Process for producing base polymer for photoresist, pattern forming method, and precursor polymer

Abstract

The present invention relates to a method for producing a base polymer for photoresist, a pattern forming method, and a precursor polymer. The present invention is a method for producing a base polymer for photoresist, comprising the following steps: (1) preparing a precursor polymer containing a repeating unit (a') of an ammonium salt compound, a repeating unit (b') of a compound in which a hydrogen atom of a carboxylic acid is protected with an acid-labile group, and a repeating unit (c') of a compound in which a phenolic hydroxyl group is protected, (2) deprotecting the aforementioned repeating unit (c') and obtaining a deprotected precursor polymer, and (3) converting the ammonium salt of the aforementioned repeating unit (a') into a sulfonium salt or a sulfoxonium salt and obtaining a base polymer for photoresist. Thus, a method for producing a base polymer for photoresist, which is included in a chemically amplified resist composition that is excellent in solvent solubility, high sensitivity, high contrast, and lithography properties such as EL, LWR, CDU, DOF, and the like in optical lithography using high-energy rays, is provided.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a base polymer for photoresist, a method for patterning, and a precursor polymer. Background Technology

[0002] With the increasing integration and speed of LSI (Light Detector System), the miniaturization of patterning is also progressing rapidly. In particular, the expansion of the flash memory market and the increase in memory capacity are driving this miniaturization. Regarding the most advanced miniaturization technologies, mass production of 65nm node devices using ArF lithography is already underway, and preparations are underway for mass production of 45nm node devices using next-generation ArF immersion lithography. For next-generation 32nm node devices, options such as immersion lithography using ultra-high nanometer (NA) lenses (combining liquids with higher refractive indices than water with high-refractive-index lenses and high-refractive-index resist films), extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm, and double exposure (dual patterning lithography) using ArF lithography are being explored.

[0003] As miniaturization progresses and the light diffraction limit approaches, the contrast of light gradually decreases. This decrease in contrast leads to a reduction in the resolution of hole patterns, groove patterns, or focal length latitude in positive resist films.

[0004] As patterns become more refined, the linewidth roughness (LWR) of the line pattern and the dimensional uniformity (CDU) of the hole pattern are considered problems. Issues cited include uneven distribution of the base polymer and acid generator, the effects of aggregation, and the influence of acid diffusion. Furthermore, the thinning of the resist film tends to increase the LWR, and the deterioration of LWR caused by thinning during refinement becomes a serious problem.

[0005] In EUV lithography resist compositions, high sensitivity, high resolution, and low light-to-weight ratio (LWR) must be achieved simultaneously. Shortening the acid diffusion distance will reduce LWR, but it will also lower sensitivity. For example, lowering the post-exposure baking (PEB) temperature will reduce LWR, but it will also lower sensitivity. Increasing the amount of quencher will also reduce LWR, but it will also lower sensitivity. Therefore, a trade-off between sensitivity and LWR needs to be struck.

[0006] To suppress acid diffusion, resist compounds containing polymers with repeating units derived from onium salts of sulfonic acids with polymerizable unsaturated bonds have been proposed (Patent Document 1). Such polymer-bonded acid generators, due to the generation of polymeric sulfonic acids upon exposure, exhibit a very short acid diffusion distance. Furthermore, sensitivity can be improved by increasing the ratio of the acid generator. Additive acid generators, while increasing the amount added, also increase sensitivity, but this also increases the acid diffusion distance. Since acid diffuses unevenly, increased acid diffusion degrades LWR and CDU. In terms of balancing sensitivity, LWR, and CDU, polymeric acid generators offer superior performance.

[0007] Iodine atoms exhibit very high absorption at EUV wavelengths of 13.5 nm, leading to the observed generation of secondary electrons during exposure, thus attracting attention in EUV lithography. Patent Document 2 describes a photoacid generator incorporating iodine atoms into anion, while Patent Document 3 describes a photoacid generator containing polymerizable groups of iodine atoms incorporating iodine atoms into anion. While this results in some improvement in lithography performance, the low solubility of iodine atoms in organic solvents raises concerns about precipitation in solvents.

[0008] Existing technical documents

[0009] Patent documents

[0010] [Patent Document 1] Japanese Patent No. 4425776

[0011] [Patent Document 2] Japanese Patent No. 6720926

[0012] [Patent Document 3] Japanese Patent No. 6973274 Summary of the Invention

[0013] [The problem that the invention aims to solve]

[0014] The goal is to develop resist compositions with higher sensitivity and improved lithographic properties such as exposure latitude (EL), light ripple (LWR), chromatic duct density (CDU), and depth of focus (DOF) in chemically amplified resist compositions using acid as a catalyst.

[0015] The present invention was made in view of the foregoing circumstances, and aims to provide a method for manufacturing a base polymer for photoresist contained in a chemically amplified photoresist composition that has excellent solvent solubility, high sensitivity, high contrast, and excellent photolithography performance such as EL, LWR, CDU, and DOF in optical lithography using high-energy rays; a patterning method using a chemically amplified photoresist composition containing the aforementioned base polymer; and a precursor polymer.

[0016] [Methods for solving the problem]

[0017] To address the aforementioned issues, the present invention provides a method for manufacturing a basic polymer for photoresist. This method comprises a repeating unit (a) of a photoacid generator containing an anionic portion and a main chain link, and whose cationic portion is a sulfonate or monazine cation; a repeating unit (b) of a compound whose hydrogen atoms of a carboxylic acid are protected by acid-instable groups; and a repeating unit (c) of a compound containing phenolic hydroxyl groups. The method includes the following steps:

[0018] (1) Precursor polymers containing repeating units (a') of ammonium salt compounds with anionic portions and main chain linkages, and whose cationic portions are quaternary ammonium cations, repeating units (b') of compounds in which the hydrogen atoms of carboxylic acids are protected by acid-instable groups, and repeating units (c') of compounds in which phenolic hydroxyl groups are protected.

[0019] (2) Deprotect the repeating unit (c') of the compound in the precursor polymer prepared in step (1) to expose the phenolic hydroxyl groups, and obtain the deprotected precursor polymer.

[0020] (3) The ammonium salt of the repeating unit (a') of the aforementioned ammonium salt compound in the deprotected precursor polymer obtained in step (2) is converted into sulfonium salt or sulfonium salt, and a base polymer for photoresist is obtained.

[0021] If such a method is used to manufacture the base polymer for photoresist, then the base polymer for photoresist contained in a chemically amplified photoresist composition that has excellent solvent solubility, high sensitivity, high contrast, and excellent photolithography performance such as EL, LWR, CDU, and DOF can be manufactured in optical lithography using high-energy rays.

[0022] Furthermore, the present invention preferably uses the repeating unit (1a') represented by the following general formula (1a') as the aforementioned repeating unit (a'), the repeating unit (1b') represented by the following general formula (1b') as the aforementioned repeating unit (b'), and the repeating unit (1c') represented by the following general formula (1c') as the aforementioned repeating unit (c').

[0023] [Chemistry 1]

[0024]

[0025] In the formula, a1 is 0 or 1. a2 is an integer from 0 to 4. a3 is an integer from 0 to 4.

[0026] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0027] R 1It can be a halogen atom, nitro group, cyano group, hydroxyl group, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms. Furthermore, when a2 is 2, 3, or 4, multiple R... 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0028] X 1 It is a linking group.

[0029] Q 1 ~Q 4 Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom.

[0030] R N1 ~R N4 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R N1 ~R N4 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to.

[0031] [Chemistry 2]

[0032]

[0033] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0034] Z 1 Single bond, phenylene, naphthylene, *-C(=O)-OZ 11 -、or *-C(=O)-NH-Z 11 - and the aforementioned phenylene or naphthylene may also be substituted by hydroxyl, nitro, cyano, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, or saturated hydrocarbon oxygen groups with 1 to 10 carbon atoms containing fluorine atoms, or halogen atoms. 11 It is a saturated alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the aforementioned saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0035] AL 1 It is an acid-labile group.

[0036] [Chemistry 3]

[0037]

[0038] In the formula, b1 is an integer from 1 to 4. b2 is an integer from 0 to 4. However, 1 ≤ b1 + b2 ≤ 5.

[0039] R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0040] Y1 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain.

[0041] R 11 It can be a halogen atom, carboxyl group, nitro group, cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl oxygen group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxygen carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When b2 is 2, 3, or 4, each R 11 They can be the same or different.

[0042] AL 2 It is an acid-instable group or a base-instable group.

[0043] The present invention is preferably made using such repeating units.

[0044] At this time, it is advisable to use the repeating unit (11a') represented by the following general formula (11a') as the aforementioned repeating unit (1a').

[0045] [Chemistry 4]

[0046]

[0047] In the formula, a1~a3, R A R 1 Q 1 ~Q 4 and R N1 ~R N4 Same as above.

[0048] If it is such a repeating unit, then considering the reasons for obtaining raw materials, the rationale for synthesis, and stability is more ideal.

[0049] At this time, it is advisable to use the repeating unit (12a') represented by the following general formula (12a') as the aforementioned repeating unit (11a').

[0050] [Chemistry 5]

[0051]

[0052] In the formula, a1, a2, R A R 1 Q 2 ~Q 4 and R N1 ~R N4 Same as above.

[0053] The present invention preferably uses such repeating units.

[0054] Furthermore, in this invention, the aforementioned repeating unit (a) contained in the aforementioned photoresist base polymer preferably has a sulfonium cation represented by the following general formula (Z-3).

[0055] [Chemistry 6]

[0056]

[0057] In the formula, m1 is 0 or 1. m2 is 0 or 1. m3 is 0 or 1. m4 is an integer from 0 to 4. m5 is an integer from 0 to 4. m6 is an integer from 0 to 6. m7 is an integer from 0 to 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 an integer from 0 to 4. m13 is 0, 1, or 2. m14 is 0, 1, or 2. However, when m1 is 0, 0 ≤ m6 + m9 ≤ 4; when m1 is 1, 0 ≤ m6 + m9 ≤ 6. When m2 is 0, 0 ≤ m7 + m10 ≤ 4; when m2 is 1, 0 ≤ m7 + m10 ≤ 6. When m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4; when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6. When m11 is 0, 0 ≤ m12 + m13 ≤ 4; when m11 is 1, 0 ≤ m12 + m13 ≤ 6. Also, m4 + m12 ≥ 1.

[0058] R F1 ~R F3 Each R is independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms. When m5 is 2, 3, or 4, each R F1 They can be the same or different. When m6 is an integer from 2 to 6, each R... F2 They can be the same or different. When m7 is an integer from 2 to 6, each R... F3 They can be the same or different.

[0059] R ct6 ~R ct9 It can be a halogen atom other than iodine and fluorine atoms, a nitro group, a cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. When m8 is 2, there are 2 R groups. ct6 They can be the same or different, and there are 2 Rs. ct6 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m9 is 2, there are 2 R atoms. ct7 They can be the same or different, and there are 2 Rs. ct7 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m10 is 2, the two R atoms... ct8 They can be the same or different, and there are 2 Rs. ct8They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m13 is 2, there are 2 R atoms. ct9 They can be the same or different, and there are 2 Rs. ct9 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0060] Furthermore, S directly bonded to the sulfonium cation + The aromatic rings can also bond with each other and with S + Together they form a ring.

[0061] L A and L B Each bond can be independently a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0062] X L It is a single bond or may contain heteroatoms and is a hydrocarbon group with 1 to 40 carbon atoms.

[0063] Such sulfonium cations are preferred for use in this invention.

[0064] Furthermore, the present invention provides a pattern forming method, comprising the following steps:

[0065] A resist film is formed on a substrate using a photoresist composition containing a photoresist base polymer prepared by the manufacturing method described above.

[0066] The aforementioned resist film was exposed to high-energy radiation, and

[0067] The previously exposed resist film was developed using a developer.

[0068] If such a pattern is to be formed, the desired pattern can be formed using a photoresist composition containing a photoresist base polymer obtained by the manufacturing method of the photoresist base polymer of the present invention.

[0069] At this time, it is advisable to use KrF excimer laser, ArF excimer laser, electron beam, or extreme ultraviolet light with a wavelength of 3~15nm as the aforementioned high-energy rays.

[0070] This invention can utilize such high-energy rays.

[0071] Furthermore, the present invention provides a precursor polymer containing repeating units (1a') represented by the following general formula (1a'), repeating units (1b') represented by the following general formula (1b'), and repeating units (1c') represented by the following general formula (1c').

[0072] [Chemistry 7]

[0073]

[0074] In the formula, a1 is 0 or 1. a2 is an integer from 0 to 4. a3 is an integer from 0 to 4.

[0075] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0076] R 1 It can be a halogen atom, nitro group, cyano group, hydroxyl group, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms. Furthermore, when a2 is 2, 3, or 4, multiple R... 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0077] X 1 It is a linking group.

[0078] Q 1 ~Q 4 Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom.

[0079] R N1 ~R N4 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R N1 ~R N4 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to.

[0080] [Chemistry 8]

[0081]

[0082] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0083] Z 1 Single bond, phenylene, naphthylene, *-C(=O)-OZ 11 -、or *-C(=O)-NH-Z 11 - and the aforementioned phenylene or naphthylene may also be substituted by hydroxyl, nitro, cyano, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, or saturated hydrocarbon oxygen groups with 1 to 10 carbon atoms containing fluorine atoms, or halogen atoms. 11 It is a saturated alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the aforementioned saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0084] AL 1 It is an acid-labile group.

[0085] [Chemistry 9]

[0086]

[0087] In the formula, b1 is an integer from 1 to 4. b2 is an integer from 0 to 4. However, 1 ≤ b1 + b2 ≤ 5.

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

[0089] Y 1 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain.

[0090] R 11 It can be a halogen atom, carboxyl group, nitro group, cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl oxygen group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxygen carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When b2 is 2, 3, or 4, each R 11 They can be the same or different.

[0091] AL 2 It is an acid-instable group or a base-instable group.

[0092] If such a precursor polymer is used, it can be used as a precursor polymer in the method for manufacturing the base polymer for photoresist of the present invention.

[0093] At this time, the aforementioned repeating unit (1a') should preferably be the repeating unit (11a') represented by the following general formula (11a').

[0094] [Chemistry 10]

[0095]

[0096] In the formula, a1~a3, R A R 1 Q 1 ~Q 4 and R N1 ~R N4 Same as above.

[0097] If it is such a repeating unit, then considering the reasons for obtaining raw materials, the rationale for synthesis, and stability is more ideal.

[0098] At this time, the aforementioned repeating unit (11a') should preferably be the repeating unit (12a') represented by the following general formula (12a').

[0099] [Chemistry 11]

[0100]

[0101] In the formula, a1, a2, R A R 1 Q 2 ~Q 4 and R N1 ~R N4 Same as above.

[0102] The present invention preferably uses such repeating units.

[0103] [The effects of the invention]

[0104] When patterning is performed using a chemically amplified resist composition containing the base polymer obtained by the manufacturing method of the photoresist base polymer of the present invention, as described above, resist patterns with high contrast and good sensitivity, as well as excellent photolithography performance such as EL, LWR, CDU, and DOF, and excellent etching resistance can be formed. Furthermore, the precursor polymer of the present invention can be the precursor polymer used in the manufacturing method of the photoresist base polymer of the present invention. Detailed Implementation

[0105] As described above, the requirements are to develop a method for manufacturing a base polymer for a chemically amplified resist composition containing a photoresist that has excellent solvent solubility, high sensitivity, high contrast, and excellent photolithography performance such as EL, LWR, CDU, and DOF in optical lithography using high-energy rays; a patterning method using a chemically amplified resist composition containing the aforementioned base polymer; and a precursor polymer.

[0106] Through repeated and in-depth exploration in order to achieve the aforementioned objectives, the inventors discovered that by using a photoresist composition containing a basic polymer for photoresist prepared from monomers with specific structures and chemically modified from the aforementioned copolymers, a chemically amplified photoresist composition with high sensitivity, improved lithographic properties such as EL, LWR, CDU, and DOF, high contrast, and high resolution can be obtained, thus completing the present invention.

[0107] That is, the present invention is a method for manufacturing a basic polymer for photoresist, which is a method for manufacturing a basic polymer for photoresist containing repeating units (a) of a photoacid generator having an anionic portion and a main chain connection, and the cationic portion being a sulfonium cation or a monazine cation, repeating units (b) of a compound in which the hydrogen atoms of a carboxylic acid are protected by acid-instable groups, and repeating units (c) of a compound containing phenolic hydroxyl groups, comprising the following steps:

[0108] (1) Precursor polymers containing repeating units (a') of ammonium salt compounds with anionic portions and main chain linkages, and whose cationic portions are quaternary ammonium cations, repeating units (b') of compounds in which the hydrogen atoms of carboxylic acids are protected by acid-instable groups, and repeating units (c') of compounds in which phenolic hydroxyl groups are protected.

[0109] (2) Deprotect the repeating unit (c') of the compound in the precursor polymer prepared in step (1) to expose the phenolic hydroxyl groups, and obtain the deprotected precursor polymer.

[0110] (3) The ammonium salt of the repeating unit (a') of the aforementioned ammonium salt compound in the deprotected precursor polymer obtained in step (2) is converted into sulfonium salt or sulfonium salt, and a base polymer for photoresist is obtained.

[0111] The present invention will now be described in detail. Furthermore, in the following description, the structure represented by the chemical formula may contain asymmetric carbon, and mirror-image isomers and non-mirror-image isomers may exist; in such cases, each isomer is represented by a single formula. These isomers may be used individually or in mixtures of two or more.

[0112] [Base polymers for photoresist]

[0113] In this invention, the photoresist base polymer is manufactured via the materials and steps described below.

[0114] That is, the present invention provides a method for manufacturing a basic polymer for photoresist, which is a method for manufacturing a basic polymer for photoresist containing repeating units (a) of a photoacid generator having an anionic portion and a main chain connection, and the cationic portion being a sulfonium cation or a monazine cation, repeating units (b) of a compound in which the hydrogen atoms of a carboxylic acid are protected by acid-instable groups, and repeating units (c) of a compound containing phenolic hydroxyl groups, comprising the following steps:

[0115] (1) Precursor polymers containing repeating units (a') of ammonium salt compounds with anionic portions and main chain linkages, and whose cationic portions are quaternary ammonium cations, repeating units (b') of compounds in which the hydrogen atoms of carboxylic acids are protected by acid-instable groups, and repeating units (c') of compounds in which phenolic hydroxyl groups are protected.

[0116] (2) Deprotect the repeating unit (c') of the compound in the precursor polymer prepared in step (1) to expose the phenolic hydroxyl groups, and obtain the deprotected precursor polymer.

[0117] (3) The ammonium salt of the repeating unit (a') of the aforementioned ammonium salt compound in the deprotected precursor polymer obtained in step (2) is converted into sulfonium salt or sulfonium salt, and a base polymer for photoresist is obtained.

[0118] Here, it is appropriate to use the repeating unit (1a') represented by the following general formula (1a') as the aforementioned repeating unit (a').

[0119] [Chemistry 12]

[0120]

[0121] In the formula, a1 is 0 or 1. a2 is an integer from 0 to 4. a3 is an integer from 0 to 4.

[0122] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0123] R 1 It can be a halogen atom, nitro group, cyano group, hydroxyl group, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms. Furthermore, when a2 is 2, 3, or 4, multiple R... 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0124] X 1 It is a linking group.

[0125] Q 1 ~Q 4 Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom.

[0126] R N1 ~R N4 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R N1 ~R N4 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to.

[0127] In the above general formula (1a'), a1 is 0 or 1. When a1 is 0, it is a benzene ring; when a1 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with a1 of 0 is more ideal. a2 is an integer from 0 to 4. Considering the availability of raw materials, it is preferable to be 0 or 1. a3 is an integer from 0 to 4. Considering the availability of raw materials, it is preferable to be 1 to 3.

[0128] In the above general formula (1a'), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Among these, a hydrogen atom or a methyl group is preferred, with a hydrogen atom being more desirable.

[0129] In the above general formula (1a'), R 1It can be a halogen atom, nitro group, cyano group, hydroxyl group, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms. The aforementioned halogen atom is preferably a fluorine atom, chlorine atom, bromine atom, or iodine atom, with fluorine or iodine atom being more preferred. Furthermore, the aforementioned hydrocarbon group can be saturated or unsaturated, and can be any of the following: straight-chain, branched, or cyclic. Specific examples include: alkyl groups with 1-20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; cyclic saturated hydrocarbon groups with 3-20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl; alkenyl groups with 2-20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3-20 carbon atoms, such as cyclohexenyl; aryl groups with 6-20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7-20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these. Among these, aryl groups are preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. This can result in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Also, when a2 is 2, 3, or 4, each R... 1 They can be the same or different.

[0130] When a2 is 2, 3, or 4, multiple R 1 They can also bond with each other and form rings together with the carbon atoms they are bonded to. Specific examples of rings formed in this case include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, norbornene ring, adamantane ring, etc. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of the -CH2- in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0131] In the above general formula (1a'), X 1 The linking group is preferably an ether bond, ester bond, sulfone bond, sulfonate bond, carbonate bond, carbamate bond, amide bond, or sulfonamide bond.

[0132] In the above general formula (1a'), R N1 ~R N4 Each group can be an independent hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. The hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1-20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; cyclic saturated hydrocarbon groups with 3-20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl; alkenyl groups with 2-20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3-20 carbon atoms, such as cyclohexenyl; aryl groups with 6-20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7-20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these. Among these, aryl groups are preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. This can result in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Also, R N1 ~R N4 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to.

[0133] It is preferable to use the repeating unit (11a') represented by the following general formula (11a') as the aforementioned repeating unit (1a'). The sulfonate bond shown in the formula is more ideal from the perspective of raw material acquisition, synthetic rationale and stability.

[0134] [Chemistry 13]

[0135]

[0136] In the formula, a1~a3, R A R 1 Q 1 ~Q 4 and R N1 ~R N4 Same as above.

[0137] In addition, the repeating unit (12a') represented by the following general formula (12a') should be used as the aforementioned repeating unit (11a').

[0138] [Chemistry 14]

[0139]

[0140] In the formula, a1, a2, R A R 1 Q 2 ~Q 4 and R N1 ~R N4 Same as above.

[0141] Examples of anions providing the monomers of the aforementioned repeating unit (a') include, but are not limited to, those shown below. Additionally, in the following formula, R... A As mentioned above, Me is methyl. Furthermore, the bonding positions of the various substituents on the aromatic ring can be interchanged.

[0142] [Chemistry 15]

[0143]

[0144] [Chemistry 16]

[0145]

[0146] [Chemistry 17]

[0147]

[0148] [Chemistry 18]

[0149]

[0150] [Chemistry 19]

[0151]

[0152] [Chemistry 20]

[0153]

[0154] [Chemistry 21]

[0155]

[0156] [Chemistry 22]

[0157]

[0158] [Chemistry 23]

[0159]

[0160] [Chemistry 24]

[0161]

[0162] [Chemistry 25]

[0163]

[0164] [Chemistry 26]

[0165]

[0166] [Chemistry 27]

[0167]

[0168] [Chemistry 28]

[0169]

[0170] [Chemistry 29]

[0171]

[0172] [Chemistry 30]

[0173]

[0174] [Chemistry 31]

[0175]

[0176] [Chemistry 32]

[0177]

[0178] [Chemistry 33]

[0179]

[0180] [Chemistry 34]

[0181]

[0182] [Chemistry 35]

[0183]

[0184] [Chemistry 36]

[0185]

[0186] [Chemistry 37]

[0187]

[0188] [Chemistry 38]

[0189]

[0190] [Chemistry 39]

[0191]

[0192] [Chemistry 40]

[0193]

[0194] [Chemistry 41]

[0195]

[0196] [Chemistry 42]

[0197]

[0198] [Chemistry 43]

[0199]

[0200] [Chemistry 44]

[0201]

[0202] Ammonium cations of monomers providing the repeating unit (a') described above may be listed below, but are not limited thereto.

[0203] [Chemistry 45]

[0204]

[0205] Specific examples of monomers providing the above repeating unit (a') can be any combination of the anions and ammonium cations illustrated above.

[0206] Next, the repeating unit (b') will be explained. It is preferable to use the repeating unit (1b') represented by the following general formula (1b') as the repeating unit (b') mentioned above.

[0207] [Chemistry 46]

[0208]

[0209] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0210] Z 1 Single bond, phenylene, naphthylene, *-C(=O)-OZ 11 -、or *-C(=O)-NH-Z 11 - and the aforementioned phenylene or naphthylene may also be substituted by hydroxyl, nitro, cyano, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, or saturated hydrocarbon oxygen groups with 1 to 10 carbon atoms containing fluorine atoms, or halogen atoms.11 It is a saturated alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the aforementioned saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0211] AL 1 It is an acid-labile group.

[0212] In the above general formula (1b'), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 Single bond, phenylene, naphthylene, *-C(=O)-OZ 11 -、or *-C(=O)-NH-Z 11 - and the aforementioned phenylene or naphthylene may also be substituted by hydroxyl, nitro, cyano, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, or saturated hydrocarbon oxygen groups with 1 to 10 carbon atoms containing fluorine atoms, or halogen atoms. 11 It is a straight-chain, branched, or cyclic saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the aforementioned saturated hydrocarbon group may also contain hydroxyl groups, ether bonds, ester bonds, or lactone rings. * indicates an atomic bond with a carbon atom in the main chain. AL 1 It is an acid-labile group.

[0213] In the above general formula (1b'), the transformation Z 1 The structure can be listed as shown below, but is not limited to these. Additionally, in the following formula, R... A and AL 1 Same as above.

[0214] [Chemistry 47]

[0215]

[0216] [Chemistry 48]

[0217]

[0218] The base polymer for photoresist containing the aforementioned repeating unit (b') will decompose and produce carboxyl groups due to the action of acid, thus becoming alkali-soluble.

[0219] AL 1 There are no particular restrictions on the acid-unstable groups represented. For example, they are preferably groups selected from the following general formulas (L1) to (L4), tertiary hydrocarbon groups with 4 to 20 carbons, preferably 4 to 15, trialkylsilyl groups with each hydrocarbon group having 1 to 6 carbons, hydrocarbon groups with 4 to 20 carbons containing carbonyl, ether, or ester bonds, benzyl groups, etc.

[0220] [Chemistry 49]

[0221]

[0222] In the formula, the dashed lines represent atomic bonds.

[0223] In the above general formula (L1), R L01 and R L02 It is a hydrogen atom or a saturated hydrocarbon group with 1 to 18 carbon atoms, preferably 1 to 10. The aforementioned saturated hydrocarbon group can be any of the following: straight-chain, branched, or cyclic. Specific examples include: alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-octyl, and 2-ethylhexyl; and cyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, norcamphenyl, tricyclodecyl, tetracyclododecyl, and adamantyl.

[0224] R L03 The hydrocarbon group has 1 to 18 carbon atoms, preferably 1 to 10, and may also contain heteroatoms. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic, but is preferably a saturated hydrocarbon group. Furthermore, some or all of the hydrogen atoms in the aforementioned saturated hydrocarbon group may be replaced by hydroxyl groups, saturated hydroxyl groups, oxo groups, amino groups, saturated hydroxyl amino groups, etc., and a portion of the -CH2- group constituting the aforementioned saturated hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms. Examples of the aforementioned saturated hydrocarbon groups include those listed above as R... L01 and R L02 The same examples represent saturated hydrocarbon groups. Furthermore, substituted saturated hydrocarbon groups can be listed as shown below, etc.

[0225] [Transformation 50]

[0226]

[0227] In the formula, the dashed lines represent atomic bonds.

[0228] R L01 R L02 and R L03 Any two atoms in the ring can bond to each other and form a ring together with the carbon atoms they are bonded to, or with both carbon and oxygen atoms. During ring formation, R participates in the ring formation. L01 R L02 and R L03 Any two of them should be alkyldiyl groups with 1 to 18 carbon atoms, and preferably 1 to 10 carbon atoms.

[0229] In the above general formula (L2), R L04 It is a tertiary hydrocarbon group having 4 to 20 carbon atoms, preferably 4 to 15; a trialkylsilyl group having each alkyl group having 1 to 6 carbon atoms; a saturated hydrocarbon group having 4 to 20 carbon atoms containing a carbonyl group, an ether bond, or an ester bond; or a group represented by the above general formula (L1). x is an integer from 0 to 6.

[0230] R L04The tertiary hydrocarbon group can be branched or cyclic, and specific examples include: tert-butyl, tert-pentyl, 1,1-diethylpropyl, 2-cyclopentylpropane-2-yl, 2-cyclohexylpropane-2-yl, 2-(bicyclo[2.2.1]heptane-2-yl)propane-2-yl, 2-(adamantane-1-yl)propane-2-yl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, etc. The aforementioned trialkylsilyl groups include: trimethylsilyl, triethylsilyl, dimethyltert-butylsilyl, etc. Examples of saturated hydrocarbon groups containing carbonyl, ether, or ester bonds include: 3-oxocyclohexyl, 4-methyl-2-oxooxacyclohexane-4-yl, 5-methyl-2-oxooxacyclopentane-5-yl, etc.

[0231] In the above general formula (L3), R L05 It can be a saturated hydrocarbon group with 1 to 8 carbon atoms that can also be substituted, or an aryl group with 6 to 20 carbon atoms that can also be substituted. The aforementioned saturated hydrocarbon groups that can be substituted can be any of straight-chain, branched, or cyclic forms. Specific examples include: alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, and n-hexyl; cyclic saturated hydrocarbon groups such as cyclopentyl and cyclohexyl; and those in which some or all of the hydrogen atoms are replaced by hydroxyl, saturated hydrocarbon oxy group with 1 to 8 carbon atoms, carboxyl, saturated hydrocarbon carbonyl group with 2 to 8 carbon atoms, oxo group, amino group, saturated hydrocarbon amino group with 1 to 8 carbon atoms, cyano group, mercapto group, saturated hydrocarbon thio group with 1 to 8 carbon atoms, sulfonyl group, etc. Examples of aryl groups that can be substituted include: phenyl, tolyl, naphthyl, anthracene, phenanthrene, pyrene, and those in which some or all of the hydrogen atoms are replaced by hydroxyl, saturated hydrocarbon oxy group with 1 to 8 carbon atoms, carboxyl, saturated hydrocarbon carbonyl group with 2 to 8 carbon atoms, oxo group, amino, saturated hydrocarbon amino group with 1 to 8 carbon atoms, cyano, mercapto, saturated hydrocarbon thio group with 1 to 8 carbon atoms, sulfonyl, etc.

[0232] In the above general formula (L3), y is 0 or 1, z is an integer from 0 to 3, and 2y + z = 2 or 3.

[0233] In the above general formula (L4), R L06 It can be a saturated hydrocarbon group with 1 to 8 carbon atoms that can be substituted, or an aryl group with 6 to 20 carbon atoms that can be substituted. Specific examples of the aforementioned saturated hydrocarbon groups that can be substituted and aryl groups that can be substituted can be listed and illustrated as R. L05 The same example represents the same thing.

[0234] In the above general formula (L4), R L07 ~R L16Each group consists independently of a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, which may also be substituted. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic, but are preferably saturated hydrocarbon groups. Examples of such hydrocarbon groups include: alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, and n-decyl; cyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, and cyclohexylbutyl; and cyclic saturated hydrocarbon groups in which some or all of the hydrogen atoms are substituted with hydroxyl, saturated hydrocarbon oxy group having 1 to 8 carbon atoms, carboxyl, saturated hydrocarbon oxycarbonyl group having 2 to 8 carbon atoms, oxo group, amino, saturated hydrocarbon amino group having 1 to 8 carbon atoms, cyano, mercapto, saturated hydrocarbon thio group having 1 to 8 carbon atoms, sulfonyl, etc. R L07 ~R L16 In this context, two atoms selected from these atoms can also bond to each other and form a ring together with the carbon atoms they are bonded to (e.g., R). L07 With R L08 R L07 With R L09 R L07 With R L10 R L08 With R L10 R L09 With R L10 R L11 With R L12 R L13 With R L14 (etc.), in this case, the group participating in ring formation is a hydrocarbon group having 1 to 15 carbon atoms. Examples of such hydrocarbon groups include those formed by removing one hydrogen atom from those exemplified as hydrocarbon groups. Furthermore, R L07 ~R L16 In this context, bonds between adjacent carbon atoms can also form double bonds without any atoms in between (e.g., R1). L07 With R L09 R L09 With R L15 R L13 With R L15 R L14 With R L15 wait).

[0235] The straight-chain or branched groups among the acid-labile groups represented by the above general formula (L1) can be listed below, but are not limited to these groups.

[0236] [Chemistry 51]

[0237]

[0238] In the formula, the dashed lines represent atomic bonds.

[0239] Examples of cyclic groups among the acid-labile groups represented by the above general formula (L1) include: tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropiperan-2-yl, 2-methyltetrahydropiperan-2-yl, etc.

[0240] Examples of acid-labile groups represented by the general formula (L2) above include: tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-pentoxycarbonyl, tert-pentoxycarbonylmethyl, 1,1-diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl, 2-tetrahydrofuranyloxycarbonylmethyl, etc.

[0241] The acid-labile groups represented by the above general formula (L3) can be listed as follows: 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec-butylcyclopentyl, 1-cyclohexylcyclopentyl, 1-(4-methoxy-n-butyl)cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexen-3-yl, 3-ethyl-1-cyclohexen-3-yl, etc.

[0242] The acid-instable group represented by the above general formula (L4) is preferably the group represented by the following general formulas (L4-1) to (L4-4).

[0243] [Chemistry 52]

[0244]

[0245] In the above general formulas (L4-1) to (L4-4), the dashed lines represent the bond positions and bond directions. R L41 Each hydrocarbon group is an independent hydrocarbon group having 1 to 10 carbon atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic, but are preferably saturated hydrocarbon groups. Examples of such hydrocarbon groups include: alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, and n-hexyl; and cyclic saturated hydrocarbon groups such as cyclopentyl and cyclohexyl.

[0246] The groups represented by the above general formulas (L4-1) to (L4-4) may have stereoisomers (mirror image isomers or non-mirror image isomers), but the above general formulas (L4-1) to (L4-4) represent all of these stereoisomers. When the aforementioned acid-instable group is a group represented by the above general formula (L4), it may also contain multiple stereoisomers.

[0247] For example, the above general formula (L4-3) is defined as representing a mixture of one or two groups selected from those represented by the following general formulas (L4-3-1) and (L4-3-2).

[0248] [Chemistry 53]

[0249]

[0250] In the formula, R L41 Same as above. Dashed lines represent atomic bonds.

[0251] Furthermore, the above general formula (L4-4) is defined as representing a mixture of one or more groups selected from those represented by the following general formulas (L4-4-1) to (L4-4-4).

[0252] [Chemistry 54]

[0253]

[0254] In the formula, R L41 Same as above. Dashed lines represent atomic bonds.

[0255] The above general formulas (L4-1)~(L4-4), (L4-3-1), (L4-3-2), and (L4-4-1)~(L4-4-4) are defined as representing their mirror isomers and mixtures of mirror isomers.

[0256] Furthermore, the bonding directions of the above general formulas (L4-1)~(L4-4), (L4-3-1), (L4-3-2), and (L4-4-1)~(L4-4-4), with the exo side relative to the bicyclic [2.2.1]heptane ring respectively, achieve high reactivity in acid catalyst leaving reactions (see Japanese Patent Application Publication No. 2000-336121). In the manufacture of monomers with tertiary exo-saturated hydrocarbon groups having a bicyclic [2.2.1]heptane skeleton as substituents, when the monomers are endo-alkyl substituted as represented by the following general formulas (L4-1-endo)~(L4-4-endo), in order to achieve good reactivity, the exo ratio is preferably 50 mol% or more, and more preferably 80 mol% or more.

[0257] [Chemistry 55]

[0258]

[0259] In the formula, R L41 Same as above. Dashed lines represent atomic bonds.

[0260] The acid-instable groups represented by the above general formula (L4) can be listed as shown below, but are not limited to these groups.

[0261] [Chemistry 56]

[0262]

[0263] In the formula, the dashed lines represent atomic bonds.

[0264] Also, AL 1 The acid-unstable groups represented by tertiary hydrocarbon groups with 4-20 carbon atoms, trialkylsilyl groups with each hydrocarbon group having 1-6 carbon atoms, and saturated hydrocarbon groups with 4-20 carbon atoms containing carbonyl groups, ether bonds, or ester bonds can be listed separately as R. L04 The same examples are illustrated in the description.

[0265] The repeating unit (1b') represented by the above general formula (1b') can be listed as shown below, but is not limited to these. Additionally, in the following formula, R... A Same as above.

[0266] [Chemistry 57]

[0267]

[0268] [Chem.58]

[0269]

[0270] [Chemistry 59]

[0271]

[0272] [Transformation 60]

[0273]

[0274] [Chemistry 61]

[0275]

[0276] [Chemistry 62]

[0277]

[0278] Also, AL 1 When it is a secondary hydrocarbon group, it can sometimes function as an unstable group in acids. Specifically, the following structures are examples.

[0279] [Chemistry 63]

[0280]

[0281] Furthermore, these specific examples are Z in the above general formula (1b'). 1 For the case of a single bond, but even in Z 1 In cases other than single bonds, it can also combine with the same acid-labile groups. Z1 Specific examples of cases other than single bonds, as described above, especially Z. 1 Phenylidene is more ideal.

[0282] The repeating unit (c') will then be described in detail. The repeating unit (c') mentioned above should preferably be represented by the following general formula (1c').

[0283] [Chemistry 64]

[0284]

[0285] In the formula, b1 is an integer from 1 to 4. b2 is an integer from 0 to 4. However, 1 ≤ b1 + b2 ≤ 5.

[0286] R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0287] Y 1 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain.

[0288] R 11 It can be a halogen atom, carboxyl group, nitro group, cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl oxygen group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxygen carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When b2 is 2, 3, or 4, each R 11 They can be the same or different.

[0289] AL 2 It is an acid-instable group or a base-instable group.

[0290] In the above general formula (1c'), b1 is an integer from 1 to 4, preferably 1 or 2. b2 is an integer from 0 to 4, preferably 0, 1, or 2. However, 1 ≤ b1 + b2 ≤ 5. R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain.

[0291] R 11The group may contain halogen atoms, carboxyl groups, nitro groups, cyano groups, or hydrocarbon groups with 1 to 20 carbon atoms containing heteroatoms; hydrocarbon oxy groups with 1 to 20 carbon atoms containing heteroatoms; hydrocarbon carbonyl groups with 2 to 20 carbon atoms containing heteroatoms; hydrocarbon carbonyloxy groups with 2 to 20 carbon atoms containing heteroatoms; or hydrocarbon oxycarbonyl groups with 2 to 20 carbon atoms containing heteroatoms. The aforementioned hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include: alkyl groups with 1-20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; cyclic saturated hydrocarbon groups with 3-20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl; alkenyl groups with 2-20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3-20 carbon atoms, such as cyclohexenyl; aryl groups with 6-20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7-20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these. Among these, aryl groups are preferred. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. This can result in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Also, when b2 is 2, 3, or 4, each R... 11 They can be the same or different.

[0292] AL 2 These are acid-labile or base-labile unstable groups. Examples of acid-labile unstable groups include those mentioned above (AL). 1 Similarly, an example of an acid-instable group is preferably an acetal-type substituent represented by the aforementioned general formula (L1). AL 2 As will be described later, during the synthesis of the base polymer for photoresist, deprotection eventually occurs, exposing the phenolic hydroxyl groups. Therefore, AL 2 Substituents should ideally be highly reactive. AL 2 When reactivity is low, in AL 2 During deprotection treatment, there is a concern that the acid-labile groups of the repeating unit (b') may also react. The acetal-type substituents represented by the aforementioned general formula (L1) are highly reactive to acids; therefore, regarding AL... 2 Ideally, this is the case. Especially R in the aforementioned general formula (L1) L01 Methyl, RL02 For hydrogen atoms, R L03 For compounds that are ethyl groups, ease of acquisition is a more desirable consideration.

[0293] AL 2 When the substituent is a base-instable group, there are no particular restrictions on its structure if it can be deprotected by reaction with a basic compound; for example, substituents with ester bonds are preferred. Specifically, examples include acetyl, trifluoroacetyl, and trifluoropropylcarbonyl groups; considering ease of acquisition and cost, acetyl is particularly good. Furthermore, basic compounds that can deprotect the base-instable group include caustic soda and amine compounds.

[0294] The repeating unit (1c') represented by the above general formula (1c') can be specifically exemplified by the structure shown below, but is not limited thereto. Furthermore, in the following formula, R... A and AL 2 Same as above.

[0295] [Chemistry 65]

[0296]

[0297] [Chemistry 66]

[0298]

[0299] [Chemistry 67]

[0300]

[0301] [Chemistry 68]

[0302]

[0303] [Chemistry 69]

[0304]

[0305] [Manufacturing method of base polymer for photoresist]

[0306] The method for manufacturing the base polymer for photoresist of the present invention comprises step (1) of preparing a precursor polymer containing at least the aforementioned repeating units (a'), (b'), and (c'). The polymerization method of this precursor polymer can be carried out using known methods. Specifically, a method can be listed as polymerizing a monomer providing the aforementioned repeating units by adding a free radical polymerization initiator to an organic solvent and heating it.

[0307] Furthermore, it is advisable to use the repeating unit (1a') represented by the above general formula (1a') as the aforementioned repeating unit (a'), the repeating unit (1b') represented by the above general formula (1b') as the aforementioned repeating unit (b'), and the repeating unit (1c') represented by the above general formula (1c') as the aforementioned repeating unit (c').

[0308] Examples of organic solvents used in polymerization include: toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Examples of free radical polymerization initiators include: 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(dimethyl isobutyrate), 2,2'-azobis(2,4-dimethylpentanonitrile), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The amount of these free radical polymerization initiators added relative to the total amount of monomers used in polymerization should preferably be 0.01–30 mol%. The reaction temperature should preferably be 50–150 °C, preferably 60–100 °C. The reaction time should preferably be 2–24 hours, but considering production efficiency, 2–12 hours is preferred.

[0309] The aforementioned free radical polymerization initiator can be added to the aforementioned monomer solution and supplied to the reactor, or an initiator solution different from the aforementioned monomer solution can be prepared separately and supplied to the reactor independently. Since the polymerization reaction may proceed and generate ultrapolymers due to free radicals generated from the free radical polymerization initiator during standby time, from a quality management perspective, the monomer solution and initiator solution should preferably be prepared separately and added dropwise. Furthermore, to adjust the molecular weight, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can also be used in combination. In this case, the amount of these chain transfer agents added relative to the total amount of monomers used to polymerize should preferably be 0.01 to 20 mol%. Alternatively, thiocarbonyl sulfur compounds, also known as RAFT agents, can be used as chain transfer agents. Examples of RAFT agents include S,S-dibenzyl trithiocarbonate manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd. By using RAFT agents, the dispersion of the polymer can be narrowed.

[0310] The precursor polymer of the present invention may also contain other repeating units (d'). Other repeating units (d') may include aromatic compounds such as styrene, indene, and acenaphthene for enhancing etching resistance, methacrylate compounds containing lactone or carbonate sites for adjusting developer solubility, or fluorinated methacrylate compounds.

[0311] In the precursor polymer of the present invention, the content ratios of the repeating units a', b', c', and d' should be 0 < a' ≤ 0.5, 0 < b' ≤ 0.8, 0 < c' ≤ 0.8, 0 ≤ d' ≤ 0.6, and it is more preferable that 0 < a' ≤ 0.3, 0 < b' ≤ 0.7, 0 < c' ≤ 0.6, 0 ≤ d' ≤ 0.4. However, 0 < a' + b' + c' + d' ≤ 1.0.

[0312] The weight-average molecular weight (Mw) of the precursor polymer of the present invention should be 1,000 to 500,000, and it is more preferable that it is 3,000 to 100,000. If Mw is within this range, sufficient etching resistance can be obtained when derived into a polymer for a photoresist, and there is no concern about a decrease in resolution caused by the inability to ensure the difference in dissolution rate before and after exposure. In addition, in the present invention, Mw is a polystyrene conversion measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as a solvent.

[0313] Regarding the molecular weight distribution (Mw / Mn) of the precursor polymer of the present invention, considering the view that the influence of Mw / Mn tends to become larger as the pattern rule is miniaturized, in order to obtain a resist composition that can be ideally used for fine pattern sizes, Mw / Mn should preferably be a narrow dispersion of 1.0 to 2.0. If it is within the above range, when derived into a polymer for a photoresist, there are fewer polymers with low Mw and high Mw, and defects such as foreign matter on the pattern and deterioration of the pattern shape after exposure can be suppressed.

[0314] The obtained precursor polymer can enter the deprotection step (step (2)) continuously without going through the steps of separating or crystallizing the precursor polymer from the reaction solution, or the reaction solution can also be added to a poor solvent, and after being made into the obtained powder by a purification step such as the reprecipitation method for obtaining the powder, then enter step (2).

[0315] As described above, step (2) is a step of deprotecting the repeating unit (c') of the compound in which the phenolic hydroxyl group in the precursor polymer prepared in step (1) is protected and exposing the phenolic hydroxyl group to obtain a deprotected precursor polymer. When the repeating unit (c') is deprotected, it becomes the repeating unit (c). For the protecting group, an acid-labile group or a base-labile group can be selected as described above. There is no particular limitation on the deprotection of the acid-labile group. For example, it can be carried out by adding a weak acid and, if necessary, water to the precursor polymer obtained in step (1). Examples of the weak acid include acetic acid, oxalic acid, etc. On the other hand, for the removal of the base-labile group, for example, base hydrolysis using ammonia water, triethylamine, ethanolamine, etc. can be exemplified. However, the deprotection method of the base-labile group is not limited to this.

[0316] For the deprotected precursor polymer obtained in step (2), it can also be introduced into the final step (step (3)) without going through the step of separating or crystallizing the deprotected precursor polymer from the reaction solution, just like the precursor polymer obtained in step (1). Alternatively, the reaction solution can be added to a poor solvent and purified by a reprecipitation method or other purification steps to obtain the powder before entering step (3).

[0317] Step (3) involves converting the ammonium cation of the repeating unit (a') of the aforementioned ammonium salt compound in the deprotected precursor polymer obtained in step (2) into a sulfonium cation or a sulfonium cation to obtain a base polymer for photoresist. The cation of the repeating unit (a') becomes the repeating unit (a) upon conversion. By converting it into such a photosensitive cation, the base polymer for photoresist functions as a photoresist material.

[0318] In repeating unit (a), the aforementioned sulfonium cation or monium cation is preferably a sulfonium cation represented by the following general formula (Z-1) or a monium cation represented by the following general formula (Z-2).

[0319] [Chemistry 70]

[0320]

[0321] In the above general formulas (Z-1) and (Z-2), R ct1 ~R ct5 Each is a hydrocarbon group with 1 to 30 carbon atoms, which may be independently composed of halogen atoms or may contain heteroatoms.

[0322] R ct1 ~R ct5 Specific examples of halogen atoms that can be represented include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0323] R ct1 ~R ct5The hydrocarbon group represented can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl; alkenyl groups with 2 to 30 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 30 carbon atoms such as cyclohexenyl; aryl groups with 6 to 30 carbon atoms such as phenyl, naphthyl, and thiophene; aralkyl groups with 7 to 30 carbon atoms such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these groups, which should preferably be aryl. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0324] Also, R ct1 and R ct2 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. Specific examples of the aforementioned ring structures can be shown in the following formulas, etc.

[0325] [Chemistry 71]

[0326]

[0327] In the formula, the dashed line represents R. ct3 Atomic bonds.

[0328] Specific examples of sulfonium cations represented by the above general formula (Z-1) can be listed, such as those described in paragraphs

[0102] to

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

[0070] to

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

[0329] Specific examples of citric acid represented by the above general formula (Z-2) can be found in paragraph

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

[0330] The aforementioned repeating unit (a) contained in the base polymer of the aforementioned photoresist preferably has a sulfonium cation represented by the following general formula (Z-3).

[0331] [Chemistry 72]

[0332]

[0333] In the formula, m1 is 0 or 1. m2 is 0 or 1. m3 is 0 or 1. m4 is an integer from 0 to 4. m5 is an integer from 0 to 4. m6 is an integer from 0 to 6. m7 is an integer from 0 to 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 an integer from 0 to 4. m13 is 0, 1, or 2. m14 is 0, 1, or 2. However, when m1 is 0, 0 ≤ m6 + m9 ≤ 4; when m1 is 1, 0 ≤ m6 + m9 ≤ 6. When m2 is 0, 0 ≤ m7 + m10 ≤ 4; when m2 is 1, 0 ≤ m7 + m10 ≤ 6. When m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4; when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6. When m11 is 0, 0 ≤ m12 + m13 ≤ 4; when m11 is 1, 0 ≤ m12 + m13 ≤ 6. Also, m4 + m12 ≥ 1.

[0334] R F1 ~R F3 Each R is independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms. When m5 is 2, 3, or 4, each R F1 They can be the same or different. When m6 is an integer from 2 to 6, each R... F2 They can be the same or different. When m7 is an integer from 2 to 6, each R... F3 They can be the same or different.

[0335] R ct6 ~R ct9 It can be a halogen atom other than iodine and fluorine atoms, a nitro group, a cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. When m8 is 2, there are 2 R groups. ct6 They can be the same or different, and there are 2 Rs. ct6 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m9 is 2, there are 2 R atoms. ct7 They can be the same or different, and there are 2 Rs. ct7 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m10 is 2, the two R atoms... ct8 They can be the same or different, and there are 2 Rs. ct8 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m13 is 2, there are 2 R atoms. ct9 They can be the same or different, and there are 2 Rs. ct9 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0336] Furthermore, S directly bonded to the sulfonium cation + The aromatic rings can also bond with each other and with S + Together they form a ring.

[0337] L A and L B Each bond can be independently a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0338] X L It is a single bond or may contain heteroatoms and is a hydrocarbon group with 1 to 40 carbon atoms.

[0339] In the above general formula (Z-3), m1 is 0 or 1. When m1 is 0, it is a benzene ring; when m1 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with m1 = 0 is more ideal. m2 is 0 or 1. When m2 is 0, it is a benzene ring; when m2 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with m1 = 0 is more ideal. m3 is 0 or 1. When m3 is 0, it is a benzene ring; when m3 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with m3 = 0 is more ideal.

[0340] In the above general formula (Z-3), m4 is an integer from 0 to 4. The more iodine atoms in the cationic structure, the higher the absorption of EUV, but the solvent solubility will become more lacking and there is a concern about precipitation in the resist composition. Therefore, m4 should preferably be an integer from 0 to 3, and 0, 1 or 2 is better.

[0341] In the above general formula (Z-3), m5 is an integer from 0 to 4. Considering the availability of raw materials, m5 should preferably be an integer from 0 to 3, with 0, 1, or 2 being more preferred. m6 is an integer from 0 to 6. Considering the availability of raw materials, m6 should preferably be an integer from 0 to 3, with 0, 1, or 2 being more preferred. m7 is an integer from 0 to 6. Considering the availability of raw materials, m7 should preferably be an integer from 0 to 3, with 0, 1, or 2 being more preferred.

[0342] In the above general formula (Z-3), m8 is 0, 1, or 2. Considering the availability of raw materials, m8 should preferably be 0 or 1. m9 is 0, 1, or 2. Considering the availability of raw materials, m9 should preferably be 0 or 1. m10 is 0, 1, or 2. Considering the availability of raw materials, m10 should preferably be 0 or 1.

[0343] In the above general formula (Z-3), m11 is 0 or 1. When m11 is 0, it is a benzene ring; when m11 is 1, it is a naphthalene ring. Considering solvent solubility, a benzene ring with m11 of 0 is more ideal.

[0344] In the above general formula (Z-3), m12 is an integer from 0 to 4. The more iodine atoms in the cationic structure, the higher the absorption of EUV, but the solvent solubility will become more lacking and there is a concern about precipitation in the resist composition. Therefore, m12 should preferably be an integer from 0 to 3, and 0, 1 or 2 is better.

[0345] In the above general formula (Z-3), m13 is 0, 1, or 2. From the perspective of raw material availability, m13 is preferably 0 or 1. m14 is 0, 1, or 2. From a synthetic perspective, m14 is preferably 0 or 1.

[0346] However, when m1 is 0, 0 ≤ m6 + m9 ≤ 4; when m1 is 1, 0 ≤ m6 + m9 ≤ 6. When m2 is 0, 0 ≤ m7 + m10 ≤ 4; when m2 is 1, 0 ≤ m7 + m10 ≤ 6. When m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4; when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6. When m11 is 0, 0 ≤ m12 + m13 ≤ 4; when m11 is 1, 0 ≤ m12 + m13 ≤ 6. Also, m4 + m12 ≥ 1.

[0347] In the above general formula (Z-3), R F1 ~R F3 Each R is independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms. Among these, trifluoromethyl, trifluoromethoxy, and trifluorothiomethoxy are preferred. When m5 is 2, 3, or 4, each R... F1 They can be the same or different. When m6 is an integer from 2 to 6, each R... F2 They can be the same or different. When m7 is an integer from 2 to 6, each R... F3 They can be the same or different.

[0348] In the above general formula (Z-3), R ct6 ~R ct9 The radical can be a halogen atom other than iodine or fluorine, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms, a hydrocarbon oxygen group with 1 to 20 carbon atoms that may contain heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms that may contain heteroatoms. The hydrocarbon group, as well as the hydrocarbon oxygen and hydrocarbon thio groups, can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated in the description of the above general formula (1a') as R. 1The same example applies to the hydrocarbon group. Furthermore, some or all of the hydrogen atoms in the hydrocarbon group, as well as the hydrocarbon group of the alkyl group and alkyl thio group, can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. Also, a portion of the -CH2- group of the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0349] Also, when m8 is 2, there are 2 Rs. ct6 They can be the same or different, and there are 2 Rs. ct6 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m9 is 2, there are 2 R atoms. ct7 They can be the same or different, and there are 2 Rs. ct7 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m10 is 2, the two R atoms... ct8 They can be the same or different, and there are 2 Rs. ct8 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m13 is 2, there are 2 R atoms. ct9 They can be the same or different, and there are 2 Rs. ct9 They can also bond with each other and form rings together with the carbon atoms they are bonded to. Specific examples of rings formed in this case include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, norbornene ring, adamantane ring, etc. Furthermore, some or all of the hydrogen atoms in the aforementioned rings can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of the -CH2- in the aforementioned rings can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, they may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0350] Furthermore, the S directly bonded to the sulfonium cation represented by the above general formula (Z-3) + The aromatic rings can also bond with each other and with S + Together they form a ring. Specific examples of the aforementioned ring structure can be represented by the following formulas, etc.

[0351] [Chemistry 73]

[0352]

[0353] In the formula, the dashed lines represent atomic bonds.

[0354] In the above general formula (Z-3), LA and L B These can be independently identified as single bonds, ether bonds, ester bonds, amide bonds, sulfonate bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds. Among them, L... A The bonds should ideally be single bonds, ether bonds, ester bonds, or sulfonate bonds, with ester bonds or sulfonate bonds being more preferred. B It is preferable to have a single bond, ether bond, or ester bond, with a single bond being better.

[0355] In the above general formula (Z-3), X L It is a single-bonded or heteroatom-containing alkylene group with 1 to 40 carbon atoms. The aforementioned alkylene group can be linear, branched, or cyclic; specific examples include alkyldiyl, cyclic saturated alkylene groups, and arylene groups. Specific examples of the aforementioned heteroatom include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0356] X L Examples of hydrocarbon groups containing 1 to 40 carbon atoms that may also contain heteroatoms are shown below, but are not limited to these. Additionally, in the following formula, * indicates that they are related to L... A and L B Atomic bonds.

[0357] [Chemistry 74]

[0358]

[0359] [Chemistry 75]

[0360]

[0361] [Chemistry 76]

[0362]

[0363] [Chemistry 77]

[0364]

[0365] Among them, X is the most suitable. L -0~X L -22 and X L -47~X L -58.

[0366] The sulfonium cation represented by the above general formula (Z-3) should preferably be represented by the following general formula (Z-3-1).

[0367] [Chemistry 78]

[0368]

[0369] In the formula, m4~m10, m12~m14, R F1 ~RF3 R ct6 ~R ct9 L A L B and X L Same as above.

[0370] The sulfonium cation represented by the above general formula (Z-3-1) should preferably be represented by the following general formula (Z-3-2).

[0371] [Chemistry 79]

[0372]

[0373] In the formula, m4~m10, R F1 ~R F3 and R ct6 ~R ct8 Same as above.

[0374] Specific examples of sulfonium cations represented by the above general formula (Z-3) are shown below, but are not limited thereto. Additionally, in the following formula, Me is a methyl group.

[0375] [Chemistry 80]

[0376]

[0377] [Chemistry 81]

[0378]

[0379] [Chemistry 82]

[0380]

[0381] [Chemistry 83]

[0382]

[0383] [Chemistry 84]

[0384]

[0385] [Chemistry 85]

[0386]

[0387] [Chemistry 86]

[0388]

[0389] [Chemistry 87]

[0390]

[0391] [Chemistry 88]

[0392]

[0393] [Chemistry 89]

[0394]

[0395] [Chemistry 90]

[0396]

[0397] [Chemistry 91]

[0398]

[0399] [Chemistry 92]

[0400]

[0401] [Chemistry 93]

[0402]

[0403] [Chemistry 94]

[0404]

[0405] [Chem. 95]

[0406]

[0407] [Chemistry 96]

[0408]

[0409] [Chemistry 97]

[0410]

[0411] [Chem. 98]

[0412]

[0413] [Chemistry 99]

[0414]

[0415] [Chemistry 100]

[0416]

[0417] [Chemistry 101]

[0418]

[0419] [Chemistry 102]

[0420]

[0421] [Chemistry 103]

[0422]

[0423] [Chemistry 104]

[0424]

[0425] [Chemistry 105]

[0426]

[0427] [Chemistry 106]

[0428]

[0429] [Chemistry 107]

[0430]

[0431] Specific examples of repeating unit (a) can be listed as any combination of the aforementioned anions with sulfonium cations or sulfonium cations.

[0432] The method for converting the ammonium salt of the repeating unit (a') of the aforementioned ammonium salt compound in the deprotected precursor polymer obtained in step (2) into a sulfonium salt or sulfonium salt can be achieved using known organic chemical methods, for example, by referring to the method described in the embodiment of Japanese Patent No. 6841183. Furthermore, the deprotected precursor polymer obtained in step (2) can proceed to step (3) after separation, or it can proceed without separation in its bolded state.

[0433] The photoresist base polymer obtained in step (3) can be recovered in powder form by onion salt exchange reaction and reprecipitation method, and used as the final product. Alternatively, the polymer solution dissolved in the photoresist solvent can be used as the final product instead of being made into powder.

[0434] When dissolving the base polymer of a photoresist in a photoresist solvent, it is advisable to perform filtration. Filtration removes foreign matter and gel that could cause defects, effectively stabilizing the quality.

[0435] The materials used for the aforementioned filters include fluorocarbon, cellulose, nylon, polyester, and hydrocarbon materials. In the polymer solution filtration step, filters made of fluorocarbon (such as Teflon, a registered trademark), polyethylene, polypropylene, or nylon are preferred. The pore size of the filter can be appropriately selected according to the target cleanliness level, preferably below 100 nm, and more preferably below 20 nm. Furthermore, these filters can be used individually or in combination. The filtration method can be to pass the solution only once, but it is better to circulate the solution and perform multiple filtrations. In the method for manufacturing the base polymer for photoresist of the present invention, the filtration steps in steps (1) to (3) can be performed in any order and number of times, and it is particularly preferable to perform filtration after the preparation of the polymer solution in step (3).

[0436] Here, the advantages of the method for manufacturing the base polymer for photoresist according to the present invention are described. The base polymer for photoresist manufactured by the method of the present invention incorporates a photoacid generating unit, thus enabling a high degree of control over acid diffusion and significantly improving resolution and roughness. It is particularly effective in the formation of fine patterns used in EUV lithography.

[0437] Numerous reports have documented PAG-bonded polymers formed by incorporating photoacid generators (PAGs) into polymers. In recent EUV lithography, highly reactive cations are ideally used to improve sensitivity. Examples include sulfonium salts and ferromonite salts, which are formed by incorporating fluorine or iodine and have low lowest unoccupied molecular orbital (LUMO) energies. However, due to their high reactivity, these cations also carry a risk of decomposition during polymer manufacturing. Examples include decomposition caused by thiol-based chain transfer agents used during polymerization and by the base used to deprotect phenolic hydroxyl groups.

[0438] In contrast, the method for manufacturing the base polymer for photoresist of the present invention converts it into sulfonium salt or sulfonium salt only after obtaining a stable polymer containing ammonium salt (precursor polymer), thus eliminating the decomposition during the polymerization step.

[0439] International Publication No. 2025 / 041781, paragraphs

[0503] to

[0505] , describes a synthetic example of a PAG-bonded polymer having a bis(difluorophenyl)iodophenylsulfonium cation. Although there are concerns about decomposition during polymerization, as mentioned above, due to the low energy of the lowest unoccupied molecular orbital of this cation, no decomposition was actually observed. It is speculated that this is because, as described in paragraph

[0503] , no chain transfer agent was used for the polymerization conditions, or because the unit containing the phenolic hydroxyl group was protected with an acid-labile group, and therefore no base was used during deprotection, thus leading to successful synthesis.

[0440] However, the method in International Publication No. 2025 / 041781 has the drawback of being limited to acid-labile units. The acid-labile unit described in the examples of International Publication No. 2025 / 041781, namely 1-methylcyclopentyl=2-methylprop-2-enoate, has low acid reactivity (for example, the acid reactivity of 1-tert-butylcyclopentyl=2-methylprop-2-enoate is much higher). This is self-evident in the field of organic chemistry, considering the stability of the cations generated during acid reactions. Therefore, if the protecting group of the phenolic hydroxyl group is deprotected with acetic acid as described in the examples, the acid-labile unit will not decompose and its structure can be maintained.

[0441] On the other hand, in the method for manufacturing the base polymer for photoresist of the present invention, as described above, there is no problem in carrying out the deprotection of the protected phenolic hydroxyl groups under alkaline conditions. Therefore, even if highly reactive acid-instable units are copolymerized, there will be no decomposition. Introducing highly reactive acid-instable groups can significantly improve sensitivity and contrast, which is ideal.

[0442] Example 14 of polymer synthesis in International Publication No. 2025 / 164208

[0235] synthesizes a polymer composed of a highly reactive acid-instable unit (M-5), a unit containing an unprotected phenolic hydroxyl group (M-18), and a photoacid generator unit with a highly reactive cationic group (M-16). It is presumed that there is no step to deprotect the phenolic hydroxyl group, so (M-5) and (M-16) will not decompose due to acid or alkali, and the target product can be synthesized. However, there are other concerns regarding the use of unprotected phenolic hydroxyl groups. It is believed that phenolic hydroxyl groups will be consumed as phenoxy radicals in free radical polymerization to generate free radicals. Therefore, polymerization control is difficult, and the composition of the copolymer is difficult to be uniform. For example, a large amount of acid-instable units may be introduced into one molecular chain, while another molecular chain may have an excess of photoacid generator units. In this case, there are concerns about the degradation of resolution and process window during photolithography.

[0443] On the other hand, in the method for manufacturing the base polymer for photoresist of the present invention, the unit containing phenolic hydroxyl groups undergoes a protection-deprotection step, so it is not easy to cause changes in the above composition, and the photolithography performance is well maintained.

[0444] The method for manufacturing the base polymer for photoresist of the present invention preferably protects the unit containing phenolic hydroxyl groups (repeating unit (c')) with a base-insecure group. The reason is as described above, because a base is used instead of an acid during deprotection, so that even if a highly reactive acid-insecure unit is copolymerized, the deprotection reaction (step (2) of the present invention) can be carried out without decomposition.

[0445] Furthermore, the structure of the anionic portion in the repeating unit (a) is preferably a sulfonate ester, as described in the above general formulas (11a') or (12a'). Sulfonate esters have high resistance to alkalis, so deprotection of units containing phenolic hydroxyl groups protected by alkali-instable groups can be easily suppressed. On the other hand, the photoacid generating unit (M-15) described, for example, in paragraph

[0226] of International Publication No. 2025 / 164208, has a carboxylic acid ester with low resistance to alkalis. Therefore, if the protected phenolic hydroxyl units are treated with alkali when synthesizing PAG-bonded polymers containing it, there is a concern about ester decomposition. This point can also be considered a significant advantage in the manufacturing method of the base polymer for photoresist of the present invention.

[0446] [Chemical Amplifying Resist Composition (Photoresist Composition)]

[0447] This invention enables the manufacture of chemically amplified resist compositions containing a photoresist base polymer obtained using the manufacturing method described above. Hereinafter, the components contained in the chemically amplified resist composition will be described in detail.

[0448] [(A) Base polymer for photoresist]

[0449] Regarding component (A), the aforementioned chemically amplified photoresist composition contains a photoresist base polymer prepared by the aforementioned manufacturing method as the main component.

[0450] The aforementioned (A) photoresist base polymer can be used alone or in combination with two or more polymers having different composition ratios, Mw, and / or Mw / Mn.

[0451] [(B) Organic solvents]

[0452] The aforementioned chemically amplified resist composition may also contain an organic solvent as component (B). There are no particular restrictions on the organic solvent in component (B) if it is capable of dissolving the aforementioned components and the components described below. Specific examples of such organic solvents include: ketones such as cyclopentanone, cyclohexanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ketols such as DAA; ethers such as PGME, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as GBL; and mixtures thereof.

[0453] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, ethyl lactate, DAA, and mixed solvents thereof are particularly suitable for the photoresist base polymer of component (A).

[0454] In the above-mentioned chemically amplified photoresist composition, the content of (B) organic solvent relative to 80 parts by weight of the base polymer for (A) photoresist is preferably 200-7,000 parts by weight, and more preferably 400-5,000 parts by weight. (B) Organic solvent may be used alone or in combination with two or more types.

[0455] [(C) Quenching agent]

[0456] The aforementioned chemically amplified resist composition may also contain a quencher as component (C). Furthermore, in this specification, a quencher refers to a material used to prevent the acid generated by the photoacid generator in the chemically amplified resist composition from diffusing towards the unexposed area and forming a desired pattern.

[0457] (C) Specific examples of quenching agents can be listed as onion salts represented by the following general formulas (1) or (2).

[0458] [Chemistry 108]

[0459]

[0460] In the above general formula (1), R q1 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain hydrogen atoms or heteroatoms, but excludes those in which the hydrogen atom at the α-position of the sulfonate group is replaced by a fluorine atom or a fluoroalkyl group. In the above general formula (2), R q2 Hydrocarbon groups consisting of 1 to 40 carbon atoms, which may also contain heteroatoms.

[0461] R q1 The hydrocarbon groups representing carbon numbers from 1 to 40 can be specifically listed as follows: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with carbon numbers from 1 to 40; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6[Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl and adamantyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, these groups may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc.]

[0462] R q2 The hydrocarbon group represented can be specifically exemplified as R. q1 In addition to the specific examples of substituents, examples include fluorinated saturated hydrocarbon groups such as trifluoromethyl and trifluoroethyl, and fluorinated aryl groups such as pentafluorophenyl and 4-trifluoromethylphenyl.

[0463] Specific examples of onium salt anions represented by the above general formula (1) are listed below, but are not limited thereto.

[0464] [Chemistry 109]

[0465]

[0466] [Chemical 110]

[0467]

[0468] [Chemistry 111]

[0469]

[0470] [Chemistry 112]

[0471]

[0472] [Chemistry 113]

[0473]

[0474] Specific examples of onium salt anions represented by the above general formula (2) are listed below, but are not limited thereto.

[0475] [Chemistry 114]

[0476]

[0477] [Chemistry 115]

[0478]

[0479] [Chemistry 116]

[0480]

[0481] [Chemistry 117]

[0482]

[0483] [Chemistry 118]

[0484]

[0485] In the above general formulas (1) and (2), Mq + The cation is a sulfonium cation. Examples of the aforementioned sulfonium cations include: sulfonium cations, monazine cations, ammonium cations, etc. Specific examples of the aforementioned sulfonium cations include: examples of sulfonium cations represented by the above general formula (Z-1) and sulfonium cations represented by the above general formula (Z-3), those described in paragraphs

[0102] to

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

[0044] to

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

[0035] to

[0046] of Japanese Patent Publication No. 7491173, etc., but are not limited thereto.

[0486] Specific examples of the aforementioned citric acid can be cited from paragraph

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

[0487] Specific examples of the aforementioned ammonium cations can be listed below using the general formula (am-1).

[0488] [Chemistry 119]

[0489]

[0490] In the above general formula (am-1), R q11 ~R q14 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R q11 and R q12 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to. Specific examples of the aforementioned hydrocarbon groups can be listed and illustrated in the description of the above general formula (1a') as R. N1 ~R N4 The same example represents hydrocarbon groups.

[0491] Specific examples of ammonium cations represented by the above general formula (am-1) are listed below, but are not limited thereto.

[0492] [Chemistry 120]

[0493]

[0494] Specific examples of onium salts represented by the above general formula (1) or (2) can be listed as any combination of the aforementioned anions and cations. Furthermore, these onium salts can be readily prepared using ion exchange reactions employing known organic chemical methods. For example, Japanese Patent Application Publication No. 2007-145797 can be consulted regarding ion exchange reactions.

[0495] The onium salts represented by the above general formula (1) or (2) function as quenchers in the above chemically amplified photoresist composition. This is because the relative anions of the aforementioned onium salts are conjugate bases of weak acids. Here, "weak acid" means an acid that exhibits an acidity that cannot deprotect the acid-insecure groups of the units containing acid-insecure groups used in the base polymer of the photoresist of component (A). The onium salts represented by the above general formula (1) or (2) function as quenchers when used in combination with onium salt-type photoacid generators that have a conjugate base of a strong acid, such as sulfonic acid with fluorinated α-position, as relative anions. In other words, when onium salts that produce strong acids such as sulfonic acid with fluorinated α-positions are mixed with onium salts that produce weak acids such as sulfonic acid and carboxylic acid with unfluorinated α-positions, collisions between the strong acid generated from the photoacid generator by high-energy radiation and the unreacted onium salt with weak acid anions will release the weak acid through salt exchange and generate onium salt with strong acid anions. During this process, the strong acid is exchanged for a weak acid with low catalytic activity, thus apparent acid deactivation allows for the control of acid diffusion.

[0496] Furthermore, (C) the quenching agent may be an onium salt having a sulfonium cation and a benzene oxide anion site within the same molecule as described in Japanese Patent No. 6848776, or an onium salt having a sulfonium cation and a carboxylate anion site within the same molecule as described in Japanese Patent No. 6583136, Japanese Patent Application Publication No. 2020-200311, or an onium salt having a monazine cation and a carboxylate anion site within the same molecule as described in Japanese Patent No. 6274755.

[0497] Here, it is believed that when the photoacid generator that produces strong acids is an onium salt, as mentioned above, the strong acid generated by high-energy ray irradiation can be exchanged for a weak acid. On the other hand, the weak acid generated by high-energy ray irradiation is not easily exchanged with the unreacted onium salt that produces strong acids. This is because onium cations more readily form ion pairs with the anions of strong acids.

[0498] When the above-mentioned chemically amplified photoresist composition contains an onium salt represented by the above-mentioned general formula (1) or (2) as a quencher in (C), its content relative to 80 parts by mass of the base polymer for photoresist in (A) is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass. If the content of the onium salt-type quencher in component (C) is within the aforementioned range, the resolution is good and there is no significant reduction in sensitivity, which is ideal. The onium salt represented by the above-mentioned general formula (1) or (2) can be used alone or in combination of two or more.

[0499] The aforementioned chemically amplified resist composition may also contain a nitrogen-containing compound as a (C) quencher. Specific examples of nitrogen-containing compounds as (C) can be listed as first-, second-, or third-order amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103, and particularly as amine compounds having hydroxyl groups, ether bonds, ester bonds, lactone rings, cyano groups, or sulfonate bonds. Furthermore, compounds formed by protecting first- or second-order amines with urethane groups, as described in Japanese Patent Publication No. 3790649, can also be listed.

[0500] Alternatively, sulfonate sulfonates with nitrogen-containing substituents can be used as nitrogen-containing compounds. Such compounds function as quenchers in the unexposed areas, but lose their quenching ability in the exposed areas due to neutralization with the acid they generate, thus functioning as so-called photodegrading bases. By using photodegrading bases, the contrast between the exposed and unexposed areas can be enhanced. For example, Japanese Patent Application Publication No. 2009-109595 and Japanese Patent Application Publication No. 2012-046501 can be referenced for photodegrading bases.

[0501] When the above-mentioned chemically amplified photoresist composition contains a nitrogen-containing compound as (C) quencher, its content relative to 80 parts by mass of the base polymer for (A) photoresist is preferably 0.001 to 12 parts by mass, and more preferably 0.01 to 8 parts by mass. The aforementioned nitrogen-containing compound may be used alone or in combination of two or more.

[0502] [(D) Other photoacid generating agents]

[0503] The aforementioned chemically amplified photoresist composition contains photoacid-generating units in the base polymer of the photoresist in component (A), but may also contain other photoacid-generating agents as component (D). There are no particular limitations on the aforementioned other photoacid-generating agents if they are compounds that generate acid upon irradiation with high-energy rays. Ideal other photoacid-generating agents can be represented by the following general formulas (3) or (4).

[0504] [Chemistry 121]

[0505]

[0506] In the above general formula (3), R 101 ~R 105 Each group consists independently of a halogen atom or may contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. Also, R 101 R 102 and R 103 Any two of them can also bond to each other and form a ring together with the sulfur atoms they are bonded to.

[0507] Specific examples of sulfonium salt cations represented by the above general formula (3) can be listed as follows: examples of sulfonium cations represented by the above general formula (Z-1) and sulfonium cations represented by the above general formula (Z-3), those described in paragraphs

[0102] to

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

[0044] to

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

[0035] to

[0046] of Japanese Patent Application Publication No. 7491173, etc., but are not limited thereto. Specific examples of ferrous salt cations represented by the above general formula (4) can be listed in paragraph

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

[0508] In the above general formulas (3) and (4), Xa - It is the anion of a strong acid. The anions of the aforementioned strong acids can be represented by any of the following general formulas (Xa-1) to (Xa-4).

[0509] [Chemistry 122]

[0510]

[0511] In the above general formula (Xa-1), R fa It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain fluorine atoms or heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in the general formula (Xa-1-1) described later. fa1 The same example represents hydrocarbon groups.

[0512] The anion represented by the above general formula (Xa-1) should preferably be represented by the following general formula (Xa-1-1).

[0513] [Chemistry 123]

[0514]

[0515] In the above general formula (Xa-1-1), Q 1 and Q 2Each group is independently composed of a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; to improve solvent solubility, at least one of these groups is preferably trifluoromethyl. m is an integer from 0 to 4, with 1 being particularly preferred. R fa1 The hydrocarbon group may contain heteroatoms and has 1 to 35 carbon atoms. The aforementioned heteroatoms are preferably oxygen, nitrogen, sulfur, or halogen atoms, with oxygen atoms being more preferred. Considering the high resolution achieved in the formation of fine patterns, hydrocarbon groups with 6 to 30 carbon atoms are particularly preferred.

[0516] In the above general formula (Xa-1-1), R fa1 The hydrocarbon group represented by carbon number 1 to 35 can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 35 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecanyl, and eicosyl; cyclic saturated hydrocarbon groups with 3 to 35 carbon atoms, such as cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norcamphenyl, norcamphenylmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl; unsaturated aliphatic hydrocarbon groups with 2 to 35 carbon atoms, such as 2-propenyl and 3-cyclohexenyl; aryl groups with 6 to 35 carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, and 9-fluorenyl; aralkyl groups with 7 to 35 carbon atoms, such as benzyl and diphenylmethyl; and groups obtained by combining them.

[0517] Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. This can result in the presence of hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Specific examples of hydrocarbon groups containing heteroatoms include: tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidemethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, 3-oxocyclohexyl, etc.

[0518] In the above general formula (Xa-1-1), L a1 The bonds can be single bonds, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, or carbamate bonds. From a synthetic point of view, ether bonds or ester bonds are preferred, with ester bonds being even better.

[0519] Specific examples of anions represented by the above general formula (Xa-1) are shown below, but are not limited to these. Additionally, in the following formula, Q... 1 As mentioned above, Ac is an acetyl group.

[0520] [Chemistry 124]

[0521]

[0522] [Chemistry 125]

[0523]

[0524] [Chemistry 126]

[0525]

[0526] [Chemistry 127]

[0527]

[0528] [Chemistry 128]

[0529]

[0530] [Chemistry 129]

[0531]

[0532] [Chemistry 130]

[0533]

[0534] [Chemistry 131]

[0535]

[0536] [Chemistry 132]

[0537]

[0538] [Chemistry 133]

[0539]

[0540] [Chemistry 134]

[0541]

[0542] [Chemistry 135]

[0543]

[0544] In the above general formula (Xa-2), R fb1 and R fb2Each of the above-mentioned hydrocarbon groups consists independently of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. These hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in the above general formula (Xa-1-1). fa1 The same example represents a hydrocarbon group. R fb1 and R fb2 It should preferably be a fluorine atom or a straight-chain fluorinated alkyl group having 1 to 4 carbon atoms. Also, R fb1 and R fb2 They can also bond to each other and to the groups they are bonded to (-CF2-SO2-N). - -SO2-CF2-) together form a ring, at which point R fb1 and R fb2 The groups formed by mutual bonding should preferably be fluorinated ethylidene or fluorinated propyleneide.

[0545] In the above general formula (Xa-3), R fc1 R fc2 and R fc3 Each of the above-mentioned hydrocarbon groups consists independently of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. These hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in the above general formula (Xa-1-1). fa1 The same example represents a hydrocarbon group. R fc1 R fc2 and R fc3 It should preferably be a fluorine atom or a straight-chain fluorinated alkyl group having 1 to 4 carbon atoms. Also, R fc1 and R fc2 They can also bond to each other and to the groups they are bonded to (-CF2-SO2-C). - -SO2-CF2-) together form a ring, at which point R fc1 and R fc2 The groups formed by mutual bonding should preferably be fluorinated ethylidene or fluorinated propyleneide.

[0546] In the above general formula (Xa-4), R fd It can be a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in the above general formula (Xa-1-1). fa1 The same example represents hydrocarbon groups.

[0547] Specific examples of anions represented by the above general formula (Xa-4) can be listed below, but are not limited thereto.

[0548] [Chemistry 136]

[0549]

[0550] [Chemistry 137]

[0551]

[0552] The examples of the aforementioned non-nucleophilic relative ions can be further illustrated by anions having aromatic rings substituted with iodine or bromine atoms. Specific examples of such anions can be represented by the following general formula (Xa-5).

[0553] [Chemistry 138]

[0554]

[0555] In the above general formula (Xa-5), x is 1, 2, or 3. y is an integer from 1 to 5. z is an integer from 0 to 3. However, 1 ≤ y + z ≤ 5. y should preferably be 1, 2, or 3, with 2 or 3 being more preferable. z should preferably be 0, 1, or 2.

[0556] In the above general formula (Xa-5), X BI It is an iodine atom or a bromine atom. When x and / or y are 2 or more, each X BI They can be the same or different.

[0557] In the above general formula (Xa-5), L 1 It is a saturated hydrocarbon group with 1 to 6 carbon atoms, consisting of a single bond, ether bond, ester bond, or possibly containing an ether bond or ester bond. The aforementioned saturated hydrocarbon group can be linear, branched, or cyclic.

[0558] In the above general formula (Xa-5), L 2 When x is 1, it is a single bond or a divalent linker with 1 to 20 carbon atoms; when x is 2 or 3, it is a (x+1) valent linker with 1 to 20 carbon atoms. The aforementioned linker may also contain oxygen, sulfur, or nitrogen atoms.

[0559] In the above general formula (Xa-5), R fe The carbon group may be a hydroxyl, carboxyl, fluorine, chlorine, bromine, or amino group, or may contain a fluorine, chlorine, bromine, hydroxyl, amino, or ether bond, and may be a hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbon oxygen group with 1 to 20 carbon atoms, a hydrocarbon carbonyl group with 2 to 20 carbon atoms, a hydrocarbon carbonyloxy group with 2 to 20 carbon atoms, or a hydrocarbon sulfonyloxy group with 1 to 20 carbon atoms, or -N(R) feA (R) feB ), -N(R feC )-C(=O)-R feD or -N(R) feC )-C(=O)-OR feD R feA and R feBEach can be independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. R feC It is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl oxygen group having 2 to 6 carbon atoms. R feD It is an aliphatic hydrocarbon group with 1 to 16 carbon atoms, an aryl group with 6 to 12 carbon atoms, or an aralkyl group with 7 to 15 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated alkyloxy group with 1 to 6 carbon atoms, a saturated alkylcarbonyl group with 2 to 6 carbon atoms, or a saturated alkylcarbonyloxy group with 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned hydrocarbon group, alkyloxy group, alkylcarbonyl group, alkyloxycarbonyl group, alkylcarbonyloxy group, and alkylsulfonyloxy group can be linear, branched, or cyclic. When x and / or z are 2 or more, each R fe They can be the same or different.

[0560] Among them, R fe It is advisable to use hydroxyl groups, -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.

[0561] In the above general formula (Xa-5), Rf 11 ~Rf 14 Each of these can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of them must be a fluorine atom or a trifluoromethyl group. Also, Rf 11 With Rf 12 They can also combine to form carbonyl groups. Especially Rf 13 and Rf 14 Both are ideally composed of fluorine atoms.

[0562] Specific examples of anions represented by the above general formula (Xa-5) are shown below, but are not limited to these. Furthermore, in the following formula, X... BI Same as above.

[0563] [Chemistry 139]

[0564]

[0565] [Chemistry 140]

[0566]

[0567] [Chemistry 141]

[0568]

[0569] [Chemistry 142]

[0570]

[0571] [Chemistry 143]

[0572]

[0573] [Chemistry 144]

[0574]

[0575] [Chemistry 145]

[0576]

[0577] [Chemistry 146]

[0578]

[0579] [Chemistry 147]

[0580]

[0581] [Chemistry 148]

[0582]

[0583] [Chemistry 149]

[0584]

[0585] [Chemistry 150]

[0586]

[0587] [Chemistry 151]

[0588]

[0589] [Chemistry 152]

[0590]

[0591] [Chemistry 153]

[0592]

[0593] [Chemistry 154]

[0594]

[0595] [Chemistry 155]

[0596]

[0597] [Chemistry 156]

[0598]

[0599] [Chemistry 157]

[0600]

[0601] [Chemistry 158]

[0602]

[0603] [Chemistry 159]

[0604]

[0605] [Chemistry 160]

[0606]

[0607] [Chemistry 161]

[0608]

[0609] [Chemistry 162]

[0610]

[0611] The aforementioned non-nucleophilic relative ions may also include the fluorobenzenesulfonic acid anion bonded to an aromatic group containing an iodine atom as described in Japanese Patent No. 6648726, the anion with a mechanism of decomposition due to acid as described in International Publication No. 2021 / 200056 and Japanese Patent Application Publication No. 2021-070692, the anion with a cyclic ether group as described in Japanese Patent Application Publication No. 2018-180525 and Japanese Patent Application Publication No. 2021-035935, and the anion as described in Japanese Patent Application Publication No. 2018-092159.

[0612] The aforementioned non-nucleophilic relative ions can also be further described in Japanese Patent Application Publication Nos. 2006-276759, 2015-117200, 2016-065016, and 2019-202974 as anions of bulky benzenesulfonic acid derivatives without fluorine atoms, and in Japanese Patent Application Publication No. 6645464 as benzenesulfonic acid anions and alkylsulfonic acid anions bonded to aromatic groups containing iodine atoms without fluorine atoms.

[0613] The aforementioned non-nucleophilic relative ions may further include the anions of disulfonic acid as described in Japanese Patent Application Publication No. 2015-206932, the anions of sulfonic acid on one side and sulfonamide or sulfonylimide on the other side as described in International Patent Application Publication No. 2020 / 158366, and the anions of sulfonic acid on one side and carboxylic acid on the other side as described in Japanese Patent Application Publication No. 2015-024989.

[0614] Furthermore, other photoacid generating agents of component (D) should also be represented by the following general formula (5).

[0615] [Chemistry 163]

[0616]

[0617] In the above general formula (5), R 201 and R 202 Each can be independently a hydrocarbon group with 1 to 30 carbon atoms, which may also contain heteroatoms. R 203 It can also contain a hydrocarbon group with 1 to 30 carbon atoms and a heteroatom. Also, R 201 R 202 and R 203 Any two of them can also bond to each other and form a ring together with the sulfur atoms they are bonded to.

[0618] R 201 and R 202 The hydrocarbon groups representing 1 to 30 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 30 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, oxanorbornel, tricyclic [5.2.1.0] 2,6[Cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms, such as decyl and adamantyl; aryl groups with 6 to 30 carbon atoms, such as phenyl, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, tert-butylnaphthyl, and anthracene; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and some of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, groups may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups.]

[0619] R 203 The alkylene groups representing carbon atoms from 1 to 30 can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane, and heptadecane. Alkyl groups with 1 to 30 carbon atoms, such as alkyl-1,17-diyl; cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norcamphenediyl, and adamantanediyl; and aryl groups with 6 to 30 carbon atoms, such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, isobutylphenylene, sec-butylphenylene, tert-butylphenylene, naphthylene, methylnaphthylene, ethylnaphthylene, n-propylnaphthylene, isopropylnaphthylene, n-butylnaphthylene, isobutylnaphthylene, sec-butylnaphthylene, and tert-butylnaphthylene. Furthermore, some or all of the hydrogen atoms in the aforementioned alkylene group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned alkylene group can also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. This can result in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. The aforementioned heteroatoms should preferably be oxygen atoms.

[0620] In the above general formula (5), L 11It is a hydrocarbon group with 1 to 20 carbon atoms, which can be a single bond, an ether bond, or may contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 203 The same example represents the subhydrocarbon group.

[0621] In the above general formula (5), X a X b X c and X d Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group. However, X a X b X c and X d At least one of them is a fluorine atom or a trifluoromethyl group.

[0622] Other photoacid generators represented by the above general formula (5) should preferably be represented by the following general formula (5').

[0623] [Chemistry 164]

[0624]

[0625] In the above general formula (5'), L 11 Same as above. X e It can be a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. R 301 R 302 and R 303 Each hydrocarbon group consists independently of a hydrogen atom or may contain heteroatoms and has 1 to 20 carbon atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in the above general formula (Xa-1-1). fa1 The same example represents hydrocarbon groups. s and t are independent integers from 0 to 5, and u is an integer from 0 to 4.

[0626] Specific examples of other photoacid generators represented by the above general formula (5) can be cited as the same examples as those exemplified in Japanese Patent Application Publication No. 2017-026980 as photoacid generators represented by formula (2).

[0627] Among the aforementioned photoacid generators, those containing anions represented by the above general formula (Xa-1-1) or (Xa-4) exhibit low acid diffusion and excellent solvent solubility, making them particularly desirable. Furthermore, those represented by the above general formula (5') exhibit extremely low acid diffusion, making them particularly desirable.

[0628] When the above-mentioned chemically amplified resist composition contains (D) other photoacid generating agents, their content relative to 80 parts by weight of the base polymer for (A) photoresist is preferably 0.1 to 40 parts by weight, and more preferably 0.5 to 20 parts by weight. If the amount of (D) other photoacid generating agents added is within the aforementioned range, the resolution is good, and there is no concern about the generation of foreign matter in the resist film after development or during peeling, which is ideal. (D) Other photoacid generating agents can be used alone or in combination of two or more.

[0629] [(E) Surfactant]

[0630] The aforementioned chemically amplified resist composition may also contain a surfactant as component (E). The surfactant in component (E) is preferably a surfactant that is insoluble or sparingly soluble in water but soluble in alkaline developing solution, or a surfactant that is insoluble or sparingly soluble in both water and alkaline developing solution. Such surfactants can be referred to in Japanese Patent Application Publication Nos. 2010-215608 and 2011-016746.

[0631] Surfactants that are insoluble or poorly soluble in water and alkaline developing solutions, among those listed in the aforementioned announcement, are preferably FC-4430 (manufactured by 3M Corporation), SURFLON (registered trademark) S-381 (manufactured by AGC SEIMI CHEMICAL), OLFINE (registered trademark) E1004 (manufactured by Nissin Chemical Industry Co., Ltd.), KH-20, KH-30 (manufactured by AGC SEIMI CHEMICAL), and oxane ring-opening polymers represented by the following general formula (surf-1).

[0632] [Chemistry 165]

[0633]

[0634] Here, R, Rf, A, B, C, m, and n are not related to the foregoing description, but only apply to the above general formula (surf-1). R is an aliphatic group with 2 to 5 carbon atoms, valent to 2 to 4. Examples of the aforementioned aliphatic groups, for those with a valent charge, include: ethylene, 1,4-butylene, 1,2-propylene, 2,2-dimethyl-1,3-propylene, 1,5-pentane, etc.; examples of those with a valent charge or a tetravalent charge include the following.

[0635] [Chemistry 166]

[0636]

[0637] In the formula, the dashed lines represent atomic bonds, which are partial structures derived from glycerol, trimethylolethane, trimethylolpropane, and neopentyl tertrol, respectively.

[0638] Among them, 1,4-butylene, 2,2-dimethyl-1,3-propylene, etc. are preferred.

[0639] Rf is trifluoromethyl or pentafluoroethyl, preferably trifluoromethyl. m is an integer from 0 to 3, n is an integer from 1 to 4, the sum of n and m is the valence of R, and is an integer from 2 to 4. A is 1. B is an integer from 2 to 25, preferably an integer from 4 to 20. C is an integer from 0 to 10, preferably 0 or 1. Furthermore, the arrangement of the constituent units in the above general formula (surf-1) is not specified; they can be block-bonded or random-bonded. For details on the manufacture of surfactants based on partially fluorinated oxyheterocyclic butane ring-opening polymer systems, please refer to the specification of US Patent No. 5,650,483, etc.

[0640] Surfactants that are insoluble or sparingly soluble in water but soluble in alkaline developing solutions are useful in ArF immersion lithography when no resist film is used. They reduce water penetration and leaching by aligning with the surface of the resist film. Therefore, they are useful for suppressing the leaching of water-soluble components from the resist film and reducing damage to the exposure equipment. Furthermore, they are useful because they are soluble in alkaline aqueous solutions after exposure or post-exposure baking (PEB) and are unlikely to become foreign matter causing defects. Such surfactants, which are insoluble or sparingly soluble in water but soluble in alkaline developing solutions, are polymeric surfactants, also known as hydrophobic resins, and are particularly desirable for those with high water repellency and improved hydrophobic properties.

[0641] Specific examples of such polymeric surfactants include those containing at least one repeating unit selected from any of the following general formulas (6A) to (6E).

[0642] [Chemistry 167]

[0643]

[0644] In the above general formulas (6A)~(6E), R B It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. W 1 It can be -CH2-, -CH2CH2-, -O-, or two separate -H groups. R s1 Each can be independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R s2 It is a single bond, or a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms. R s3 Each can be independently a hydrogen atom, a hydrocarbon group with 1 to 15 carbon atoms, a fluorinated hydrocarbon group, or an acid-labile group. R s3 When the group is a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group can also be inserted between the carbon-carbon bonds. R s4 R is a hydrocarbon group or fluorinated hydrocarbon group with a (w+1) valence having 1 to 20 carbon atoms. w can be 1, 2, or 3. s5Each can be independently a hydrogen atom, or -C(=O)-OR sa The group indicated by R. sa It is a fluorinated hydrocarbon group with 1 to 20 carbon atoms. R s6 It is a hydrocarbon group or a fluorinated hydrocarbon group with 1 to 15 carbon atoms, and an ether bond or a carbonyl group may also be inserted between its carbon-carbon bonds.

[0645] R s1 The hydrocarbon group representing 1 to 10 carbon atoms should preferably be a saturated hydrocarbon group, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornel. Among these, those with 1 to 6 carbon atoms are preferred.

[0646] R s2 The alkylene group representing 1 to 5 carbon atoms should preferably be a saturated alkylene group, and can be linear, branched, or cyclic. Specific examples include: methylene, ethylene, propylene, butylene, and pentylene.

[0647] R s3 Or R s6 The hydrocarbon group representing 1 to 15 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: saturated hydrocarbon groups; aliphatic unsaturated hydrocarbon groups such as alkenyl and alkynyl groups, which are preferably saturated hydrocarbon groups. Specific examples of the aforementioned saturated hydrocarbon groups can be listed as R. s1 In addition to the hydrocarbon groups indicated by R, other examples include undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. s3 Or R s6 The fluorinated hydrocarbon groups representing carbon numbers 1 to 15 can be categorized as groups in which some or all of the hydrogen atoms of the carbon atoms bonded to the aforementioned hydrocarbon groups are replaced by fluorine atoms. As mentioned above, ether bonds or carbonyl groups may also be inserted between their carbon-carbon bonds.

[0648] R s3 Specific examples of acid-instable groups can be listed, such as groups represented by the above general formulas (L1) to (L4), trialkylsilyl groups with alkyl groups having 1 to 6 carbon atoms, and alkyl groups containing oxygen groups having 4 to 20 carbon atoms.

[0649] R s4 The hydrocarbon group or fluorinated hydrocarbon group with a carbon number of 1 to 20 and a valence of (w+1) can be any of the following: straight chain, branched, or cyclic. Specific examples can be listed as groups obtained by further removing w hydrogen atoms from the aforementioned hydrocarbon group or fluorinated hydrocarbon group.

[0650] Rsa The fluorinated hydrocarbon group representing 1 to 20 carbon atoms should preferably be saturated and can be linear, branched, or cyclic. Specific examples include those where some or all of the hydrogen atoms in the aforementioned hydrocarbon group are replaced by fluorine atoms, such as trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoro-1-propyl, 3,3,3-trifluoro-2-propyl, 2,2,3,3-tetrafluoropropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 2,2,3,3,4,4,4-heptafluorobutyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 2,2,3,3,4,4,5,5,6,6,7,7-dodecylfluoroheptyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, etc.

[0651] Specific examples of the repeating units represented by any of the general formulas (6A) to (6E) above can be listed below, but are not limited thereto. Furthermore, in the following formula, R... B Same as above.

[0652] [Chemistry 168]

[0653]

[0654] [Chemistry 169]

[0655]

[0656] [Chemistry 170]

[0657]

[0658] [Chemistry 171]

[0659]

[0660] [Chemistry 172]

[0661]

[0662] [Chemistry 173]

[0663]

[0664] The aforementioned polymeric surfactants may also contain repeating units other than those represented by the general formulas (6A) to (6E). Specific examples of other repeating units include repeating units derived from methacrylic acid, α-trifluoromethacrylic acid derivatives, etc. In polymeric surfactants, the content of repeating units represented by the general formulas (6A) to (6E) is preferably 20 mol% or more, more preferably 60 mol% or more, and even more preferably 100 mol% of all repeating units.

[0665] The Mw of the aforementioned polymeric surfactant is preferably 1,000 to 500,000, and more preferably 3,000 to 100,000. The Mw / Mn ratio is preferably 1.0 to 2.0, and more preferably 1.0 to 1.6.

[0666] Methods for synthesizing the aforementioned polymeric surfactants include: monomers containing unsaturated bonds, representing repeating units of the above general formulas (6A) to (6E) and other repeating units as needed, are polymerized in an organic solvent by adding a free radical initiator and heating. Specific examples of organic solvents used in polymerization include: toluene, benzene, THF, diethyl ether, dioxane, etc. Specific examples of polymerization initiators include: AIBN, 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2'-azobis(2-methylpropionic acid) ester, benzoyl peroxide, lauroyl peroxide, etc. The reaction temperature is preferably 50–100°C. The reaction time is preferably 4–24 hours. Acid-labile groups can be directly introduced into the monomer, or they can be protected or partially protected after polymerization.

[0667] When synthesizing the aforementioned polymeric surfactants, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can be used to adjust the molecular weight. In this case, the amount of these chain transfer agents added relative to the total molar number of monomers used to polymerize them should preferably be 0.01 to 10 mol%.

[0668] When the above-mentioned chemically amplified resist composition contains surfactant (E), its content, relative to 80 parts by weight of the base polymer for photoresist (A), is preferably 0.1 to 50 parts by weight, and more preferably 0.5 to 10 parts by weight. If the content of surfactant (E) is 0.1 parts by weight or more, it will sufficiently improve the receding contact angle between the resist film surface and water; if it is 50 parts by weight or less, the dissolution rate of the resist film surface to the developer is low, and the height of the formed fine pattern is sufficiently maintained. Surfactant (E) can be used alone or in combination of two or more.

[0669] [(F) Other ingredients]

[0670] The chemically amplified resist composition of the present invention may also contain compounds that decompose due to acid and produce acid (acid-increasing compounds), organic acid derivatives, fluorinated alcohols, and compounds with a Mw of 3,000 or less whose solubility in the developer changes due to acid (dissolution inhibitors) as other components in (F). The aforementioned acid-increasing compounds can be referred to in Japanese Patent Application Publication No. 2009-269953 or Japanese Patent Application Publication No. 2010-215608. When containing the aforementioned acid-increasing compounds, their content is preferably 0 to 5 parts by mass, and more preferably 0 to 3 parts by mass, relative to 80 parts by mass of the base polymer for photoresist in (A). If the content is within this range, acid diffusion is easier to control, and it is less likely to cause degradation of resolution or pattern shape. The aforementioned organic acid derivatives, fluorinated alcohols, and dissolution inhibitors can be referred to in Japanese Patent Application Publication No. 2009-269953 or Japanese Patent Application Publication No. 2010-215608.

[0671] [Pattern Formation Method]

[0672] The pattern forming method of the present invention includes the following steps:

[0673] A resist film is formed on a substrate using a photoresist composition containing a photoresist base polymer prepared by the manufacturing method described above.

[0674] The aforementioned resist film was exposed to high-energy radiation, and

[0675] The previously exposed resist film was developed using a developer.

[0676] The aforementioned substrates may be, for example, substrates used in integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.) or substrates used in mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.).

[0677] The resist film can be formed by applying the aforementioned chemically amplified resist composition onto a substrate using methods such as spin coating, with a film thickness preferably of 0.05 to 2 μm, and then pre-baking it on a hot plate at a temperature preferably of 60 to 150°C for 1 to 10 minutes, more preferably at 80 to 140°C for 1 to 5 minutes.

[0678] Examples of high-energy rays used for photoresist film exposure include: KrF excimer lasers, ArF excimer lasers, electron beams (EB), and extreme ultraviolet (EUV) rays with wavelengths of 3–15 nm. When using KrF excimer lasers, ArF excimer lasers, or EUV for exposure, a mask for forming the desired pattern can be used, and the exposure dose should preferably be 1–200 mJ / cm². 2And preferably, it should be 10~100mJ / cm 2 The process is carried out by irradiation. When using EB, a mask is used to form the desired pattern, or the exposure dose should be 1~300 μC / cm. 2 And preferably, it should be 10~200μC / cm 2 Irradiation is performed in this manner.

[0679] In addition to the conventional exposure method, exposure can also be performed using an immersion method, in which a liquid with a refractive index of 1.0 or higher is inserted between the resist film and the projection lens. In this case, a water-insoluble protective film can also be used.

[0680] The aforementioned water-insoluble protective film is used to prevent leaching from the resist film and to improve the hydrophobicity of the film surface. It is broadly classified into two types. One type is an organic solvent-stripping type, which must be stripped using an organic solvent that does not dissolve the resist film before alkaline aqueous solution development. The other type is an alkaline aqueous solution-soluble type, which is soluble in alkaline aqueous solutions and removes the protective film while removing the soluble portion of the resist film. The latter is particularly well-suited to materials based on polymers containing 1,1,1,3,3,3-hexafluoro-2-propanol residues that are insoluble in water but soluble in alkaline aqueous solutions, and which are dissolved in alcohol solvents with 4 or more carbon atoms, ether solvents with 8 to 12 carbon atoms, or mixtures thereof. Materials can also be prepared by dissolving the aforementioned water-insoluble but alkaline aqueous solution-soluble surfactants in alcohol solvents with 4 or more carbon atoms, ether solvents with 8 to 12 carbon atoms, or mixtures thereof.

[0681] PEB can also be performed after exposure. PEB can be performed, for example, by heating on a hot plate at a temperature of 60-150°C for 1-5 minutes, preferably at 80-140°C for 1-3 minutes.

[0682] For example, a developing solution containing 0.1-5% by mass, preferably 2-3% by mass, such as tetramethylammonium hydroxide (TMAH), can be used. Common methods such as dip, immersion, and spray can be employed for 0.1-3 minutes, preferably 0.5-2 minutes. This allows the exposed areas to dissolve and form the desired pattern on the substrate.

[0683] Furthermore, after the resist film is formed, it can be rinsed with pure water to extract acid-generating agents or wash away particulate matter from the film surface. It can also be rinsed to remove water remaining on the film after exposure.

[0684] In addition, a double patterning method can also be used to form patterns. Examples of double patterning methods include: a trench method that uses a first exposure and etching to process a 1:3 trench pattern substrate, then offsets the position and uses a second exposure to form a 1:3 trench pattern, thus forming a 1:1 pattern; and a line method that uses a first exposure and etching to process a 1:3 isolated residual pattern on a first substrate, then offsets the position and uses a second exposure under the first substrate to form a 1:3 isolated residual pattern, and then processes this second substrate to form a 1:1 pattern with a pitch of half.

[0685] In the pattern forming method of the present invention, a negative tone development method can also be used, in which the aforementioned alkaline aqueous solution is replaced with an organic solvent as the developer to dissolve the unexposed portion.

[0686] In the aforementioned negative tone development, the following developers may be used: 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butyl acetate, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl valerate, methyl valerate, methyl crotonate. Esters, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, etc. These organic solvents can be used alone or in combination of two or more.

[0687] [Precursor polymers]

[0688] The present invention is a precursor polymer containing repeating units (1a') represented by the following general formula (1a'), repeating units (1b') represented by the following general formula (1b'), and repeating units (1c') represented by the following general formula (1c').

[0689] [Chemistry 174]

[0690]

[0691] In the formula, a1 is 0 or 1. a2 is an integer from 0 to 4. a3 is an integer from 0 to 4.

[0692] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0693] R 1It can be a halogen atom, nitro group, cyano group, hydroxyl group, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms. Furthermore, when a2 is 2, 3, or 4, multiple R... 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0694] X 1 It is a linking group.

[0695] Q 1 ~Q 4 Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom.

[0696] R N1 ~R N4 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R N1 ~R N4 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to.

[0697] [Chemistry 175]

[0698]

[0699] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0700] Z 1 Single bond, phenylene, naphthylene, *-C(=O)-OZ 11 -、or *-C(=O)-NH-Z 11 - and the aforementioned phenylene or naphthylene may also be substituted by hydroxyl, nitro, cyano, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, or saturated hydrocarbon oxygen groups with 1 to 10 carbon atoms containing fluorine atoms, or halogen atoms. 11 It is a saturated alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the aforementioned saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0701] AL 1 It is an acid-labile group.

[0702] [Chemistry 176]

[0703]

[0704] In the formula, b1 is an integer from 1 to 4. b2 is an integer from 0 to 4. However, 1 ≤ b1 + b2 ≤ 5.

[0705] R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0706] Y 1 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain.

[0707] R 11 It can be a halogen atom, carboxyl group, nitro group, cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl oxygen group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxygen carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When b2 is 2, 3, or 4, each R 11 They can be the same or different.

[0708] AL 2 It is an acid-instable group or a base-instable group.

[0709] Furthermore, the aforementioned repeating unit (1a') should preferably be a repeating unit (11a') represented by the following general formula (11a').

[0710] [Chemistry 177]

[0711]

[0712] In the formula, a1~a3, R A R 1 Q 1 ~Q 4 and R N1 ~R N4 Same as above.

[0713] Furthermore, the aforementioned repeating unit (11a') should preferably be a repeating unit (12a') represented by the following general formula (12a').

[0714] [Chemistry 178]

[0715]

[0716] In the formula, a1, a2, R A R 1 Q 2 ~Q 4 and R N1 ~R N4 Same as above.

[0717] Specific examples of the repeating units (1a'), (1b'), and (1c') described above are the same as those described in the manufacturing method of the base polymer for photoresist described above.

[0718] Furthermore, the precursor polymer of the present invention can be manufactured using the method described in step (1) of the method for manufacturing the base polymer for photoresist of the present invention.

[0719] Example

[0720] The present invention will be specifically described below by way of examples of synthesis, comparative synthesis, preparation, comparative preparation, examples, and comparative examples, but the present invention is not limited to the following examples. Furthermore, the apparatus used is described below.

[0721] IR: NICOLET 6700, manufactured by Thermo Fisher Scientific

[0722] 1 H-NMR: ECA-500 manufactured by Nippon Electronics Co., Ltd.

[0723] MALDI TOF-MS: S3000 manufactured by Nippon Electronics Co., Ltd.

[0724] [1A] Synthesis of ammonium salt monomers

[0725] [Synthetic Example 1-1] Synthesis of PrePAG-1

[0726] [Chemistry 179]

[0727]

[0728] Under nitrogen atmosphere, benzyltrimethylammonium = 2-hydroxy-1,1-difluoroethane sulfonate (31.1 g), triethylamine (13.2 g), and dimethylaminopyridine (1.2 g) were dissolved in dichloromethane (200 g). The reaction mixture was then cooled to below 10°C. After cooling, 4-vinylbenzenesulfonyl chloride (20.3 g) was added dropwise at an internal temperature below 20°C. After the addition, the reaction mixture was heated to room temperature and matured for 12 hours. After maturation, the reaction mixture was cooled, and water (150 g) was added to stop the reaction. The organic layer was then extracted, washed with water, and concentrated under reduced pressure to remove the solvent. The residue was crystallized with diisopropyl ether to obtain 42.0 g of PrePAG-1 (88% yield) as white crystals.

[0729] [Synthetic Examples 1-2] Synthesis of PrePAG-2

[0730] [Chemistry 180]

[0731]

[0732] Under nitrogen atmosphere, benzyltrimethylammonium (2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate) (119.1 g), triethylamine (44.5 g), and dimethylaminopyridine (3.8 g) were dissolved in dichloromethane (800 g). The reaction mixture was then cooled to below 10°C. After cooling, 4-vinylbenzenesulfonyl chloride (70.0 g) was added dropwise at an internal temperature below 20°C. After the addition, the reaction mixture was heated to room temperature and matured for 12 hours. After maturation, the reaction mixture was cooled, and water (500 g) was added to stop the reaction. The organic layer was then extracted, washed with water, and concentrated under reduced pressure to remove the solvent. The residue was crystallized with diisopropyl ether to obtain 152.0 g of PrePAG-2 (88% yield) as white crystals.

[0733] PrePAG-3 was synthesized with reference to Japanese Patent Application Publication No. 2023-172918. PrePAG-4 was synthesized with reference to International Patent Application Publication No. 2024 / 014462. Their structures are shown below.

[0734] [Chemistry 181]

[0735]

[0736] [1B] Comparison of the synthesis of sulfonium salt monomers

[0737] [Comparative Synthesis Example 1-1] Synthesis of P-3

[0738] [Chemistry 182]

[0739]

[0740] The feedstock [Synthetic Example 1-1], consisting of PrePAG-1 (37.6 g), bis(4-trifluoromethylphenyl)-phenylsulfonium chloride (46.7 g), dichloromethane (300 g), and water (150 g), was stirred at room temperature for 30 minutes. The organic layer was separated and extracted, washed with water, and then concentrated under reduced pressure. The residue was crystallized with diisopropyl ether to obtain 53.3 g of the comparative sulfonium salt monomer P-3 (yield 94%) as white crystals.

[0741] [Comparative Synthesis Examples 1-2 to 1-7] Comparative synthesis using sulfonium salt type monomers P-4, P-6 to P-10

[0742] Using the corresponding raw materials and various organic synthesis reactions, and in the same manner as in [Comparative Synthesis Example 1-1], the comparative sulfonate monomers P-4, P-6~P-10 were synthesized as shown below.

[0743] [Chemistry 183]

[0744]

[0745] [2A] Step (1): Synthesis of precursor polymer

[0746] [Synthetic Example 2A-1] Synthesis of Prepolymer-1a

[0747] [Chemistry 184]

[0748]

[0749] Under nitrogen atmosphere, PrePAG-1 (14.3 g), monomer a-3 (22.5 g), monomer b-11 (13.0 g), V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 2.30 g), and MEK (75 g) were measured in a flask to prepare a monomer-polymerization initiator solution. In another flask already prepared under nitrogen atmosphere, 25 g of MEK was measured, and the mixture was heated to 80°C with stirring. The aforementioned monomer-polymerization initiator solution was then added dropwise over 4 hours. After the addition was complete, the temperature of the polymerization solution was maintained at 80°C and stirred continuously for 2 hours, then cooled to room temperature. The resulting polymer solution was added dropwise to 500 g of vigorously stirred hexane, and the precipitated polymer was separated by filtration. The obtained polymer was then washed twice with 150 g of diisopropyl ether and vacuum dried at 50°C for 20 hours to obtain a white powdery prepolymer-1a (yield 46.3 g, 93% yield). The Mw of prepolymer-1a is 9,100, and the Mw / Mn ratio is 1.81. Additionally, Mw is a polystyrene conversion value determined by GPC using DMF as a solvent.

[0750] [Synthetic Examples 2A-2 to 2A-25] Synthesis of Prepolymer-2a to Prepolymer-25a

[0751] By changing the type and blending ratio of each monomer, the prepolymers-2a to-25a shown in Table 1 below are produced using the same method as in Synthesis Example 2A-1.

[0752] [Table 1]

[0753]

[0754] Table 1 provides the monomers other than PrePAG-1 to PrePAG-4, monomer a-3, and monomer b-11 in each unit as follows.

[0755] [Chemistry 185]

[0756]

[0757] [2B] Step (2): Synthesis of the deprotected precursor polymer

[0758] [Synthetic Example 2B-1] Synthesis of Prepolymer-1b

[0759] [Chemistry 186]

[0760]

[0761] Under nitrogen atmosphere, prepolymer-1a (50.0 g) was dissolved in 200 g of MEK in a flask, and triethylamine (10.1 g) was added. The mixture was heated and stirred at 50 °C for 12 hours. The reaction solution was then cooled to room temperature, and ethyl acetate (300 g) and water (150 g) were added. The mixture was separated by liquid-liquid extraction to obtain the organic layer. The organic layer was then washed three times with water (75 g), and the solvent was removed by vacuum distillation. The remaining solid was dissolved in PGME (propylene glycol monomethyl ether) (200 g), and the solvent was removed by vacuum distillation. After azeotropic dehydration, PGME (150 g) was added to obtain the polymer solution. The obtained polymer solution was added dropwise to 600 g of diisopropyl ether under vigorous stirring, and the precipitated polymer was separated by filtration. The obtained polymer was then washed twice with 200g of diisopropyl ether and vacuum dried at 50°C for 20 hours to obtain a white powdery prepolymer-1b (yield 46g, 93% yield). The Mw of prepolymer-1b was 9,100, and the Mw / Mn ratio was 1.81. Furthermore, Mw is a polystyrene conversion value determined by GPC using DMF as a solvent.

[0762] Synthesis of prepolymers 2B-2 to 2B-7, 2B-10 to 2B-25: Synthesis of prepolymers 2b to 7b, 10b to 25b

[0763] Using the same method as in Synthesis Example 2B-1, prepolymers-2b to-7b and prepolymers-10b to-25b as shown in Table 2 below were manufactured.

[0764] [Synthetic Example 2B-8] Synthesis of Prepolymer-8b

[0765] [Chemistry 187]

[0766]

[0767] Under nitrogen atmosphere, prepolymer-8a (30.0 g) was dissolved in 50 g of MEK in a flask, and acetic acid (2.5 g) and methanol (50 g) were added. The mixture was stirred at 30 °C for 12 hours. The resulting reaction solution was added dropwise to 1,000 g of a vigorously stirred methanol-water mixture, and the precipitated polymer was separated by filtration. The obtained polymer was then washed twice with 200 g of water and vacuum dried at 50 °C for 20 hours to obtain a white powdery polymer prepolymer-8b (yield 29 g, 96% yield). The Mw of prepolymer-8b was 9,500, and the Mw / Mn ratio was 1.86. Mw is a polystyrene conversion value determined by GPC using DMF as a solvent.

[0768] [Synthetic Example 2B-9] Synthesis of Prepolymer-9b

[0769] Prepolymer-9b, as shown in Table 2 below, was produced using the same method as in Synthesis Example 2B-8.

[0770] [Table 2]

[0771]

[0772] Table 2 provides the monomers b-1 and b-2 of unit B as follows.

[0773] [Chemistry 188]

[0774]

[0775] [2C] Step (3): Synthesis of polymer for photoresist

[0776] [Synthetic Example 2C-1] Synthesis of Polymer-1

[0777] [Chemistry 189]

[0778]

[0779] Under nitrogen atmosphere, prepolymer-1b (50.0 g), cation-1 (22.3 g) as shown in the above chemical formula, 400 g of dichloromethane, and 200 g of water were mixed in a flask and stirred at room temperature for 2 hours. The organic layer was then separated from the reaction solution. The organic layer was washed three times with water (100 g), and the solvent was removed by vacuum distillation. 200 g of methyl isobutyl ketone was added to the concentrated residue, followed by vacuum distillation to achieve azeotropic dehydration. Another 200 g of methyl isobutyl ketone was then added to obtain a polymer solution. The obtained polymer solution was added dropwise to 600 g of diisopropyl ether under vigorous stirring, and the precipitated polymer was separated by filtration. The obtained polymer was washed twice with 100 g of diisopropyl ether and then vacuum dried at 50°C for 20 hours to obtain a white powder, polymer-1 (yield 47 g, 94% yield). The Mw of polymer-1 was 9,200, and the Mw / Mn ratio was 1.80. In addition, Mw is the polystyrene conversion value determined by GPC using DMF as a solvent.

[0780] [Synthetic Examples 2C-2~2C-25] Synthesis of Polymer-2~Polymer-25

[0781] Polymer-2 to Polymer-25 as shown in Table 3 below were manufactured using the same method as in Synthesis Example 2C-1.

[0782] [Table 3]

[0783]

[0784] Table 3 provides the monomers P-1, P-2, and P-5 of unit P as follows.

[0785] [Chemistry 190]

[0786]

[0787] [Comparative Synthesis Example 2-1] Synthesis of Comparative Polymer-1

[0788] The types and blending ratios of the monomers were changed, but polymerization was carried out in the same manner as in [Synthesis Example 2A-1], and then the phenolic hydroxyl groups were deprotected in the same manner as in [Synthesis Example 2B-8]. However, during the deprotection reaction, it was observed that some of the methacrylic acid units in the unit (a-3) containing the acid-unstable group were leaving.

[0789] [Chemistry 191]

[0790]

[0791] [Comparative Synthesis Example 2-2] Synthesis of Comparative Polymer-2

[0792] The types and blending ratios of the monomers were changed, but polymerization was carried out in the same manner as in [Synthesis Example 2A-1], and then the phenolic hydroxyl groups were deprotected in the same manner as in [Synthesis Example 2B-1]. However, during the deprotection reaction, it was observed that some of the sulfonium cations decomposed into triethylammonium cation units, and some of the methacrylic acid units (a-5) containing acid-unstable groups left.

[0793] [Chemistry 192]

[0794]

[0795] [Comparative Synthesis Examples 2-3 to 2-8] Synthesis of Comparative Polymers-3 to Comparative Polymers-8

[0796] The types and blending ratios of the monomers were changed, but polymerization was carried out using the same method as in [Synthesis Example 2A-1]. For units containing phenolic hydroxyl groups, the hydroxyl groups were not protected and were directly supplied for polymerization.

[0797] [Comparative Synthesis Examples 2-9~2-10] Synthesis of Comparative Polymers-9~10

[0798] The types and blending ratios of the monomers were changed, but polymerization was carried out in the same manner as in [Synthesis Example 2A-1], and then the phenolic hydroxyl groups were deprotected in the same manner as in [Synthesis Example 2B-1].

[0799] The types and blending examples of monomers for each unit in Comparative Polymer-1 to Comparative Polymer-10 are shown in Table 4 below.

[0800] [Table 4]

[0801]

[0802] In Table 4, a partial decomposition was observed when comparing polymers-1 and-2.

[0803] [3] Preparation of chemically amplified resist composition

[0804] [Preparation Examples 1-31, Comparative Preparation Examples 1-16]

[0805] The base polymer (polymer-1-polymer-25), comparative base polymer (comparative polymer-1-comparative polymer-10), photoacid generator (PAG-X, PAG-Y), and quencher (Q-1 to Q-5) obtained by the manufacturing method of the present invention are dissolved in a solvent containing 0.01% by mass of surfactant A (OMNOVA) to prepare a solution. The solution is then filtered through a 0.2 μm Teflon (registered trademark) type filter to prepare chemically amplified resist compositions (R-01 to R-31) and comparative resist compositions (CR-01 to CR-16).

[0806] [Table 5]

[0807]

[0808] [Table 6]

[0809]

[0810] [Table 7]

[0811]

[0812] In Tables 5-7, the solvents, photoacid generators PAG-X and PAG-Y, and quenchers Q-1 to Q-5 are described below.

[0813] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[0814] DAA (diacetone alcohol)

[0815] Photoacid generators: PAG-X, PAG-Y

[0816] [Chemistry 193]

[0817]

[0818] Quenching agents: Q-1~Q-5

[0819] [Chemistry 194]

[0820]

[0821] Furthermore, surfactant A is described below.

[0822] Surfactant A: 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane / tetrahydrofuran / 2,2-dimethyl-1,3-propanediol copolymer (manufactured by OMNOVA).

[0823] [Chemistry 195]

[0824]

[0825] a : (b + b') : (c + c') = 1 : 4~7 : 0.01~1 (molar ratio)

[0826] Mw=1,500

[0827] [4] Evaluation of EUV lithography

[0828] [Examples 1-31, Comparative Examples 1-16]

[0829] The chemically amplified resist compositions (R-01~R-31) and the comparative resist compositions (CR-01~CR-16) shown in Tables 5-7 were spin-coated onto a Si substrate with a silicon-containing spin-coating hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., with a film thickness of 20 nm. The substrate was pre-baked at 120°C for 60 seconds using a hot plate to obtain a resist film with a thickness of 50 nm. The aforementioned resist film was then subjected to exposure using an ASML EUV scanning exposure machine NXE3400B (NA 0.33, hexapolar illumination) with varying exposure dose and focus (exposure pitch: 1 mJ / cm). 2 Exposure was performed on a contact hole pattern with a size of 18 nm and a pitch of 36 nm on the wafer edge (focal pitch: 0.020 μm). After exposure, PEB was performed for 60 seconds at the temperatures shown in Tables 8 and 9. Subsequently, immersion development was performed for 30 seconds with a 2.38% (w / w) TMAH aqueous solution, followed by rinsing with a surfactant-containing rinsing material and spin drying to obtain a positive pattern. The contact hole pattern obtained was observed using a Hitachi Advanced Technology Co., Ltd. critical dimension SEM (CG6300), and the sensitivity, EL, CDU, and depth of focus (DOF) were evaluated according to the following methods. The results are shown in Tables 8 and 9.

[0830] [Sensitivity Evaluation]

[0831] The optimal exposure (mJ / cm²) is defined as the exposure required to form a hole with a size of 18 nm. 2 ), and calculate the value. The smaller the value, the higher the sensitivity.

[0832] [EL Review]

[0833] The exposure amount formed within ±10% (16.2~19.8nm) of the 18nm spacing width in the aforementioned contact hole pattern is used to calculate the EL (unit: %) using the following formula. The larger this value, the better the performance.

[0834] EL(%) = (|E1-E2| / Eop) × 100

[0835] E1: Provides the optimal exposure for contact hole patterns with a hole diameter of 16.2nm and a pitch of 36nm.

[0836] E2: Provides optimal exposure for contact hole patterns with a hole diameter of 19.8nm and a pitch of 36nm.

[0837] Eop: Provides the optimal exposure for contact hole patterns with a hole diameter of 18nm and a pitch of 36nm.

[0838] [CDU Evaluation]

[0839] The dimensions of 50 holes at the optimal exposure were determined, and the standard deviation (σ) obtained from the results was defined as three times the value of 3σ (CDU). The smaller this value, the smaller the dimensional variation, and the more uniform the hole diameter pattern can be obtained.

[0840] [DOF Rating]

[0841] In terms of focal depth evaluation, the focal range formed within ±10% (16.2~19.8nm) of the 18nm dimension in the aforementioned contact hole pattern is determined. The larger this value, the wider the focal depth.

[0842] [Table 8]

[0843]

[0844] [Table 9]

[0845]

[0846] As shown in Table 8, Examples 1-1 to 1-31, which used chemically amplified resist compositions containing a base polymer prepared using the manufacturing method of the present invention, exhibited good sensitivity and excellent EL, CDU, and DOF. Therefore, it is evident that such chemically amplified resist compositions are suitable as materials for EUV lithography.

[0847] On the other hand, as shown in Table 9, it can be seen that the comparative examples 1-1 to 1-16, which used comparative resist compositions containing a base polymer prepared using a known manufacturing method, had worse EL, CDU, and DOF results than the examples.

[0848] This specification contains the following specifications.

[0849] [1]: A method for manufacturing a base polymer for photoresist, characterized by comprising the following steps: a repeating unit (a) of a photoacid generator containing an anionic portion and a main chain linking the photoacid generator, wherein the cationic portion is a sulfonate cation or a monazite cation; a repeating unit (b) of a compound in which the hydrogen atoms of a carboxylic acid are protected by an acid-instable group; and a repeating unit (c) of a compound containing a phenolic hydroxyl group.

[0850] (1) Precursor polymers containing repeating units (a') of ammonium salt compounds with anionic portions and main chain linkages, and whose cationic portions are quaternary ammonium cations, repeating units (b') of compounds in which the hydrogen atoms of carboxylic acids are protected by acid-instable groups, and repeating units (c') of compounds in which phenolic hydroxyl groups are protected.

[0851] (2) Deprotect the repeating unit (c') of the compound in the precursor polymer prepared in step (1) to expose the phenolic hydroxyl groups, and obtain the deprotected precursor polymer.

[0852] (3) The ammonium salt of the repeating unit (a') of the aforementioned ammonium salt compound in the deprotected precursor polymer obtained in step (2) is converted into sulfonium salt or sulfonium salt, and a base polymer for photoresist is obtained.

[0853] [2]: The method for manufacturing the base polymer for photoresist as described in [1] uses the repeating unit (1a') represented by the following general formula (1a') as the aforementioned repeating unit (a'), the repeating unit (1b') represented by the following general formula (1b') as the aforementioned repeating unit (b'), and the repeating unit (1c') represented by the following general formula (1c') as the aforementioned repeating unit (c').

[0854] [Chemistry 196]

[0855]

[0856] In the formula, a1 is 0 or 1. a2 is an integer from 0 to 4. a3 is an integer from 0 to 4.

[0857] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0858] R 1 It can be a halogen atom, nitro group, cyano group, hydroxyl group, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms. Furthermore, when a2 is 2, 3, or 4, multiple R... 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0859] X 1 It is a linking group.

[0860] Q 1 ~Q 4 Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom.

[0861] R N1 ~R N4 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R N1 ~R N4 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to.

[0862] [Chemistry 197]

[0863]

[0864] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0865] Z 1 Single bond, phenylene, naphthylene, *-C(=O)-OZ 11 -、or *-C(=O)-NH-Z 11 - and the aforementioned phenylene or naphthylene may also be substituted by hydroxyl, nitro, cyano, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, or saturated hydrocarbon oxygen groups with 1 to 10 carbon atoms containing fluorine atoms, or halogen atoms. 11 It is a saturated alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the aforementioned saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0866] AL 1 It is an acid-labile group.

[0867] [Chemistry 198]

[0868]

[0869] In the formula, b1 is an integer from 1 to 4. b2 is an integer from 0 to 4. However, 1 ≤ b1 + b2 ≤ 5.

[0870] R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0871] Y 1 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain.

[0872] R 11It can be a halogen atom, carboxyl group, nitro group, cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl oxygen group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxygen carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When b2 is 2, 3, or 4, each R 11 They can be the same or different.

[0873] AL 2 It is an acid-instable group or a base-instable group.

[0874] [3]: The method for manufacturing the base polymer for photoresist as described in [2] uses the repeating unit (11a') represented by the following general formula (11a') as the aforementioned repeating unit (1a').

[0875] [Chemistry 199]

[0876]

[0877] In the formula, a1~a3, R A R 1 Q 1 ~Q 4 and R N1 ~R N4 Same as above.

[0878] [4]: The method for manufacturing the base polymer for photoresist as described in [3] uses the repeating unit (12a') represented by the following general formula (12a') as the aforementioned repeating unit (11a').

[0879] [Chem.200]

[0880]

[0881] In the formula, a1, a2, R A R 1 Q 2 ~Q 4 and R N1 ~R N4 Same as above.

[0882] [5]: A method for manufacturing a photoresist base polymer as described in any of [1] to [4] above, wherein the aforementioned repeating unit (a) contained in the aforementioned photoresist base polymer has a sulfonium cation represented by the following general formula (Z-3).

[0883] [Chemical Engineering 201]

[0884]

[0885] In the formula, m1 is 0 or 1. m2 is 0 or 1. m3 is 0 or 1. m4 is an integer from 0 to 4. m5 is an integer from 0 to 4. m6 is an integer from 0 to 6. m7 is an integer from 0 to 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 an integer from 0 to 4. m13 is 0, 1, or 2. m14 is 0, 1, or 2. However, when m1 is 0, 0 ≤ m6 + m9 ≤ 4; when m1 is 1, 0 ≤ m6 + m9 ≤ 6. When m2 is 0, 0 ≤ m7 + m10 ≤ 4; when m2 is 1, 0 ≤ m7 + m10 ≤ 6. When m3 is 0, 1 ≤ m4 + m5 + m8 + m14 ≤ 4; when m3 is 1, 1 ≤ m4 + m5 + m8 + m14 ≤ 6. When m11 is 0, 0 ≤ m12 + m13 ≤ 4; when m11 is 1, 0 ≤ m12 + m13 ≤ 6. Also, m4 + m12 ≥ 1.

[0886] R F1 ~R F3 Each R is independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms. When m5 is 2, 3, or 4, each R F1 They can be the same or different. When m6 is an integer from 2 to 6, each R... F2 They can be the same or different. When m7 is an integer from 2 to 6, each R... F3 They can be the same or different.

[0887] R ct6 ~R ct9 It can be a halogen atom other than iodine and fluorine atoms, a nitro group, a cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. When m8 is 2, there are 2 R groups. ct6 They can be the same or different, and there are 2 Rs. ct6 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m9 is 2, there are 2 R atoms. ct7 They can be the same or different, and there are 2 Rs. ct7 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m10 is 2, the two R atoms... ct8 They can be the same or different, and there are 2 Rs. ct8 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m13 is 2, there are 2 R atoms. ct9 They can be the same or different, and there are 2 Rs. ct9 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0888] Furthermore, S directly bonded to the sulfonium cation +The aromatic rings can also bond with each other and with S + Together they form a ring.

[0889] L A and L B Each bond can be independently a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0890] X L It is a single bond or may contain heteroatoms and is a hydrocarbon group with 1 to 40 carbon atoms.

[0891] [6]: A method for forming a pattern, characterized by comprising the following steps:

[0892] A resist film is formed on a substrate using a photoresist composition containing a photoresist base polymer prepared by a manufacturing method of any one of the photoresist base polymers described in [1] to [5] above.

[0893] The aforementioned resist film was exposed to high-energy radiation, and

[0894] The previously exposed resist film was developed using a developer.

[0895] [7]: The pattern forming method described in [6] above uses a KrF excimer laser, an ArF excimer laser, an electron beam, or extreme ultraviolet light with a wavelength of 3 to 15 nm as the aforementioned high-energy rays.

[0896] [8]: A precursor polymer, characterized in that it contains repeating units (1a') represented by the following general formula (1a'), repeating units (1b') represented by the following general formula (1b'), and repeating units (1c') represented by the following general formula (1c').

[0897] [Chemical Engineering 202]

[0898]

[0899] In the formula, a1 is 0 or 1. a2 is an integer from 0 to 4. a3 is an integer from 0 to 4.

[0900] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0901] R 1 It can be a halogen atom, nitro group, cyano group, hydroxyl group, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms. Furthermore, when a2 is 2, 3, or 4, multiple R... 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0902] X 1 It is a linking group.

[0903] Q 1 ~Q 4 Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom.

[0904] R N1 ~R N4 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R N1 ~R N4 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to.

[0905] [Chemical Engineering 203]

[0906]

[0907] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0908] Z 1 Single bond, phenylene, naphthylene, *-C(=O)-OZ 11 -、or *-C(=O)-NH-Z 11 - and the aforementioned phenylene or naphthylene may also be substituted by hydroxyl, nitro, cyano, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, or saturated hydrocarbon oxygen groups with 1 to 10 carbon atoms containing fluorine atoms, or halogen atoms. 11 It is a saturated alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the aforementioned saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0909] AL 1 It is an acid-labile group.

[0910] [Chemical 204]

[0911]

[0912] In the formula, b1 is an integer from 1 to 4. b2 is an integer from 0 to 4. However, 1 ≤ b1 + b2 ≤ 5.

[0913] R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0914] Y 1 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain.

[0915] R 11It can be a halogen atom, carboxyl group, nitro group, cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxygen group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon carbonyl oxygen group with 2 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxygen carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When b2 is 2, 3, or 4, each R 11 They can be the same or different.

[0916] AL 2 It is an acid-instable group or a base-instable group.

[0917] [9]: The precursor polymer as described in [8] above, wherein the aforementioned repeating unit (1a') is a repeating unit (11a') represented by the following general formula (11a').

[0918] [Chemical Engineering 205]

[0919]

[0920] In the formula, a1~a3, R A R 1 Q 1 ~Q 4 and R N1 ~R N4 Same as above.

[0921]

[10] : The precursor polymer as described in [9] above, wherein the aforementioned repeating unit (11a') is a repeating unit (12a') represented by the following general formula (12a').

[0922] [Chemical Engineering 206]

[0923]

[0924] In the formula, a1, a2, R A R 1 Q 2 ~Q 4 and R N1 ~R N4 Same as above.

[0925] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative examples, and those having substantially the same structure as the technical concept described in the claims of the present invention and performing the same effects are all intended to be included within the technical scope of the present invention.

Claims

1. A method for manufacturing a base polymer for photoresist, comprising a repeating unit (a) of a photoacid generator containing an anionic portion and a main chain linking the photoacid generator, and the cationic portion being a sulfonium cation or a monazine cation; a repeating unit (b) of a compound in which the hydrogen atoms of a carboxylic acid are protected by acid-instable groups; and a repeating unit (c) of a compound containing a phenolic hydroxyl group, characterized by comprising the following steps: (1) Precursor polymers containing repeating units (a') of ammonium salt compounds with anionic portions and main chain linkages, and whose cationic portions are quaternary ammonium cations, repeating units (b') of compounds in which the hydrogen atoms of carboxylic acids are protected by acid-instable groups, and repeating units (c') of compounds in which phenolic hydroxyl groups are protected. (2) Deprotect the repeating unit (c') of the compound in the precursor polymer prepared in step (1) to expose the phenolic hydroxyl group, and obtain the deprotected precursor polymer. (3) The ammonium salt of the repeating unit (a') of the ammonium salt compound in the deprotected precursor polymer obtained in step (2) is converted into sulfonium salt or sulfonium salt, and a base polymer for photoresist is obtained.

2. The method for manufacturing the base polymer for photoresist according to claim 1, wherein the repeating unit (1a') represented by the following general formula (1a') is used as the repeating unit (a'), the repeating unit (1b') represented by the following general formula (1b') is used as the repeating unit (b'), and the repeating unit (1c') represented by the following general formula (1c') is used as the repeating unit (c'). In the formula, a1 is 0 or 1; a2 is an integer from 0 to 4; a3 is an integer from 0 to 4; R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R 1 It can be a halogen atom, nitro, cyano, hydroxyl, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms; also, when a2 is 2, 3 or 4, multiple R 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to; X 1 It is a linking group; Q 1 ~Q 4 Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group; R N1 ~R N4 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms; also, R N1 ~R N4 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to; In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z 1 Single bond, phenylene, naphthylene, *-C(=O)-OZ 11 -、or *-C(=O)-NH-Z 11 - and the phenylene or naphthylene group may also be substituted by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, a saturated hydrocarbon oxygen group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom; Z 11 It is a saturated alkylene group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring; * indicates an atomic bond with a carbon atom of the main chain; AL 1 It is an acid-labile group; In the formula, b1 is an integer from 1 to 4; b2 is an integer from 0 to 4; however, 1≤b1+b2≤5; R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Y 1 It represents a single bond or *-C(=O)-O-; * indicates an atomic bond with a carbon atom in the main chain; R 11 It can be a halogen atom, carboxyl group, nitro group, cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyloxy group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyloxy group with 2 to 20 carbon atoms containing heteroatoms; when b2 is 2, 3 or 4, each R 11 They can be the same or different; AL 2 It is an acid-instable group or a base-instable group.

3. The method for manufacturing the base polymer for photoresist according to claim 2, wherein the repeating unit (11a') represented by the following general formula (11a') is used as the repeating unit (1a'); In the formula, a1~a3, R A R 1 Q 1 ~Q 4 and R N1 ~R N4 Same as above.

4. The method for manufacturing the base polymer for photoresist according to claim 3, wherein the repeating unit (12a') represented by the following general formula (12a') is used as the repeating unit (11a'); In the formula, a1, a2, R A R 1 Q 2 ~Q 4 and R N1 ~R N4 Same as above.

5. The method for manufacturing the base polymer for photoresist according to any one of claims 1 to 4, wherein, The repeating unit (a) contained in the base polymer of the photoresist has a sulfonium cation represented by the following general formula (Z-3); In the formula, m1 is 0 or 1; m2 is 0 or 1; m3 is 0 or 1; m4 is an integer from 0 to 4; m5 is an integer from 0 to 4; m6 is an integer from 0 to 6; m7 is an integer from 0 to 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 an integer from 0 to 4; m13 is 0, 1, or 2; m14 is 0, 1, or 2; however, when m1 is 0, 0 ≤ m6 + When m9≤4, and 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; R F1 ~R F3 Each R is independently a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxygen group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms; when m5 is 2, 3, or 4, each R F1 They can be the same or different; when m6 is an integer from 2 to 6, each R F2 They can be the same or different; when m7 is an integer from 2 to 6, each R F3 They can be the same or different; R ct6 ~R ct9 It can be a halogen atom other than iodine and fluorine atoms, a nitro group, a cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; when m8 is 2, there are 2 R groups. ct6 They can be the same or different, and there are 2 Rs. ct6 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when m9 is 2, the two R atoms... ct7 They can be the same or different, and there are 2 Rs. ct7 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when m10 is 2, the two R atoms... ct8 They can be the same or different, and there are 2 Rs. ct8 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when m13 is 2, the two R atoms... ct9 They can be the same or different, and there are 2 Rs. ct9 They can also bond to each other and form rings together with the carbon atoms they are bonded to; Furthermore, S directly bonded to the sulfonium cation + The aromatic rings can also bond with each other and with S + Together they form a ring; L A and L B Each bond can be independently a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond; X L It is a single bond or may contain heteroatoms and is a hydrocarbon group with 1 to 40 carbon atoms.

6. A method for forming a pattern, characterized by comprising the following steps: A resist film is formed on a substrate using a photoresist composition containing a photoresist base polymer prepared by the method for manufacturing photoresist base polymer according to claim 1. The resist film was exposed to high-energy rays, and The exposed resist film was developed using a developer.

7. The pattern forming method according to claim 6, wherein a KrF excimer laser, an ArF excimer laser, an electron beam, or extreme ultraviolet light with a wavelength of 3-15 nm is used as the high-energy ray.

8. A precursor polymer, characterized in that... It contains repeating units (1a') represented by the following general formula (1a'), repeating units (1b') represented by the following general formula (1b'), and repeating units (1c') represented by the following general formula (1c'); In the formula, a1 is 0 or 1; a2 is an integer from 0 to 4; a3 is an integer from 0 to 4; R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R 1 It can be a halogen atom, nitro, cyano, hydroxyl, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms; also, when a2 is 2, 3 or 4, multiple R 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to; X 1 It is a linking group; Q 1 ~Q 4 Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group; R N1 ~R N4 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms; also, R N1 ~R N4 They can also bond to each other and form rings together with the nitrogen atoms they are bonded to; In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z 1 Single bond, phenylene, naphthylene, *-C(=O)-OZ 11 -、or *-C(=O)-NH-Z 11 - and the phenylene or naphthylene group may also be substituted by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, a saturated hydrocarbon oxygen group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom; Z 11 It is a saturated alkylene group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring; * indicates an atomic bond with a carbon atom of the main chain; AL 1 It is an acid-labile group; In the formula, b1 is an integer from 1 to 4; b2 is an integer from 0 to 4; however, 1≤b1+b2≤5; R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Y 1 It represents a single bond or *-C(=O)-O-; * indicates an atomic bond with a carbon atom in the main chain; R 11 It can be a halogen atom, carboxyl group, nitro group, cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyloxy group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon carbonyloxy group with 2 to 20 carbon atoms containing heteroatoms; when b2 is 2, 3 or 4, each R 11 They can be the same or different; AL 2 It is an acid-instable group or a base-instable group.

9. The precursor polymer according to claim 8, wherein, The repeating unit (1a') is the repeating unit (11a') represented by the following general formula (11a'); In the formula, a1~a3, R A R 1 Q 1 ~Q 4 and R N1 ~R N4 Same as above.

10. The precursor polymer according to claim 9, wherein, The repeating unit (11a') is the repeating unit (12a') represented by the following general formula (12a'); In the formula, a1, a2, R A R 1 Q 2 ~Q 4 and R N1 ~R N4 Same as above.

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