 1, 2, 3 or 4. Provided that when h1 is 0, 0 ≤ h2 + h3 ≤ 4, and when h1 is 1, 0 ≤ h2 + h3 ≤ 6.

[0352] Among equations (A8), (A9) and (A10), L 1The 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.

[0353] In Equation (A8), 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 are fluorine 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. Among these, for improved solvent solubility, Rf 3 and Rf 4 It is preferable that at least one of them is a trifluoromethyl group.

[0354] In Equation (A9), Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. provided that all Rf 5 and Rf 6 There is no case where it simultaneously becomes a hydrogen atom. Among these, to improve solvent solubility, Rf 5 and Rf 6 It is preferable that at least one of them is a trifluoromethyl group.

[0355] In Equation (A10), Rf 7 The silver, fluorine atom, C1 to C6 fluorinated alkyl group, and C1 to C6 fluorinated alkoxy group are C1 to C6 fluorinated alkyl thio group or pentafluorosulfanyl group. Rf 7As such, a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group, or a difluoromethylthio group is preferred, and a fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group is more preferred. When h2 is 2, 3, or 4, each Rf 7 They may be the same or different.

[0356] In equation (A10), R 43 It is a hydrocarbyl group having 1 to 20 carbon atoms that may include silver, halogen atoms other than fluorine atoms, or heteroatoms. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. As a specific example, in the explanation of formula (A1), R 1 and R 2 Hydrocarbyl groups represented by may include, but are not limited to, those exemplified. Additionally, when h3 is 2, 3, or 4, each R 43 They may be the same or different.

[0357] Also, when h3 is 2, 3, or 4, multiple R 43These 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.

[0358] Specific examples of the anion of the repeating unit A8 include 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.

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371]

[0372] Other specific examples of repetition unit A8 include those described in paragraphs

[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.

[0373] Specific examples of the anion of the repeating unit A9 include those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385] Specific examples of the anion of the repeating unit A10 include those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397]

[0398]

[0399]

[0400]

[0401]

[0402]

[0403] Specific examples of the anion of the repeating unit A11 include those shown below, but are not limited thereto. In addition, among the following formulas, R A It is the same as above.

[0404]

[0405] Among formulas (A8) to (A11), A +is an onium cation. As the above onium cation, it is preferable that it be a sulfonium cation or an iodonium cation. Specific examples of the above sulfonium cation include those exemplified as specific examples of the sulfonium cation represented by formula (Z-1) described below or those exemplified as specific examples of the sulfonium cation represented by formula (Z-3) described below, but are not limited thereto. Specific examples of the above iodonium cation include those exemplified as specific examples of the iodonium cation represented by formula (Z-2) described below, but are not limited thereto.

[0406] As specific structures of repeating units A7 to A11, any combination of the aforementioned anions and cations may be cited.

[0407] Repeating units A7 to A11 are units that generate acid upon irradiation with high-energy rays. It is believed that by incorporating these units into the polymer, acid diffusion is appropriately suppressed, thereby enabling the acquisition of a pattern with reduced LER. Furthermore, by including these units in the polymer, the phenomenon in which acid volatilizes from the exposed area and re-attaches to the unexposed area during vacuum baking is suppressed. This is considered effective for reducing LER and mitigating shape degradation caused by unwanted film reduction in the unexposed area.

[0408] Among repeating units A7 to A11, repeating units A8 to A11 are preferred as units for processing photomask blanks, as the acid strength is optimal for suppressing acid diffusion and designing acid instability groups of the polymer, and repeating units A9, A10, and A11 are more preferred.

[0409] When the above polymer includes repeating units A7 to A11, the content thereof is preferably 0.1 to 30 mol% of the total repeating units of the polymer, and more preferably 0.5 to 20 mol%. Repeating units A7 to A11 may be used as a single type or in combination of two or more types.

[0410] Among the repeating units of the above polymer, the content of repeating units having an aromatic ring backbone is preferably 65 mol% or more, more preferably 75 mol% or more, and even more preferably 85 mol% or more. In cases where repeating units A7 to A11 are not included, it is preferable that all units have an aromatic ring backbone.

[0411] The above polymer may include (meth)acrylic acid ester units protected by acid instability groups that are commercially available, or (meth)acrylic acid ester units having adhesion groups such as lactone structures or hydroxyl groups other than phenolic hydroxyl groups. Fine tuning of the properties of the resist film can be performed by these repeating units, but it is not necessary to include these units.

[0412] Examples of (meth)acrylic acid ester units having the above-mentioned adhesion group include a repeating unit represented by the following formula (A12) (hereinafter also referred to as repeating unit A12), a repeating unit represented by the following formula (A13) (hereinafter also referred to as repeating unit A13), and a repeating unit represented by the following formula (A14) (hereinafter also referred to as repeating unit A14). These units do not exhibit acidity and can be used as auxiliary units to impart adhesion to a substrate or to adjust solubility.

[0413]

[0414] Among formulas (A12) to (A14), R A R is, each independently, a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 51 It is an -O- or methylene group. R52 is a hydrogen atom or a hydroxyl group. R 53 is a saturated hydrocarbyl group having 1 to 4 carbon atoms. i is 0, 1, 2, or 3.

[0415] When repeating units A12 to A14 are included, the content thereof is preferably 0 to 20 mol% of the total repeating units of the polymer, and more preferably 0 to 10 mol%. Repeating units A12 to A14 may be used as a single type or in combination of two or more types.

[0416] The above polymer can be synthesized by copolymerizing each monomer protected by a protecting group as needed by a known method, and then performing a deprotection reaction as needed. The copolymerization reaction is not particularly limited, but is preferably radical polymerization or anionic polymerization. For these methods, reference may be made to Japanese Patent Publication No. 2004-115630.

[0417] The above polymer preferably has a weight average molecular weight (Mw) of 1,000 to 50,000, and more preferably 2,000 to 20,000. If Mw is 1,000 or higher, there is no risk of phenomena occurring such as the pattern head becoming rounded, which reduces resolution and degrades LER, as is conventionally known. On the other hand, if Mw is 50,000 or lower, there is no risk of LER degradation, particularly when forming a pattern with a pattern line width of 100 nm or less. Furthermore, in the present invention, Mw is a polystyrene equivalent measurement value obtained by gel permeation chromatography (GPC) using THF or DMF as a solvent.

[0418] The above polymer preferably has a narrowly dispersed molecular weight distribution (Mw / Mn), preferably 1.0 to 2.0, more preferably 1.0 to 1.9, and even more preferably 1.0 to 1.8. In such a narrowly dispersed case, there is no occurrence of foreign matter on the pattern or deterioration of the pattern shape after development.

[0419] In addition, regarding the above base polymer design, the dissolution rate for the alkaline developer is preferably 10 nm / min or less, more preferably 7 nm / min or less, and even more preferably 5 nm / min or less. In the advanced generation, when the coating film on the substrate is in the thin film region (100 nm or less), the effect of pattern film reduction due to alkaline development becomes large, and if the alkaline dissolution rate of the polymer is greater than 10 nm / min, the pattern collapses, making it impossible to form a fine pattern. This is particularly noticeable in the fabrication of photomasks where defect-free status is required, as the development process tends to be strong. In addition, the dissolution rate of the base polymer in the alkaline developer in the present invention is a value calculated from the amount of film reduction when a polymer solution (polymer concentration: 16.7 mass%, solvent: propylene glycol monomethyl ether acetate (PGMEA)) is spin-coated onto an 8-inch silicon wafer, baked at 100°C for 90 seconds to form a film with a thickness of 1000 nm, and then developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for 100 seconds.

[0420] (A) The base polymer of the component may include other polymers other than the above polymer. As other polymers, those conventionally known as base polymers for resist compositions may be used. The content of other polymers is not particularly limited as long as it does not impair the effects of the present invention.

[0421] [(B) Mineral Generator]

[0422] The chemical amplification positive type resist composition of the present invention comprises a photoacid generator comprising an onium salt represented by the following formula (B) as component (B).

[0423]

[0424] In formula (B), 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, 2, 3, or 4. From the perspective of raw material procurement, it is preferable for n2 to be 0 or 1. n3 is 2, 3, or 4. However, when n1 is 0, 2 ≤ n2 + n3 ≤ 5, and when n1 is 1, 2 ≤ n2 + n3 ≤ 7.

[0425] In Equation (B), R 101The halogen atom is a carbon atom having 1 to 20 hydrocarbyl group that may contain a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a carbon atom having 1 to 20 hydrocarbyl group that may contain a heteroatom, a carbon atom having 1 to 20 hydrocarbylthio group that may contain a heteroatom, or a carbon atom having 2 to 20 hydrocarbyloxycarbonyl group that may contain a heteroatom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., but it is preferable that it be a fluorine atom or an iodine atom. The hydrocarbyl 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, a tert-butyl 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.; an alkenyl group having 2 to 20 carbon atoms, such as a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, etc.; a cyclic unsaturated hydrocarbyl group having 3 to 20 carbon atoms, such as a cyclohexenyl group; an aryl group having 6 to 20 carbon atoms, such as a phenyl group or a naphthyl group; and an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group, a 1-phenylethyl group, or a 2-phenylethyl group. Examples include energy 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, sulfur, nitrogen, or halogen atoms, and some of the -CH2- constituting 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, a haloalkyl group, etc. When n2 is 2, 3, or 4, each R. 101 They may be the same or different.

[0426] Also, when n2 is 2, 3, or 4, multiple R 101 These may combine with each other to form a ring together with the carbon atom to which they are bonded. In this case, a 5 to 8-membered ring is preferred as the ring.

[0427] In formula (B), Ar AL ... is an acid instability group containing the following formula (AL). provided that at least one Ar AL silver, -SO3 - It is bonded to the carbon atom adjacent to the carbon atom it is bonding to.

[0428]

[0429] (In the formula, * indicates a joining hand.)

[0430] In formula (AL), n4 is 0 or 1. When n4 is 0, it is a benzene ring, and when n4 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable for n4 to be a benzene ring of 0. n5 is 0, 1, 2, 3, or 4. From the perspective of raw material procurement, it is preferable for n5 to be 0 or 1. n6 is 0, 1, 2, 3, or 4. From the perspective of raw material procurement, it is preferable for n6 to be 0, 1, or 2. n7 is 1 or 2. However, when n4 is 0, 1 ≤ n5 + n6 + n7 ≤ 5, and when n4 is 1, 1 ≤ n5 + n6 + n7 ≤ 7.

[0431] In formula (AL), R 102 is a halogen atom other than a fluorine 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. Examples of halogen atoms other than the fluorine atom include chlorine atoms, bromine atoms, iodine atoms, etc., but it is preferable that it be an iodine atom. The hydrocarbyl group may be saturated or unsaturated, and may be straight, branched, or cyclic. Specific examples thereof include R 101 Hydrocarbyls represented by may be similar to those exemplified, but are not limited to these. When n5 is 2, 3, or 4, each R 102 They may be the same or different.

[0432] Also, when n5 is 2, 3, or 4, multiple R 102 a. They may combine with each other to form a ring together with the carbon atom to which they are bonded. In this case, a 5 to 8-membered ring is preferred as the ring.

[0433] In formula (AL), R F is 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, a fluorinated saturated hydrocarbylthio group having 1 to 6 carbon atoms, or a pentafluorosulfanyl group. Among these, it is preferable that it is a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, a trifluoromethylthio group, or a pentafluorosulfanyl group, and it is more preferable that it is a fluorine atom, a trifluoromethoxy group, or a pentafluorosulfanyl group. When n6 is 2, 3, or 4, each R F They may be the same or different.

[0434] In Equation (AL), when n6 is 2, 3, or 4, at least one R F is, -OC(R L1 )(R L2 )(R L3 It is preferable that ) is bonded to a carbon atom adjacent to the carbon atom on the aromatic ring to which it is bonded. -OC(R L1 )(R L2 )(R L3 ) and R F By being adjacent, the acidity of the phenols produced after deprotection of the tertiary ether is improved, and the affinity for the alkaline developer is improved, thereby increasing the dissolution contrast.

[0435] In formula (AL), R L1 and R L2 is, each independently, a hydrocarbyl group having 1 to 12 carbon atoms. R L3 It is a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms. R L1 , R L2 and R L3A 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 or a multiple bond, some or all of the hydrogen atoms bonded to the carbon atoms constituting the said aromatic ring or multiple bond 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 If this does not include a cyclic structure, a directional ring, and multiple bonds, R L1 and R L2 They bond with each other to form a ring with the carbon atoms they bond to, and some of the -CH2- in the ring may be substituted with -O- or -S-. That is, -C(R L1 )(R L2 )(R L3 The acid instability group denoted by ) must include at least one cyclic structure or multiple bond. In addition, R L3 In the case of this hydrogen atom, R L1 and R L2 It is desirable for them to bond with each other to form a ring containing multiple bonds with the carbon atoms they bond to.

[0436] In equation (AL), -C(R L1 )(R L2 )(R L3 Specific examples of acid instability groups represented by ) are shown below, but are not limited to these. * indicates a bond loss with an adjacent -O-.

[0437]

[0438]

[0439]

[0440]

[0441]

[0442]

[0443]

[0444]

[0445]

[0446]

[0447]

[0448] As for the onium salt represented by formula (B), it is preferable that it be represented by the following formula (B1).

[0449]

[0450] (Eating, n1, n2, n3, n5, n6, n7, R 101 , R 102 , R F and R L1 to R L3 is the same as above. Z + (This will be discussed later.)

[0451] As for the onium salt represented by formula (B1), it is preferable that it be represented by the following formula (B2).

[0452]

[0453] (Eating, n2, n3, n5, n6, n7, R 101 , R 102 , R F and R L1 to R L3 is the same as above. Z + (This will be discussed later.)

[0454] Examples of anions of the onium salt represented by formula (B) include those shown below, but are not limited to these. In addition, the bonding positions of various substituents on the aromatic ring may be interchanged.

[0455]

[0456]

[0457]

[0458]

[0459]

[0460]

[0461]

[0462]

[0463]

[0464]

[0465]

[0466]

[0467]

[0468]

[0469]

[0470]

[0471]

[0472]

[0473]

[0474]

[0475]

[0476]

[0477]

[0478]

[0479]

[0480]

[0481]

[0482]

[0483]

[0484]

[0485]

[0486]

[0487]

[0488]

[0489]

[0490]

[0491]

[0492]

[0493]

[0494]

[0495]

[0496]

[0497]

[0498]

[0499]

[0500]

[0501]

[0502]

[0503]

[0504]

[0505]

[0506]

[0507]

[0508]

[0509]

[0510]

[0511]

[0512]

[0513]

[0514]

[0515]

[0516]

[0517]

[0518]

[0519]

[0520]

[0521]

[0522]

[0523]

[0524]

[0525]

[0526]

[0527]

[0528]

[0529]

[0530]

[0531]

[0532]

[0533]

[0534]

[0535]

[0536]

[0537]

[0538]

[0539]

[0540]

[0541]

[0542]

[0543]

[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] In Equation (B), Z + is an onium cation. As the onium cation, a sulfonium cation represented by the following formula (Z-1) or an iodonium cation represented by the following formula (Z-2) is preferred.

[0584]

[0585] Among equations (Z-1) and (Z-2), R ct1 to R ct5 Each is a hydrocarbyl group having 1 to 30 carbon atoms that may independently contain a halogen atom or a heteroatom.

[0586] R ct1 to R ct5 Specific examples of halogen atoms represented by include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0587] R ct1 to R ct5The hydrocarbyl group represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include: an alkyl group having 1 to 30 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, or a tert-butyl group; a cyclic saturated hydrocarbyl group having 3 to 30 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, or adamantyl group; an alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, a 1-propenyl group, a 2-propenyl group, a butenyl group, or a hexenyl group; and a cyclic unsaturated hydrocarbyl group having 3 to 30 carbon atoms, such as a cyclohexenyl group. Examples include aryl groups having 6 to 30 carbon atoms, such as phenyl groups, naphthyl groups, and thienyl groups; aralkyl groups having 7 to 30 carbon atoms, such as benzyl groups, 1-phenylethyl groups, and 2-phenylethyl groups; and groups obtained by combining these, but aryl groups are preferred. 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.

[0588] Also, R ct1 and R ct2 a. They may combine with each other to form a ring together with the sulfur atom to which they combine. In this case, specific examples of the structure of the ring include those represented by the following formula.

[0589]

[0590] (In the food, the dashed line is R ct3 It is a combined hand with.)

[0591] Specific examples of the sulfonium cation represented by formula (Z-1) include those described in paragraphs

[0102] to

[0125] of Japanese Patent Publication No. 2024-003744 and those described in paragraphs

[0070] to

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

[0592] Specific examples of iodium cations represented by formula (Z-2) include those described in paragraph

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

[0593] Z + As for the onium cation represented by, a sulfonium cation represented by the following formula (Z-3) is also preferred.

[0594]

[0595] In formula (Z-3), 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 with a value of 0. m2 is 0 or 1. When m2 is 0, it is a benzene ring, and when m2 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable that m2 is a benzene ring with a value of 0. m3 is 0 or 1. When m3 is 0, it is a benzene ring, and when m3 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable that m3 is a benzene ring with a value of 0.

[0596] In formula (Z-3), m4 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 m4 is 0, 1, 2, or 3, and more preferable that it is 0, 1, or 2.

[0597] In formula (Z-3), m5 is 0, 1, 2, 3, or 4. From the perspective of raw material procurement, it is preferable that m5 is 0, 1, 2, or 3, and more preferable that it is 0, 1, or 2. m6 is 0, 1, 2, 3, 4, 5, or 6. From the perspective of raw material procurement, it is preferable that m6 is 0, 1, 2, or 3, and more preferable that it is 0, 1, or 2. m7 is 0, 1, 2, 3, 4, 5, or 6. From the perspective of raw material procurement, it is preferable that m7 is 0, 1, 2, or 3, and more preferable that it is 0, 1, or 2.

[0598] In Equation (Z-3), m8 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable that m8 is 0 or 1. m9 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable that m9 is 0 or 1. m10 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable that m10 is 0 or 1.

[0599] In formula (Z-3), m11 is 0 or 1. When m11 is 0, it is a benzene ring, and when m11 is 1, it is a naphthalene ring, but from the perspective of solvent solubility, it is preferable for m11 to be a benzene ring of 0.

[0600] In formula (Z-3), m12 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 m12 is 0, 1, 2, or 3, and more preferable that it is 0, 1, or 2.

[0601] In formula (Z-3), m13 is 0, 1, or 2. From the perspective of raw material procurement, it is preferable that m13 is 0 or 1. m14 is 0, 1, or 2. From the perspective of synthesis, it is preferable that m14 is 0 or 1.

[0602] However, when m1 is 0, 0 ≤ m6 + m9 ≤ 4, and when m1 is 1, 0 ≤ m6 + m9 ≤ 6. When m2 is 0, 0 ≤ m7 + m10 ≤ 4, and when m2 is 1, 0 ≤ m7 + m10 ≤ 6. When m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4, and when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6. When m11 is 0, 0 ≤ m12 + m13 ≤ 4, and when m11 is 1, 0 ≤ m12 + m13 ≤ 6. Also, m4 + m12 ≥ 1.

[0603] In equation (Z-3), 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 to be a trifluoromethyl group, a trifluoromethoxy group, or a trifluorothiomethoxy group. When m5 is 2, 3, or 4, each R F1 They may be the same or different. When m6 is 2, 3, 4, 5, or 6, each R F2 may be the same or different. When m7 is 2, 3, 4, 5, or 6, each R F3 They may be the same or different.

[0604] In equation (Z-3), R ct6 to R ct9 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), R1 Examples of hydrocarbyl groups represented by [ ] 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.

[0605] Also, when m8 is 2, 2 R ct6 They may be identical or different, and 2 R ct6 These may bond with each other to form a ring with the carbon atom they bond to. When m9 is 2, 2 R ct7 They may be identical or different, and 2 R ct7 These may bond with each other to form a ring with the carbon atom to which they bond. When m10 is 2, 2 R ct8 They may be identical or different, and 2 R ct8 These may bond with each other to form a ring with the carbon atom to which they bond. When m13 is 2, 2 R ct9 They may be the same or different, and 2 R ct9They 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.

[0606] In addition, S in the sulfonium cation represented by formula (Z-3) + 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.

[0607]

[0608] In equation (Z-3), L A and L B Each is independently a single bond, ether bond, ester bond, amide bond, sulfonic acid ester bond, sulfonamide bond, carbonate bond, or 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 ester bond or a sulfonic acid ester bond. L B 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.

[0609] In equation (Z-3), X L The hydrocarbylene group having 1 to 40 carbon atoms may include a single bond or a heteroatom. The hydrocarbylene group may be straight, branched, or cyclic, and specific examples include an alkanedyl group, a cyclic saturated hydrocarbylene group, etc. Specific examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0610] X L 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 respectively. A and L B It represents the bonding loss with.

[0611]

[0612]

[0613]

[0614]

[0615] Among these, X L -0 to X L -22 and X L -47 to X L -61 is desirable.

[0616] As for the sulfonium cation represented by formula (Z-3), it is preferable to represent it by the following formula (Z-3-1).

[0617]

[0618] (among the formulas, m4 to m10, m12 to m14, R F1 to R F3 , R ct6 to R ct9 , L A , L B and X L is the same as above.)

[0619] As for the cation represented by formula (Z-3-1), it is preferable to represent it by the following formula (Z-3-2).

[0620]

[0621] (among the formulas, m4 to m10, R F1 to R F3 and R ct6 to R ct8 is the same as above.)

[0622] Specific examples of the sulfonium cation represented by formula (Z-3) include those shown below, but are not limited to these. In addition, in the following formula, Me is a methyl group.

[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] Specific examples of the above-mentioned onium salt include any combination of the aforementioned anion and cation.

[0652] The above onium salt can be synthesized by known methods. Specifically, it can be synthesized by using the synthesis examples described in

[0363] to

[0368] of Japanese Patent Publication No. 7032549, but the synthesis method is not limited thereto.

[0653] In the chemical amplification resist composition of the present invention, the onium salt represented by formula (B) is an onium salt of an aromatic sulfonic acid, so it can generate an acid of appropriate strength upon high-energy irradiation. In addition, the onium salt is -SO3 - It is characterized by having 2, 3, or 4 aryl groups having ether-type acid instability groups on the aromatic ring to which it is bonded. -SO3 - The aryl group bonded to the aromatic ring to which it is bonded is at least one -SO3 - It is desirable for it to bond to a carbon atom adjacent to the carbon atom to which it bonds, and two of them are -SO3 -It is more desirable for it to bond to a carbon atom adjacent to the carbon atom to which it is bonded. -SO3 -Since bulky aromatic rings are bonded to the carbon atoms on both sides of the carbon atom to which the sulfonic acid is bonded, the area near the generated sulfonic acid is shielded, thereby suppressing the excessive deprotection reaction of the acid instability group of the base polymer. It is preferable that the ether-type acid instability group be a cyclic tertiary ether; in this case, the activation energy of the acid deprotection reaction is lowered due to the cyclic structure, making it easier for the deprotection reaction to proceed. On the other hand, if the ether-type acid instability group does not have a cyclic ether structure, the carbon atom bonded to the ether oxygen has at least one double bond, aromatic ring, or triple bond. In all cases, the deprotection reaction by acid is made easier to proceed by using the generation of an allyl cation, a benzyl cation, or a propargyl cation as a driving force. Japanese Patent Publication No. 7032549 describes a structure in which tert-butyl ether, acetal, tert-butoxycarbonyl, or tert-butyl ester is introduced as an acid-unstable group. However, since acetal and tert-butoxycarbonyl are functional groups sensitive to acid, there are concerns regarding storage stability, and it is thought that tert-butyl ether and tert-butyl ester are difficult to proceed with sufficient deprotection reactions because the activation energy of the deprotection reaction by acid is high. In the onium salt represented by formula (B), it is preferable that a fluorine atom or a functional group containing a fluorine atom is bonded to the carbon atom adjacent to the carbon atom to which the ether-type acid-unstable group is bonded. A fluorine atom or a functional group containing a fluorine atom can increase solubility in a solvent and allow for uniform dissolution in a solvent. In addition, ether-type acid instability groups produce phenols after a deprotection reaction by acid proceeds, but can increase the acidity of phenols by having a fluorine atom or a functional group containing a fluorine atom at an adjacent position.Phenols have the characteristic of being resistant to swelling in alkaline developers, and when developed with an alkaline developer, their affinity for the alkaline developer increases, allowing for improved dissolution contrast while suppressing development residue in the exposed area. Patent Publication No. 7531671 describes an aromatic sulfonic acid anion with a similar structure that introduces a tertiary ester-type acid instability group. It is known that tertiary esters generate carboxyl groups after the acid deprotection reaction proceeds, but they swell in alkaline developers. Consequently, the LER of the resist pattern deteriorates. Multiple aromatic rings in the anion improve compatibility through mutual interaction (π-π stacking interaction) with the aromatic rings of the base polymer, and an effect of suppressing excessive acid diffusion can be expected. Due to these effects, acid with controlled excessive acid intensity and diffusion can be uniformly generated within the resist film, resulting in good resolution even in fine patterns and small LER patterns; furthermore, in the case of a positive-type resist composition using an alkaline developer, a pattern with good rectangularity is obtained due to appropriate dissolution inhibition.

[0654] In the chemical amplification positive type resist composition of the present invention, the content of (B) a photoacid generator is preferably 0.1 to 40 parts by mass and more preferably 1 to 20 parts by mass with respect to 80 parts by mass of (A) base polymer. When the content of (B) a photoacid generator is within the above range, an amount of acid necessary for deprotection of acid unstable groups is generated, and storage stability is also good. (B) A photoacid generator may be used as a single type or in combination of two or more types.

[0655] [(C) Organic solvent]

[0656] The chemically amplified positive type resist composition of the present invention may include an organic solvent as component (C). The organic solvent is not particularly limited as long as it is capable of dissolving each component. Examples of such organic solvents include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone, as described in paragraphs

[0144] to

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

[0657] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, PGME, cyclohexanone, EL, γ-butyrolactone, and mixtures thereof are preferred.

[0658] When the chemically amplified positive type resist composition of the present invention includes (C) an organic solvent, the content thereof is preferably 200 to 10,000 parts by mass and more preferably 400 to 5,000 parts by mass with respect to 80 parts by mass of (A) base polymer. (C) The organic solvent may be used alone or in a mixture of two or more types.

[0659] [(D) Quencher]

[0660] The chemically amplified positive type resist composition of the present invention may, if necessary, include a quencher as component (D). Furthermore, in the present invention, a quencher refers to a compound that captures acid generated from an acid generator. By doing so, the diffusion rate of acid generated from an acid generator when it diffuses into the resist film can be suppressed, and even when a substrate is used in which the outermost surface is a material containing chromium, the effect of the acid generated within the resist film on the material containing chromium can be suppressed.

[0661] Examples of the above-mentioned quencher include conventional basic compounds. Examples of conventional basic compounds include primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, carbamates, etc. In particular, primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Publication No. 2008-111103, 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, or compounds having a carbamate group described in Japanese Patent Publication No. 3790649 are preferred. Preferably, tris[2-(methoxymethoxy)ethyl]amine, tris[2-(methoxymethoxy)ethyl]amine-N-oxide, dibutylaminobenzoic acid, morpholine derivatives, imidazole derivatives, etc. By adding such basic compounds, the diffusion rate of acid within the resist film can be further suppressed, for example, or the shape can be corrected.

[0662] In addition, as the above-mentioned quencher, onium salts such as sulfonium salts, iodonium salts, and ammonium salts of a carboxylic acid in which the α-position is not fluorinated may be cited as described in Japanese Patent Publication No. 2008-158339. Sulfonic acid, imidic acid, or methic acid in which the α-position is fluorinated is required to deprotect the acid unstable group, but a carboxylic acid in which the α-position is not fluorinated is released through salt exchange with an onium salt in which the α-position is not fluorinated. Since the carboxylic acid in which the α-position is not fluorinated hardly undergoes a deprotection reaction, it functions as a quencher.

[0663] As an onium salt of a carboxylic acid in which the α position is not fluorinated, for example, it can be represented by the following formula (D1).

[0664]

[0665] In equation (D1), R 201 It is a hydrocarbyl group having 1 to 40 carbon atoms that may include a hydrogen atom or a heteroatom, but excludes cases where the hydrogen atom bonded to the carbon atom at the α-position of the carboxyl group is substituted with a fluorine atom or a fluoroalkyl group.

[0666] R 201 The hydrocarbyl group represented by may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples include alkyl groups having 1 to 40 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.0 2,6 ] Cyclic saturated hydrocarbyl groups having 3 to 40 carbon atoms, such as decyl groups, adamantyl groups, adamantylmethyl groups, etc.; alkenyl groups having 2 to 40 carbon atoms, such as vinyl groups, allyl groups, propenyl groups, butenyl groups, hexenyl groups, etc.; cyclic unsaturated aliphatic hydrocarbyl groups having 3 to 40 carbon atoms, such as cyclohexenyl groups; Examples include aryl groups having 6 to 40 carbon atoms, such as phenyl groups, naphthyl groups, alkylphenyl groups (2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-n-butylphenyl group, etc.), di or trialkylphenyl groups (2,4-dimethylphenyl group, 2,4,6-triisopropylphenyl group, etc.), alkylnaphthyl groups (methylnaphthyl group, ethylnaphthyl group, etc.), and dialkylnaphthyl groups (dimethylnaphthyl group, diethylnaphthyl group, etc.); and aralkyl groups having 7 to 40 carbon atoms, such as benzyl groups, 1-phenylethyl groups, and 2-phenylethyl groups.

[0667] 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 carbonyl group, an ether bond, a thioether 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 a hydrocarbyl group containing heteroatoms, a heteroaryl group such as a thienyl group; Examples include alkoxyphenyl groups such as 4-hydroxyphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 4-tert-butoxyphenyl group, 3-tert-butoxyphenyl group; alkoxynaphthyl groups such as methoxynaphthyl group, ethoxynaphthyl group, n-propoxynaphthyl group, n-butoxynaphthyl group; diallkoxynaphthyl groups such as dimethoxynaphthyl group, diethoxynaphthyl group; and aryloxoalkyl groups such as 2-aryl-2-oxoethyl group, 2-(1-naphthyl)-2-oxoethyl group, 2-(2-naphthyl)-2-oxoethyl group.

[0668] In Equation (D1), Mq A + is an onium cation. As the onium cation, a sulfonium cation, an iodonium cation, or an ammonium cation is preferred, and a sulfonium cation or an iodonium cation is more preferred. Specific examples of the sulfonium cation include those similar to the sulfonium cation represented by formula (Z-1) and the sulfonium cation represented by formula (Z-3) that were exemplified. Specific examples of the iodonium cation include those similar to the iodonium cation represented by formula (Z-2) that were exemplified.

[0669] Examples of anions of the onium salt represented by formula (D1) include those shown below, but are not limited to these.

[0670]

[0671]

[0672]

[0673]

[0674] As the above quencher, a sulfonium salt of a carboxylic acid containing an iodinated benzene ring represented by the following formula (D2) can also be suitably used.

[0675]

[0676] In Equation (D2), s is 1, 2, 3, 4, or 5. t is 0, 1, 2, or 3, provided that 1 ≤ s + t ≤ 5. u is 1, 2, or 3.

[0677] In equation (D2), R 211 Silver, hydroxyl group, fluorine atom, chlorine atom, bromine atom, amino group, nitro group, cyano group, saturated hydrocarbyl group having 1 to 6 carbon atoms, saturated hydrocarbyloxy group having 1 to 6 carbon atoms, saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms, saturated hydrocarbylsulfonyloxy group having 1 to 4 carbon atoms, -N(R 211A )-C(=O)-R 211B or -N(R 211A )-C(=O)-OR 211B And, some or all of the hydrogen atoms of the corresponding saturated hydrocarbyl group, saturated hydrocarbyloxy group, saturated hydrocarbylcarbonyloxy group, or saturated hydrocarbylsulfonyloxy group may be substituted with halogen atoms. R 211A is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. R 211B is a saturated hydrocarbyl group having 1 to 6 carbon atoms or an unsaturated aliphatic hydrocarbyl group having 2 to 8 carbon atoms. When t and / or u is 2 or more, each R211 They may be the same or different.

[0678] In equation (D2), L 21 It may be a single bond or a (u+1) linker having 1 to 20 carbon atoms, and may include at least one selected from ether bonds, carbonyl groups, ester bonds, amide bonds, sulfone rings, lactam rings, carbonate bonds, halogen atoms, hydroxyl groups, and carboxyl groups. The saturated hydrocarbyl group, saturated hydrocarbyloxy group, saturated hydrocarbylcarbonyloxy group, and saturated hydrocarbylsulfonyloxy group may be straight-chain, branched, or cyclic.

[0679] In equation (D2), R 212 , R 213 and R 214 Each is a hydrocarbyl group having 1 to 20 carbon atoms, which may independently contain a halogen atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, etc. Additionally, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, a nitro group, a sulfonyl ring, a sulfo group, or a sulfonium salt-containing group, and some of the -CH2- of the hydrocarbyl group may be substituted with an ether bond, an ester bond, a carbonyl group, an amide bond, a carbonate bond, or a sulfonic acid ester bond. Also, R 212 and R 213 These may combine with each other to form a ring together with the sulfur atom to which they combine.

[0680] Specific examples of the compound represented by formula (D2) include those described in Japanese Patent Publication No. 2017-219836. The compound represented by formula (D2) has high absorption, a high increase / decrease effect, and a high acid diffusion control effect.

[0681] As the above quencher, a nitrogen atom-containing carboxylate-type compound represented by the following formula (D3) may also be used.

[0682]

[0683] In Equation (D3), R 221 to R 224 is, each independently, a hydrogen atom, -L 22 -CO2 - , or is a hydrocarbyl group having 1 to 20 carbon atoms that may contain heteroatoms. R 221 and R 222 Wow, R 222 and R 223 and, or R 223 and R 224 a, they may combine with each other to form a ring together with the carbon atom to which they bond. L 22 is a hydrocarbylene group having 1 to 20 carbon atoms that may include single bonds or heteroatoms. 225 It is a hydrocarbyl group having 1 to 20 carbon atoms that may include hydrogen atoms or heteroatoms.

[0684] Among the formula (D3), the patient R r Silver is a ring having 2 to 6 carbon atoms comprising carbon atoms and nitrogen atoms in the formula, wherein some or all of the hydrogen atoms bonded to the carbon atoms of the ring are hydrocarbyl groups having 1 to 20 carbon atoms, or -L 22 -CO2 -It may be substituted with, and a portion of the -CH2- of the ring may be substituted with a sulfur atom, an oxygen atom, or a nitrogen atom. The ring may be an alicyclic ring or an aromatic ring, and it is also preferable that it be a five-membered or six-membered ring. Specific examples thereof include a pyridine ring, a pyrrole ring, a pyrrolidine ring, a piperidine ring, a pyrazol ring, an imidazoline ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, an imidazoline ring, an oxazole ring, a thiazole ring, a morpholine ring, a thiazine ring, a triazole ring, etc.

[0685] The onium carboxylate salt represented by formula (D3) comprises at least one -L 22 -CO2 - Possesses energy. That is, R 221 to R 224 At least one of them is -L 22 -CO2 - is, and / or ring R r At least one hydrogen atom bonded to a carbon atom is -L 22 -CO2 - It has been replaced with.

[0686] In Equation (D3), Mq B + The sulfonium cation is a sulfonium cation, an iodonium cation, or an ammonium cation, but a sulfonium cation is preferred. Specific examples of the sulfonium cation can be the same as those exemplified as the sulfonium cation represented by formula (Z-1) and the sulfonium cation represented by formula (Z-3).

[0687] Examples of anions of the compound represented by formula (D3) include those shown below, but are not limited to these.

[0688]

[0689]

[0690]

[0691]

[0692]

[0693]

[0694] In addition, a weak acid betaine-type compound may be used as the above quencher. Specific examples thereof are shown below, but are not limited to these.

[0695]

[0696] As for the above-mentioned quencher, a polymer-type quencher described in Japanese Patent Publication No. 2008-239918 can be cited. This improves the rectangularity of the resist pattern by orienting it on the surface of the resist film. The polymer-type quencher also has the effect of preventing film reduction of the pattern or rounding of the pattern top when a protective film for immersion exposure is applied.

[0697] When the chemically amplified positive type resist composition of the present invention includes (D) a quencher, the content thereof is preferably 0 to 50 parts by mass and more preferably 0.1 to 40 parts by mass with respect to 80 parts by mass of the (A) base polymer. The quencher may be used as a single type or in combination of two or more types.

[0698] [(E) Fluorine-containing polymer]

[0699] For the purpose of suppressing chemical flare of acid during high contrast or high-energy irradiation, shielding acid mixing from the antistatic film during the process of applying an antistatic film material onto the resist film, and suppressing unexpected and unnecessary pattern degradation, the chemical amplification positive type resist composition of the present invention may include, as a component (E), at least one selected from a repeating unit represented by the following formula (E1) (hereinafter also referred to as repeating unit E1), a repeating unit represented by the following formula (E2) (hereinafter also referred to as repeating unit E2), a repeating unit represented by the following formula (E3) (hereinafter also referred to as repeating unit E3), and a repeating unit represented by the following formula (E4) (hereinafter also referred to as repeating unit E4), and additionally may include at least one selected from a repeating unit represented by the following formula (E5) (hereinafter also referred to as repeating unit E5) and a repeating unit represented by the following formula (E6) (hereinafter also referred to as repeating unit E6). Since the above fluorine atom-containing polymer also functions as a surfactant, it can prevent the reattachment of insoluble matter to the substrate that may occur during the development process, and thus also exhibits an effect against development defects.

[0700]

[0701] In equations (E1) through (E6), j1 is 1, 2, or 3. j2 is an integer satisfying 0 ≤ j2 ≤ 5 + 2(j3) - j1. j3 is 0 or 1. k is 1, 2, or 3. R B R is, each independently, a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. C is, independently, a hydrogen atom or a methyl group. R 301 , R 302 , R 304 and R 305is, each independently, a hydrogen atom or a saturated hydrocarbyl group having 1 to 10 carbon atoms. R 303 , R 306 , R 307 and R 308 Each independently is a hydrogen atom, a hydrocarbyl group having 1 to 15 carbon atoms, a fluorinated hydrocarbyl group having 1 to 15 carbon atoms, or an acid instability group, and R 303 , R 306 , R 307 and R 308 When this is a hydrocarbyl group or a fluorinated hydrocarbyl group, an ether bond or a carbonyl group may be interposed between the carbon-carbon bonds. R 309 is a straight-chain or branched hydrocarbyl group having 1 to 5 carbon atoms, which may include a hydrogen atom or a group containing a heteroatom between carbon-carbon bonds. When j1 is 2 or 3, each R 309 They may be the same or different. R 310 It is a straight-chain or branched hydrocarbyl group having 1 to 5 carbon atoms, wherein a group containing a heteroatom may be interposed between carbon-carbon bonds. When j2 is 2 or more, each R 310 They may be the same or different. R 311 Silver is a saturated hydrocarbyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and a portion of the -CH2- of the saturated hydrocarbyl group may be substituted by an ester bond or an ether bond. W 1 is a (k+1) valent hydrocarbon group having 1 to 20 carbon atoms or a (k+1) valent fluorinated hydrocarbon group having 1 to 20 carbon atoms. W 2 is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-. * is a bond with a carbon atom in the main chain. W 3 is a single bond, -O-, *-C(=O)-OW 31 -W 32 - or *-C(=O)-N(H)-W 31-W 32 -is. W 31 It is a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms. W 32 is a single bond, ester bond, ether bond, or sulfonamide bond. * is a bond with a carbon atom of the main chain.

[0702] Among equations (E1) and (E2), R 301 , R 302 , R 304 and R 305 The saturated hydrocarbyl group having 1 to 10 carbon atoms, represented by, may be linear, 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, a saturated hydrocarbyl group having 1 to 6 carbon atoms is preferred.

[0703] Among equations (E1) to (E4), R 303 , R 306 , R 307 and R 308The hydrocarbyl group having 1 to 15 carbon atoms represented by [characteristic] may be straight-chain, branched, or cyclic, and specific examples thereof include an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkynyl group having 2 to 15 carbon atoms, etc., but an alkyl group having 1 to 15 carbon atoms is preferred. As for the alkyl group, in addition to those mentioned above, examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, etc. In addition, as a fluorinated hydrocarbyl group, 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 can be cited.

[0704] In Equation (E4), W 1 As a (k+1) valence hydrocarbon group having 1 to 20 carbon atoms represented by, examples include a group in which k additional hydrogen atoms have been excluded from an alkyl group having 1 to 20 carbon atoms or a cyclic saturated hydrocarbyl group having 3 to 20 carbon atoms. In addition, W 1 As a (k+1) fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by, an example is a group in which at least one hydrogen atom of the aforementioned (k+1) fluorinated hydrocarbon group is substituted with a fluorine atom.

[0705] Specific examples of repeating units E1 to E4 are those shown below, but are not limited thereto. In addition, among the following formulas, R B It is the same as above.

[0706]

[0707]

[0708]

[0709] In Equation (E5), R 309 and R 310Examples of hydrocarbyl groups having 1 to 5 carbon atoms represented by [the name] include alkyl groups, alkenyl groups, alkynyl groups, etc., but alkyl groups are preferred. Examples of the alkyl groups include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, n-pentyl groups, etc. Additionally, a group containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms may be interposed between the carbon-carbon bonds of the hydrocarbyl groups.

[0710] In Equation (E5), -OR 309 It is preferable that is a hydrophilic group. In this case, R 309 As such, hydrogen atoms, carbon-1 to carbon-5 alkyl groups in which oxygen atoms are interposed between carbon-carbon bonds are preferred.

[0711] In Equation (E5), W 2 It is preferable that is *-C(=O)-O- or *-C(=O)-N(H)-. Also, R C It is preferable that is a methyl group. W 2 The presence of a carbonyl group enhances the acid trapping ability of the antistatic film. In addition, R C If the group is a methyl group, it becomes a rigid polymer with a higher glass transition temperature (Tg), so the diffusion of acid is suppressed. As a result, the long-term stability of the resist film is good, and there is no deterioration in resolution or pattern shape.

[0712] Examples of iteration units E5 include those shown below, but are not limited to these. Also, among the following expressions, R C It is the same as above.

[0713]

[0714]

[0715] In Equation (E6), W 3The saturated hydrocarbylene group having 1 to 10 carbon atoms represented by [the name] may be in a straight chain, branched chain, or cyclic form, and specific examples thereof include methane diyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,1-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, 1,1-dimethylethane-1,2-diyl group, etc.

[0716] In Equation (E6), R 311 A saturated hydrocarbyl group having 1 to 20 carbon atoms, in which at least one hydrogen atom represented by is substituted with a fluorine atom, may be straight, branched, or cyclic, and specific examples thereof include an alkyl group having 1 to 20 carbon atoms or a cyclic saturated hydrocarbyl group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

[0717] Examples of iteration units E6 include those shown below, but are not limited to them. Also, among the following expressions, R C It is the same as above.

[0718]

[0719]

[0720]

[0721]

[0722] The content of repeating units E1 to E4 is preferably 15 to 95 mol% of the total repeating units of the fluorine atom-containing polymer, and more preferably 20 to 85 mol%. The content of repeating units E5 and / or E6 is preferably 5 to 85 mol% of the total repeating units of the fluorine atom-containing polymer, and more preferably 15 to 80 mol%. Repeating units E1 to E6 may be used as a single type or in combination of two or more types.

[0723] (E) The fluorine atom-containing polymer may include other repeating units other than the repeating units described above. Examples of such repeating units include those described in paragraphs

[0046] to

[0078] of Japanese Patent Publication No. 2014-177407. (E) When the fluorine atom-containing polymer includes other repeating units, the content thereof is preferably 50 mol% or less of the total repeating units of the fluorine atom-containing polymer.

[0724] (E) A polymer containing a fluorine atom can be synthesized by copolymerizing each monomer protected by a protecting group as needed by a known method, and then performing a deprotection reaction as needed. The copolymerization reaction is not particularly limited, but is preferably radical polymerization or anionic polymerization. For such a method, reference may be made to Japanese Patent Publication No. 2004-115630.

[0725] (E) The Mw of the fluorine atom-containing polymer is preferably 2,000 to 50,000, and more preferably 3,000 to 20,000. If the Mw is 2,000 or higher, acid does not diffuse, resolution does not deteriorate, and stability over time is not compromised. If the Mw is 50,000 or lower, solubility in solvents is sufficient, so coating defects do not occur. In addition, (E) the fluorine atom-containing polymer is preferably 1.0 to 2.2, and more preferably 1.0 to 1.7.

[0726] When the chemically amplified positive type resist composition of the present invention comprises (E) a fluorine atom-containing polymer, the content thereof is preferably 0.01 to 30 parts by mass and more preferably 0.1 to 20 parts by mass with respect to 80 parts by mass of (A) base polymer. (E) The fluorine atom-containing polymer may be used alone or in combination of two or more types.

[0727] [(F) Other Mining Agents]

[0728] The chemically amplified positive type resist composition of the present invention may include a photoacid generator other than the photoacid generator comprising an onium salt represented by formula (B) as component (F) (hereinafter also referred to as other photoacid generators). The above other 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 include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type photoacid generators, etc.

[0729] Specific examples of the above other photoacid generating agents include nonafluorobutanesulfonate, partially fluorinated sulfonate described in paragraphs

[0247] to

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

[0261] to

[0265] of Japanese Patent Publication No. 2013-101271, paragraphs

[0122] to

[0142] of Japanese Patent Publication No. 2008-111103, that described in paragraphs

[0080] to

[0081] of Patent No. 5368270, that described in paragraphs

[0027] to

[0029] of Patent No. 6248882, that described in paragraphs

[0029] to

[0034] of Patent No. 6648726, and Patent No. 7067271 What is described in paragraphs

[0028] to

[0029] of the publication, what is described in paragraphs

[0037] to

[0060] of Japanese Patent Publication No. 2024-104830, what is described in paragraphs

[0040] to

[0071] of Japanese Patent Publication No. 2025-000201, what is described in paragraphs

[0039] to

[0066] of Japanese Patent Publication No. 2023-177038, what is described in paragraphs

[0033] to

[0093] of Japanese Patent Publication No. 2024-140135, what is described in paragraphs

[0220] to

[0225] of Patent Publication No. 7032549, what is described in paragraphs

[0229] to

[0231] of Japanese Patent Publication No. 2024-077330, and the International Publication Examples include those described in paragraphs

[0056] to

[0059] of Patent No. 2024 / 241820. Among the above specific examples, an arenesulfonate-type or alkansulfonate-type photoacid generator is preferred because it generates an acid of suitable strength to deprotect the acid instability group of repeating unit B2.

[0730] As the above-mentioned photoacid generator, salt compounds containing anions having the structure shown below may be cited, but are not limited to these.

[0731]

[0732]

[0733]

[0734]

[0735]

[0736]

[0737] (F) In other photoacid generators, as the cation paired with the aforementioned anion, a sulfonium cation or an iodine cation is preferred. Specific examples of the sulfonium cation include those exemplified as specific examples of the sulfonium cation represented by formula (Z-1) or those exemplified as specific examples of the sulfonium cation represented by formula (Z-3), but are not limited thereto. Specific examples of the iodine cation include those exemplified as specific examples of the iodine cation represented by formula (Z-2), but are not limited thereto.

[0738] The acid generated by the above-mentioned other acid-generating agents preferably has a pKa of -2.0 or higher, and more preferably -1.0 or higher. Additionally, the upper limit of the pKa is preferably 2.0. Furthermore, the pKa value is calculated using the pKa DB in the software ACD / Chemsketch ver: 9.04 of Advanced Chemistry Development, Inc.

[0739] When the chemically amplified positive type resist composition of the present invention includes (F) other photoacid generators, the content thereof is preferably 1 to 10 parts by mass and more preferably 1 to 5 parts by mass with respect to 80 parts by mass of the (A) base polymer. By including other photoacid generators, the amount of generated acid in the exposed part and the dissolution inhibition of the unexposed part can be appropriately controlled. (F) Other photoacid generators may be used as a single type or in combination of two or more types.

[0740] [(G) Surfactant]

[0741] The chemically amplified positive type resist composition of the present invention may include a surfactant that is commonly used as component (G) to improve the applicability to a substrate. Many of the surfactants are known as described in International Publication No. 2006 / 121096, Japanese Patent Publication No. 2008-102383, Japanese Patent Publication No. 2008-304590, Japanese Patent Publication No. 2004-115630, and Japanese Patent Publication No. 2005-8766, and may be selected by reference.

[0742] When the chemically amplified positive type resist composition of the present invention includes (G) a surfactant, the content thereof is preferably 2 parts by mass or less, more preferably 1 part by mass or less, with respect to 80 parts by mass of (A) base polymer, and the lower limit thereof is preferably 0.01 parts by mass or more. (G) surfactant may be used alone or in combination of two or more types.

[0743] [Resist Pattern Formation Method]

[0744] The method for forming a resist pattern according to the present invention comprises a process of forming a resist film on a substrate using the aforementioned chemically amplified positive type resist composition, a process of irradiating a pattern onto the resist film using a high-energy ray (i.e., a process of exposing the resist film using a high-energy ray), and a process of developing the resist film irradiated with the pattern using an alkaline developer to obtain a resist pattern.

[0745] As the above substrate, for example, a substrate for manufacturing integrated circuits (Si, SiO, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.) or a substrate for manufacturing mask circuits (Cr, CrO, CrON, MoSi2, Si, SiO, SiO2, etc.) may be used. On the above substrate, the chemically amplified positive type resist composition is applied by a method such as spin coating so that the film thickness is 0.03 to 2 μm, and the above is prebaked on a hot plate, preferably at 60 to 150°C for 1 to 20 minutes, more preferably at 80 to 140°C for 1 to 10 minutes, to form a resist film.

[0746] Next, the resist film is exposed using high-energy rays to irradiate the pattern. Examples of high-energy rays include ultraviolet rays, far-ultraviolet rays, excimer laser light (KrF, ArF, etc.), EB, EUV, X-rays, γ-rays, synchrotron radiation, etc.

[0747] When ultraviolet rays, far-ultraviolet rays, excimer laser light, EUV, X-rays, γ-rays, or synchrotron radiation are used as the high-energy rays, a mask is used to form the desired pattern, and irradiation is performed such that the exposure amount is preferably 1 to 300 mJ / cm², more preferably 10 to 200 mJ / cm². When EB is used as the high-energy rays, direct drawing is performed such that the exposure amount is preferably 1 to 300 μC / cm², more preferably 10 to 200 μC / cm². Furthermore, the chemical amplification positive type resist composition of the present invention is particularly useful for EUV or EB lithography.

[0748] In addition to the conventional exposure method, it is also possible to use an immersion method in which a liquid is inserted between the mask and the resist film, depending on the case. In that case, it is also possible to use a protective film that is insoluble in water.

[0749] Next, the product is baked (PEB) after exposure on a hot plate, preferably at 60 to 150°C for 1 to 20 minutes, more preferably at 80 to 140°C for 1 to 10 minutes.

[0750] After that, a desired pattern is formed on a substrate by developing using a developer of an alkaline aqueous solution, such as an aqueous solution of TMAH in an amount of preferably 0.1 to 5 mass%, more preferably 2 to 3 mass%, for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as a dip method, a puddle method, or a spray method.

[0751] The chemical amplification positive type resist composition of the present invention is particularly useful when used under conditions where high etching resistance is required, and where the change in pattern linewidth is small and the LER is small even when the time from exposure to PEB is extended. In addition, the chemical amplification positive type resist composition of the present invention is particularly useful for application to substrates having a surface material that is prone to pattern delamination or pattern collapse due to the difficulty in achieving adhesion of the resist pattern. Examples of such substrates include metallic chromium or substrates sputtered with a chromium compound containing one or more light elements selected from oxygen, nitrogen, and carbon. The chemical amplification positive type resist composition of the present invention is particularly useful for pattern formation using a photomask blank as a substrate.

[0752] [Example]

[0753] 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.

[0754] · IR: Thermo Fisher Scientific NICOLET 6700

[0755] · 1 H-NMR: ECA-500 manufactured by Nihon Denshi Corporation

[0756] · MALDI TOF-MS: S3000 manufactured by Nihon Denshi Co., Ltd.

[0757] [1] Synthesis of onium salts

[0758] [Synthesization Example 1-1] Synthesis of Onium Salt PAG-1

[0759]

[0760] (1) Synthesis of Onium Salt PAG-1

[0761] Under a nitrogen atmosphere, raw material SM-1 (8.7g), an aqueous solution of raw material SM-2 (30.5g, equivalent to 25.1 mol), and methylene chloride (50g) were added to a reaction vessel, and after stirring for 15 minutes, the organic layer was taken off and washed with water, and then concentrated under reduced pressure. Methyl isobutyl ketone (50g) was added to the concentrate to perform azeotropic dehydration, and diisopropyl ether was additionally added to crystallize, thereby obtaining 16.7g of the target product PAG-1 as white crystals (yield 95%).

[0762] The IR spectrum data and TOF-MS results of PAG-1 are shown below.

[0763] IR(D-ATR): ν=3067, 2965, 2870, 1606, 1585, 1505, 1468, 1439, 1376, 1327, 1273, 1229, 1206, 1124, 1061, 1017, 1003, 927, 889, 856, 833, 758, 706, 667, 608, 557, 534, 494, 481, 437cm -1 .

[0764] MALDI TOF-MS: POSITIVE M + 277(C 18 H 13 OS + (Significant)

[0765] NEGATIVE M - 679(C 42 H 47 O6S - (Significant)

[0766] [Synthesized Examples 1-2 to 1-10] Synthesis of Onium Salts PAG-2 to PAG-10

[0767] Onium salts PAG-2 to PAG-10 represented by the following formulas were synthesized using corresponding raw materials and known organic synthesis reactions.

[0768]

[0769]

[0770] [Comparative Synthesis Examples 1-1 to 1-5] Synthesis of Comparative Onium Salts PAG-A to PAG-E

[0771] Comparative onium salts PAG-A to PAG-E, represented by the following formulas, were synthesized using corresponding raw materials and known organic synthesis reactions.

[0772]

[0773] [2] Synthesis of polymers

[0774] The monomers used in the synthesis of the polymer are as follows.

[0775]

[0776]

[0777]

[0778]

[0779]

[0780]

[0781]

[0782] [Synthesization Example 2-1] Synthesis of Polymer P-1

[0783] Under a nitrogen atmosphere, monomer A-1 (45.1g), monomer B-1 (54.9g), 7.52g of V-601 (manufactured by Fujifilm Wako Junyaku Co., Ltd.), and 139g of PGMEA (propylene glycol monomethyl ether acetate) were placed in a flask, and a monomer-polymerization initiator solution was prepared. 46g of PGMEA 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. 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 81.1 g, yield 81%). The Mw of polymer P-1 was 5700, and the Mw / Mn ratio was 1.41. In addition, Mw is a polystyrene equivalent measurement value by GPC using THF as a solvent.

[0784]

[0785] [Synthesization Examples 2-2 to 2-54, Comparative Synthesization Examples 2-1 to 2-25] Synthesis of Polymers P-2 to P-54 and Comparative Polymers CP-1 to CP-25

[0786] Polymers P-2 to P-54 shown in Tables 1 and 2 below, and comparative polymers CP-1 to CP-25 shown in Table 3 below, were synthesized in the same manner as in Synthesis Example 2-1, except that the type and mixing ratio of each monomer were changed. In addition, in Tables 1 to 3 below, the introduction rate is mol%.

[0787]

[0788]

[0789]

[0790] The dissolution rate of the above polymers in an alkaline developer was calculated by spin-coating a polymer solution (polymer concentration: 16.7 mass%, solvent: PGME) onto an 8-inch silicon wafer, baking at 100°C for 90 seconds to form a film with a thickness of 1000 nm, developing with a 2.38 mass% aqueous TMAH solution at 23°C for 100 seconds, and measuring the film reduction amount. As a result, the dissolution rate of polymers P-1 to P-54 was 10 nm / min or less. In addition, the dissolution rate of comparative polymers CP-1 to CP-25 was 10 nm / min or less.

[0791] [3] Preparation of a chemically amplified positive type resist composition

[0792] [Examples 1-1 to 1-90, Comparative Examples 1-1 to 1-60]

[0793] A chemically amplified positive type resist composition was prepared by dissolving each component in an organic solvent according to the compositions shown in Tables 4 to 7 below, and filtering the obtained solution through a 5 nm size nylon filter and a 1 nm size UPE filter. In addition, the organic solvent is a mixed solvent of 940 parts by mass of PGMEA, 1870 parts by mass of EL, and 1870 parts by mass of PGME.

[0794]

[0795]

[0796]

[0797]

[0798] In addition, among Tables 4 to 7, the photoacid generators PAG-Y, PAG-Z, quenchers SQ-1 to SQ-4, and fluorine atom-containing polymers FP-1 to FP-5 for blends are as follows.

[0799]

[0800]

[0801]

[0802] [4] EB lithography evaluation

[0803] [Examples 2-1 to 2-90, Comparative Examples 2-1 to 2-60]

[0804] Each chemically amplified positive type resist composition (R-1 to R-90, CR-1 to CR-60) was spin-coated onto square reflective mask blanks for EUV exposure masks, with sides of 152 mm and outermost surfaces being chromium compounds, using ACT-M (manufactured by Tokyo Electron Co., Ltd.), and pre-baked on a hot plate at 110°C for 600 seconds to produce a resist film with a thickness of 80 nm. The film thickness of the obtained resist film was measured using an optical measuring instrument called Nano Spec (manufactured by Nanometrics). Measurements were taken at 81 locations on the surface of the blank substrate, excluding the outer edge portion extending 10 mm inward from the outer periphery, and the average film thickness value and film thickness range were calculated.

[0805] Next, exposure was performed using an electron beam lithography device (NEW FLAER TECHNOLOGY EBM-5000plus, acceleration voltage 50 kV), PEB was performed at 110°C for 600 seconds, and development was carried out with a 2.38 mass% aqueous TMAH solution to obtain a positive pattern. The obtained resist pattern was evaluated as follows.

[0806] Mask blanks having the fabricated pattern were observed using an upper-air SEM (scanning electron microscope), and the exposure amount that resolves 200 nm 1:1 line and space (LS) to 1:1 was set as the optimal exposure amount (μC / cm²), the minimum dimension at the exposure amount that resolves 200 nm LS to 1:1 was set as the limiting resolution (resolution), and the LER of 200 nm LS was measured using SEM. Regarding the limiting resolution of isolated space (IS), the minimum dimension at the exposure amount that resolves 200 nm 9:1 line and space (LS) to 9:1 was set as the limiting IS resolution.

[0807] In addition, 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 ​​between 0.5 and less than 1.0 as B, values ​​between 1.0 and less than 5.0 as C, and values ​​greater than 5.0 as D. A smaller value indicates better performance. The results are shown in Tables 8 to 11.

[0808]

[0809]

[0810]

[0811]

[0812] It was confirmed that the chemically amplified positive type resist compositions (R-1 to R-90) of the present invention all exhibit good resolution and LER, and have few development defects. On the other hand, the resist compositions of the comparative examples (CR-1 to CR-60) showed deterioration in resolution, LER, and development defects due to insufficient optimization of acid diffusion and contrast.

[0813] A method for forming a resist pattern using the chemically amplified positive type resist composition of the present invention is useful for photolithography in the manufacture of semiconductor devices, particularly in the processing of transmission or reflection type photomask blanks.

Claims

Claim 1 (A) a base polymer comprising a repeating unit represented by the following formula (A1) and a polymer whose solubility in an alkaline aqueous solution is increased by the action of an acid, and (B) a photoacid generating agent comprising an onium salt represented by the following formula (B), a chemically amplified positive type resist composition. (In the equation, a1 is 0 or 1. a2 is 0, 1, 2 or 3 when a1 is 0, and 0, 1, 2, 3, 4 or 5 when a1 is 1.R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 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. 2 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. 3 and X 4 is, each independently, an oxygen atom or a sulfur atom. However, X 2 and X 4 is bonded to an adjacent carbon atom of the aromatic ring. 1 and R 2 is a hydrocarbyl group having 1 to 20 carbon atoms, which may each independently contain a hydrogen atom or a heteroatom. Also, R 1 and R 2 a, they may combine with each other to form a ring together with the carbon atom to which they bond. 3 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 3A )(R 3B ) is. R 3A and R 3B Each is independently a hydrogen atom or a hydrocarbyl group having 1 to 6 carbon atoms. When a2 is 2 or more, each R 3 They may be identical or different from each other, and multiple R 3 These may combine with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. [In the equation, n1 is 0 or 1. n2 is 0, 1, 2, 3 or 4. n3 is 2, 3 or 4. Provided that when n1 is 0, 2 ≤ n2 + n3 ≤ 5, and when n1 is 1, 2 ≤ n2 + n3 ≤ 7.R 101 It is 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, a hydrocarbylthio group having 1 to 20 carbon atoms that may contain a heteroatom, or a hydrocarbyloxycarbonyl group having 1 to 20 carbon atoms that may contain a heteroatom. When n2 is 2, 3, or 4, each R 101 They may be identical or different from each other, and multiple R 101 These may combine with each other to form a ring together with the carbon atoms they bond to. + is an onium cation.Ar AL is an acid instability group containing a group represented by the following formula (AL). provided that at least one Ar AL silver, -SO3 - It is bonded to the carbon atom adjacent to the carbon atom it is bonding to. (In the equation, n4 is 0 or 1. n5 is 0, 1, 2, 3 or 4. n6 is 0, 1, 2, 3 or 4. n7 is 1 or 2. Provided that when n4 is 0, 1 ≤ n5 + n6 + n7 ≤ 5, and when n4 is 1, 1 ≤ n5 + n6 + n7 ≤ 7.R 102 is a halogen atom other than a fluorine 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 n5 is 2, 3, or 4, each R 102 They may be identical or different from each other, and multiple R 102 They may bond with each other to form a ring together with the carbon atoms they bond to. F is 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, a fluorinated saturated hydrocarbylthio group having 1 to 6 carbon atoms, or a pentafluorosulfanyl group. When n6 is 2, 3, or 4, each R F They may be the same or different. L1 and R L2 is, each independently, a hydrocarbyl group having 1 to 12 carbon atoms. R L3 It is 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 or a multiple bond, some or all of the hydrogen atoms bonded to the carbon atoms constituting the said aromatic ring or multiple bond 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 cases where this cyclic structure, directional ring, and multiple bonds are not all included, R L1 and R L2 They bond with each other to form a ring together with the carbon atoms they bond to, and some of the -CH2- groups of the ring may be substituted with -O- or -S-.* indicates a bond loss.)] Claim 2 In paragraph 1, X 3 and X 4 A chemically amplified positive type resist composition in which all atoms are oxygen atoms. Claim 3 In paragraph 1, X 2 A chemically amplified positive type resist composition in which the carbonyl group is present. Claim 4 A chemically amplified positive type resist composition according to claim 1, wherein the light acid generating agent is represented by the following formula (B1). (Eating, n1, n2, n3, n5, n6, n7, R 101 , R 102 , R F , R L1 to R L3 and Z + is the same as above.) Claim 5 A chemically amplified positive type resist composition in which, in paragraph 4, the above-mentioned photoacid generator is represented by the following formula (B2). (Eating, n2, n3, n5, n6, n7, R 101 , R 102 , R F , R L1 to R L3 and Z + is the same as above.) Claim 6 In paragraph 1, Z + a. A chemically amplified positive type resist composition, wherein the sulfonium cation represented by the following formula (Z-1) or the iodonium cation represented by the following formula (Z-2). (during food, R ct1 to R ct5 is a hydrocarbyl group having 1 to 30 carbon atoms, which may each independently contain a halogen atom or a heteroatom. Also, R ct1 and R ct2 a. They may combine with each other to form a ring together with the sulfur atom to which they combine.) Claim 7 In paragraph 1, Z + a. A chemically amplified positive type resist composition, wherein the sulfonium cation is represented by the following formula (Z-3). (In the equation, m1 is 0 or 1. m2 is 0 or 1. m3 is 0 or 1. m4 is 0, 1, 2, 3 or 4. m5 is 0, 1, 2, 3 or 4. m6 is 0, 1, 2, 3, 4, 5 or 6. m7 is 0, 1, 2, 3, 4, 5 or 6. m8 is 0, 1 or 2. m9 is 0, 1 or 2. m10 is 0, 1 or 2. m11 is 0 or 1. m12 is 0, 1, 2, 3 or 4. m13 is 0, 1 or 2. m14 is 0, 1 or 2. provided that when m1 is 0, 0 ≤ m6 + m9 ≤ 4, and m1 is When m2 is 1, 0 ≤ m6 + m9 ≤ 6. When m2 is 0, 0 ≤ m7 + m10 ≤ 4, and when m2 is 1, 0 ≤ m7 + m10 ≤ 6. When m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4, and when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6. When m11 is 0, 0 ≤ m12 + m13 ≤ 4, and when m11 is 1, 0 ≤ m12 + m13 ≤ 6. Also, m4 + m12 ≥ 1. 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. When m5 is 2, 3, or 4, each R F1 They may be the same or different. When m6 is 2, 3, 4, 5, or 6, each R F2 may be the same or different. When m7 is 2, 3, 4, 5, or 6, each R F3 They may be the same or different. ct6 to R ct9 is a halogen atom other than an iodine atom and a fluorine atom, a nitro group, a cyano 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 m8 is 2, 2 R ct6 They may be identical or different, and 2 R ct6 These may bond with each other to form a ring with the carbon atom they bond to. When m9 is 2, 2 R ct7 They may be identical or different, and 2 R ct7 These may bond with each other to form a ring with the carbon atom to which they bond. When m10 is 2, 2 R ct8 They may be identical or different, and 2 R ct8 These may bond with each other to form a ring with the carbon atom to which they bond. When m13 is 2, 2 R ct9 They may be the same or different, and 2 R ct9 They may bond with each other to form a ring together with the carbon atom to which they bond. In addition, S in the sulfonium cation + Direction rings that directly bind to each other combine with S + It may form a ring together with.L A and L B Each is, independently, a single bond, ether bond, ester bond, amide bond, sulfonic acid ester bond, sulfonamide bond, carbonate bond, or carbamate bond. L It is a hydrocarbylene group having 1 to 40 carbon atoms that may contain single bonds or heteroatoms. Claim 8 A chemically amplified positive type resist composition according to claim 1, wherein the polymer further comprises repeating units represented by the following formula (A2). (In the expression, b1 is 0, 1, or 2. b2 is 1, 2, or 3. b3 is an integer satisfying 0 ≤ b3 ≤ 5 + 2(b1) - b2.R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 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. 11 It is a halogen atom, a nitro group, a carboxyl group, a saturated hydrocarbyl group having 1 to 6 carbon atoms that may be substituted with a halogen atom, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms that may be substituted with a halogen atom, or a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen atom. 1 ...is a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and a portion of the -CH2- of the said saturated hydrocarbylene group may be substituted with -O-.) Claim 9 A chemically amplified positive type resist composition according to claim 1, wherein the polymer comprises at least one selected from a repeating unit represented by the following formula (A3), a repeating unit represented by the following formula (A4), and a repeating unit represented by the following formula (A5). (In the expression, c is 0, 1, 2, 3, 4, 5, or 6. d is 0, 1, 2, 3, or 4. e1 is 0 or 1. e2 is 0, 1, or 2. e3 is 0, 1, 2, 3, 4, or 5.R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 21 and R 22 Each is independently a hydroxyl group, a halogen atom, a saturated hydrocarbyl group having 1 to 8 carbon atoms that may be substituted with a halogen atom, a saturated hydrocarbyloxy group having 1 to 8 carbon atoms that may be substituted with a halogen atom, or a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen atom. 23 is a saturated hydrocarbyl group having 1 to 20 carbon atoms, a saturated hydrocarbyloxy group having 1 to 20 carbon atoms, a saturated hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms, a saturated hydrocarbyloxyhydrocarbyl group having 2 to 20 carbon atoms, a saturated hydrocarbylthiohydrocarbyl group having 2 to 20 carbon atoms, a halogen atom, a nitro group, or a cyano group, and may be a hydroxyl group when e3 is 1 or 2. 2 is a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and a portion of the -CH2- of the said saturated hydrocarbylene group may be substituted with -O-.) Claim 10 A chemically amplified positive type resist composition according to claim 1, wherein the polymer further comprises at least one selected from a repeating unit represented by the following formula (A6-1) and a repeating unit represented by the following formula (A6-2). (In the expression, f1 is 0 or 1. f2 is 0, 1 or 2. f3 is an integer satisfying 0 ≤ f3 ≤ 5 + 2(f2) - f4. f4 is 1, 2 or 3. f5 is 0 or 1. f11 is 0, 1 or 2. f12 is 0, 1 or 2. f13 is 0, 1 or 2. f14 is 0, 1, 2, 3, 4 or 5. R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 3 is a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and a portion of the -CH2- of the said saturated hydrocarbylene group may be substituted with -O-.A 4 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OA 41 -is. A 41 is an aliphatic hydrocarbylene group having 1 to 20 carbon atoms, or a phenylene group or a naphthylene group, which 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. R 31 It is a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms that may be substituted with a halogen atom, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms that may be substituted with a halogen atom, or a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen atom. 32 and R 33 Each is a hydrocarbyl group having 1 to 10 carbon atoms that may independently contain a heteroatom, and R 32 and R 33 These may combine with each other to form a ring together with the carbon atoms to which they bond. 34 Each is independently a fluorine atom, a carbon-1 to carbon-5 fluorinated alkyl group, or a carbon-1 to carbon-5 fluorinated alkoxy group. 35 Each is a hydrocarbyl group having 1 to 10 carbon atoms that may independently contain a heteroatom. X is an acid unstable group when f4 is 1, and is a hydrogen atom or an acid unstable group when f4 is 2 or 3, but at least one is an acid unstable group. Claim 11 A chemically amplified positive type resist composition according to claim 1, wherein the polymer comprises at least one selected from a repeating unit represented by the following formula (A7), a repeating unit represented by the following formula (A8), a repeating unit represented by the following formula (A9), a repeating unit represented by the following formula (A10), and a repeating unit represented by the following formula (A11). (In the equation, g1 and g2 are each independently 0, 1, 2, or 3. h1 is 0 or 1. h2 is 0, 1, 2, 3, or 4. h3 is 0, 1, 2, 3, or 4. Provided that when h1 is 0, 0 ≤ h2 + h3 ≤ 4, and when h1 is 1, 0 ≤ h2 + h3 ≤ 6.R A Each is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It is a phenylene group that may have a single bond or a substituent. 2 is a single bond, **-C(=O)-OZ 21 -, **-C(=O)-N(H)-Z 21 - or **-OZ 21 -is. Z 21 It is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by a combination thereof, and may include a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 3 It is a single bond, ether bond, ester bond, sulfonic acid ester bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. 4 is a single bond, or an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by a combination thereof, and may include a halogen atom, a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 5 are, respectively, single bond, a phenylene group that may have a substituent, a naphthylene group that may have a substituent, *-C(=O)-OZ 51 - or *-C(=O)-N(R)-Z 51 -is. Z 51 is an aliphatic hydrocarbylene group, a phenylene group, or a naphthylene group having 1 to 10 carbon atoms, and the aliphatic hydrocarbylene group may include a halogen atom, a hydroxyl group, an ether bond, an ester bond, or a lactone ring. R is a hydrocarbylene group having 1 to 10 carbon atoms that may include a hydrogen atom or a heteroatom. Z 6 It is a single bond, ether bond, ester bond, sulfonic acid ester bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. 7 Silver, each independently, single bond, ***-Z 71 -C(=O)-O-, ***-C(=O)-N(R)-Z 71 - or ***-OZ 71 -is. Z 71 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms. R is the same as above. Z 8 Silver, each independently, single bond, ****-Z 81 -C(=O)-O-, ****-C(=O)-N(R)-Z 81 - or ****-OZ 81 -is. Z 81 It is a hydrocarbylene group having 1 to 20 carbon atoms that may contain heteroatoms. R is the same as above. Z 9 is a single bond, methylene group, ethylene group, phenylene group, fluorinated phenylene group, phenylene group substituted with a trifluoromethyl group, *-C(=O)-OZ 91 -, *-C(=O)-N(R)-Z 91 - or *-OZ 91 -is. Z 91 is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may include a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. R is the same as above. * indicates a loss of bond with a carbon atom of the main chain. ** is Z 1 Indicates the bonding loss with. *** is Z 6 Indicates the bond with. **** is Z 7 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. Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbyl group having 1 to 6 carbon atoms. provided that all Rf 5 and Rf 6 There is no case where it becomes a hydrogen atom at the same time. 7 The fluorine atom, the C1 to C6 fluorinated alkyl group, and the C1 to C6 fluorinated alkoxy group are C1 to C6 fluorinated alkyl thio groups or pentafluorosulfanyl groups. When h2 is 2, 3, or 4, each Rf 7 They may be the same or different. 41 and R 42 is a hydrocarbyl group having 1 to 20 carbon atoms that may each independently contain a heteroatom. Also, R 41 and R 42 a, they may combine with each other to form a ring together with the sulfur atom to which they combine. 43 It is a hydrocarbyl group having 1 to 20 carbon atoms that may contain halogen atoms other than fluorine atoms or heteroatoms. When h3 is 2, 3, or 4, each R 43 They may be identical or different from each other, and multiple R 43 These may combine with each other to form a ring together with the carbon atoms they bond to. - is a non-nucleophilic counterion. + is an onium cation.) Claim 12 A chemically amplified positive type resist composition according to claim 1, wherein the content of repeating units having an aromatic ring backbone among the total repeating units of the polymer included in the base polymer is 60 mol% or more. Claim 13 In claim 1, additionally, (C) a chemically amplified positive type resist composition comprising an organic solvent. Claim 14 In claim 1, additionally, (D) a chemically amplified positive type resist composition comprising a quencher. Claim 15 A chemically amplified positive type resist composition according to claim 1, further comprising at least one selected from a repeating unit represented by the following formula (E1), a repeating unit represented by the following formula (E2), a repeating unit represented by the following formula (E3), and a repeating unit represented by the following formula (E4), and further comprising at least one selected from a repeating unit represented by the following formula (E5) and a repeating unit represented by the following formula (E6). (In the expression, j1 is 1, 2, or 3. j2 is an integer satisfying 0 ≤ j2 ≤ 5 + 2(j3) - j1. j3 is 0 or 1. k is 1, 2, or 3.R B R is, independently, a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. C R is, independently, a hydrogen atom or a methyl group. 301 , R 302 , R 304 and R 305 R is, each independently, a hydrogen atom or a saturated hydrocarbyl group having 1 to 10 carbon atoms. 303 , R 306 , R 307 and R 308 Each independently is a hydrogen atom, a hydrocarbyl group having 1 to 15 carbon atoms, a fluorinated hydrocarbyl group having 1 to 15 carbon atoms, or an acid instability group, and R 303 , R 306 , R 307 and R 308 When this is a hydrocarbyl group or a fluorinated hydrocarbyl group, an ether bond or a carbonyl group may be interposed between the carbon-carbon bonds. 309 is a straight-chain or branched hydrocarbyl group having 1 to 5 carbon atoms, which may include a hydrogen atom or a group containing a heteroatom between carbon-carbon bonds. When j1 is 2 or 3, each R 309 They may be the same or different. 310 It is a straight-chain or branched hydrocarbyl group having 1 to 5 carbon atoms, wherein a group containing a heteroatom may be interposed between carbon-carbon bonds. When j2 is 2 or more, each R 310 They may be the same or different. 311 Silver is a saturated hydrocarbyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and a portion of the -CH2- of the saturated hydrocarbyl group may be substituted by an ester bond or an ether bond. 1 is a (k+1) valent hydrocarbon group having 1 to 20 carbon atoms or a (k+1) valent fluorinated hydrocarbon group having 1 to 20 carbon atoms. 2 is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-. * is a bond with a carbon atom in the main chain. 3 is a single bond, -O-, *-C(=O)-OW 31 -W 32 - or *-C(=O)-N(H)-W 31 -W 32 -is. W 31 It is a single bond or a saturated hydrocarbylene group having 1 to 10 carbon atoms. W 32 is a single bond, ester bond, ether bond, or sulfonamide bond. * is a bond with a carbon atom of the main chain.) Claim 16 A chemically amplified positive type resist composition according to claim 1, further comprising a photoacid generating agent other than an onium salt represented by formula (B). Claim 17 A method for forming a resist pattern, comprising: a process of forming a resist film on a substrate using a chemically amplified positive type resist composition described in any one of claims 1 to 16; a process of irradiating a pattern onto the resist film using a high-energy beam; and a process of developing the resist film irradiated with the pattern using an alkaline developer. Claim 18 A method for forming a resist pattern according to claim 17, wherein the high-energy line is an extreme ultraviolet or electron line with a wavelength of 3 to 15 nm. Claim 19 A method for forming a resist pattern according to claim 17, wherein the outermost surface of the substrate comprises a material including chromium. Claim 20 A method for forming a resist pattern according to claim 17, wherein the substrate is a photomask blank.

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