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

Abstract

The invention relates to a sulfonium salt type monomer, a polymer, a chemically amplified resist composition and a pattern forming method. The present invention addresses the problem of providing a photolithographic film having excellent solvent solubility, high sensitivity, high contrast, and excellent photolithographic properties in optical lithography using high-energy rays. The present invention relates to a sulfonium salt-type monomer used in a chemically amplified resist composition having excellent photolithography properties such as EL, LWR, CDU, and DOF, a polymer containing a repeating unit derived from the sulfonium salt-type monomer, a chemically amplified resist composition containing the polymer, and a pattern forming method using the chemically amplified resist composition. [Solution] A sulfonium salt-type monomer represented by formula (A).

Description

TECHNICAL FIELD

[0001] The present application relates to a sulfonium salt type monomer, a polymer, a chemically amplified resist composition, and a pattern forming method. BACKGROUND

[0002] With the high integration and high speed of LSI, the miniaturization of pattern rules is also rapidly progressing. In particular, the expansion of the flash memory market and the increase in memory capacity are leading to miniaturization. In terms of the most advanced miniaturization technology, mass production of 65 nm node devices obtained by ArF lithography is underway, and mass production of 45 nm node devices obtained by the next generation ArF immersion lithography is being prepared. In terms of the next generation 32 nm node devices, immersion lithography using a super-NA lens combining a liquid with a higher refractive index than water and a high refractive index lens, a high refractive index resist film, extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm, double exposure (double pattern lithography) of ArF lithography, etc. are options, and their exploration is being carried out.

[0003] With the miniaturization approaching the diffraction limit of light, the contrast of light gradually decreases. As the contrast of light decreases, the resolution or the depth of focus tolerance of hole patterns or trench patterns in positive resist films decreases.

[0004] With the miniaturization of patterns, the line width roughness (LWR) of line patterns and the size uniformity (CDU) of hole patterns are considered to be problems. The effects of uneven distribution of base polymers, acid generators, aggregation, or acid diffusion are pointed out. In addition, with the thinning of resist films, there is a tendency for LWR to increase, and the degradation of LWR caused by thinning with miniaturization becomes a serious problem.

[0005] In an EUV resist composition, high sensitivity, high resolution, and low LWR must be achieved at the same time. If the acid diffusion distance is shortened, LWR will be smaller, but it will be less sensitive. For example, by reducing the post-exposure bake (PEB) temperature, LWR will be smaller, but it will be less sensitive. Increasing the amount of quencher added will also make LWR smaller, but it will also be less sensitive. It is necessary to break the trade-off relationship between sensitivity and LWR.

[0006] To suppress acid diffusion, an antirecording agent compound containing a repeating unit of onium salt from a sulfonic acid having a polymerizable unsaturated bond has been proposed (Patent Document 1). Such a so-called polymer-bonded acid generator has a characteristic that the acid diffusion distance is very short because a polymer-type sulfonic acid is generated by exposure. Also, by increasing the ratio of the acid generator, the sensitivity can be improved. If the amount of the additive-type acid generator is increased, the sensitivity is also increased, but the acid diffusion distance is also increased. Since the acid diffuses unevenly, if the acid diffusion is increased, LWR and CDU are deteriorated. Among the balance of sensitivity, LWR, and CDU, the polymer-type acid generator has a higher ability.

[0007] Iodine atoms have a very large absorption of EUV with a wavelength of 13.5 nm, so the effect of generating secondary electrons from iodine atoms in exposure is observed, and is attracting attention in EUV lithography. Patent Document 2 describes a photoacid generator in which an iodine atom is introduced into an anion, and Patent Document 3 describes a photoacid generator containing a polymerizable group in which an iodine atom is introduced into an anion. By this, although a certain degree of improvement in lithographic performance is observed, the organic solvent solubility of iodine atoms is not high, and there are concerns about precipitation in solvents.

[0008] Patent Documents 4 and 5 describe photoacid generators in which pentafluorosulfanyl groups (-SF5 groups) and trifluoromethoxy groups (-OCF3 groups) are introduced into cations. By them, although the improvement in lithographic performance has progressed to some extent, there is still room for improvement, and the development of a more effective resist material for fine pattern formation is desired.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] [Patent Document 1] Japanese Patent No. 4425776

[0012] [Patent Document 2] Japanese Patent No. 6720926

[0013] [Patent Document 3] Japanese Patent No. 6973274

[0014] [Patent Document 4] International Publication No. 2023 / 223624

[0015] [Patent Document 5] Japanese Patent Application Publication No. 2022-59112 SUMMARY

[0016] [Problems to be Solved by the Invention]

[0017] 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.

[0018] The present invention was made in view of the foregoing, and aims to provide a sulfonium-type monomer used in a chemically amplified resist composition, particularly in optical lithography using high-energy rays such as KrF excimer lasers, ArF excimer lasers, electron beams (EB), and EUV, exhibiting excellent solvent solubility, high sensitivity, high contrast, and excellent lithographic performance such as EL, LWR, CDU, and DOF; a polymer containing repeating units from the sulfonium-type monomer; a chemically amplified resist composition containing the polymer; and a patterning method using the chemically amplified resist composition.

[0019] [Methods for solving the problem]

[0020] After repeated and in-depth exploration in order to achieve the aforementioned objectives, the inventors of this application discovered that by using a polymer containing repeating units of a sulfonate-type monomer composed of a sulfonate cation having a cyano group and an aromatic sulfonate anion having an aromatic vinyl structure and an iodine atom as a polymer bond type acid generator, it is possible to obtain a chemically amplified resist composition with high sensitivity, improved EL, LWR, CDU, DOF and other photolithographic properties, high contrast, and high resolution, thus completing this invention.

[0021] That is, the present invention provides the following composition of sulfonium salt monomer, polymer, chemically amplified resist and patterning method.

[0022] 1. A sulfonium salt type monomer, represented by the following formula (A).

[0023] [Chemistry 1]

[0024]

[0025] In the formula, p is 1, 2, or 3. n1 is 0 or 1. n2 is 1 or 2. n3 is 0, 1, 2, or 3. However, when n1 is 0, 1 ≤ n2 + n3 ≤ 5, and when n1 is 1, 1 ≤ n2 + n3 ≤ 7.

[0026] R 1 It can be a halogen atom, nitro group, hydroxyl group, carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When n3 is 2 or 3, each R 1 They can be the same or different, 2 Rs 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0027] R 2 It is a hydrocarbon group with 1 to 30 carbon atoms, which may also contain heteroatoms. When p is 1, there are 2 R groups. 2 They can be the same or different. Also, the bond is to S. + Two of the three substituents can also bond to each other and form a ring together with the sulfur atom they are bonded to.

[0028] Z - It is an aromatic sulfonate anion with an aromatic vinyl structure.

[0029] 2. Such as the sulfonium salt type monomer in 1, which is represented by the following formula (A1).

[0030] [Chemistry 2]

[0031]

[0032] In the formula, p, n1~n3, R 1 and Z - Same as above.

[0033] n4 is 0 or 1. n5 is 0, 1, 2, 3, 4 or 5.

[0034] R 3 It can be a halogen atom, nitro group, hydroxyl group, carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; or it can be a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When n5 is 2, 3, 4, or 5, each R 3 They can be the same or different, 2 Rs 3 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0035] 3. Sulfonate type monomers such as 1. or 2, wherein Z - Z represents the anion.

[0036] [Chemistry 3]

[0037]

[0038] In the formula, m1 is 0 or 1. m2 is 0, 1, 2, 3, or 4. m3 is 0, 1, 2, or 3. m4 is 0 or 1. m5 is 0, 1, 2, 3, or 4. m6 is 0, 1, 2, or 3. m7 is 0 or 1. m8 is 1, 2, 3, or 4. m9 is 0, 1, 2, or 3. m10 is 0 or 1. m11 is 0, 1, 2, 3, or 4. m12 is 0, 1, 2, or 3. m13 is 0 or 1. m14 is 0 or 1. m15 is 0 or 1. However, when m1 is 0, 0 ≤ m2 + m3 + m14 ≤ 4; when m1 is 1, 0 ≤ m2 + m3 + m14 ≤ 6. When m4 is 0, 0 ≤ m5 + m6 ≤ 4; when m4 is 1, 0 ≤ m5 + m6 ≤ 6. When m7 is 0, 0 ≤ m8 + m9 ≤ 5; when m7 is 1, 0 ≤ m8 + m9 ≤ 7. When m10 is 0, 0 ≤ m11 + m12 ≤ 4; when m10 is 1, 0 ≤ m11 + m12 ≤ 6. Also, 1 ≤ m2 + m5 + m8 ≤ 4.

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

[0040] R 11 R 12 and R 13 Each R can be independently a halogen atom other than iodine, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When m3 is 2 or 3, each R 11 They can be the same or different, 2 Rs 11 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m6 is 2 or 3, each R 12 They can be the same or different, 2 Rs 12 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When m9 is 2 or 3, each R 13 They can be the same or different, 2 Rs 13 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0041] R 14 It can be a halogen atom other than fluorine and iodine atoms, a nitro group, a hydroxyl 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 m12 is 2 or 3, each R 14 They can be the same or different, 2 Rs 14 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0042] R FIt is a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms. When m11 is 2, 3, or 4, each R F They can be the same or different.

[0043] L A L B L C L D and L E Each bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond.

[0044] X L1 and X L2 Each is an independent single bond or may contain a heteroatom and consist of 1 to 40 carbon atoms, forming an alkylene group.

[0045] However, m13 and m14 cannot both be 0 at the same time, L A L B L C L D X L1 and X L2 It cannot be a single key at the same time.

[0046] 4. As in 3., the sulfonium salt type monomer, where m15 is 1.

[0047] 5. A monomeric photoacid generator, composed of a sulfonium salt monomer as described in any one of 1. to 4.

[0048] 6. A polymer comprising repeating units from a monomeric photoacid generator as described in 5.

[0049] 7. The polymer of 6. further comprises at least one repeating unit selected from the repeating unit represented by formula (a1), the repeating unit represented by formula (a2) and the repeating unit represented by formula (a3).

[0050] [Chemistry 4]

[0051]

[0052] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0053] X 1 Single bond, phenylene, naphthylene, *-C(=O)-OX 11 -or *-C(=O)-NH-X 11- and the phenylene or naphthylene group may also be replaced by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, or a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom. X 11 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring.

[0054] X 2 It is a single bond, *-C(=O)-O- or *-C(=O)-NH-.

[0055] * indicates an atomic bond with a carbon atom in the main chain.

[0056] R 21 It can be a halogen atom, cyano group, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When a1 is 2, 3, or 4, each R 21 They can be the same or different.

[0057] AL 1 and AL 2 Each is an acid-labile group.

[0058] a1 can be 0, 1, 2, 3 or 4.

[0059] [Chemistry 5]

[0060]

[0061] In the formula, b1 is 0 or 1. b2 is 0, 1, 2 or 3 when b1 is 0, and 0, 1, 2, 3, 4 or 5 when b1 is 1.

[0062] R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0063] X 3 It represents a single bond, *-C(=O)-O-, or *-C(=O)-NH-. * indicates an atomic bond with a carbon atom in the main chain.

[0064] X 4 It is a single bond, an aliphatic alkylene group, carbonyl group, sulfonyl group, or a combination thereof, having 1 to 4 carbon atoms.

[0065] X 5 and X 6 Each can be independently an oxygen atom or a sulfur atom. However, X 4 and X 6Adjacent carbon atoms bonded to an aromatic ring.

[0066] R 22 and R 23 Each group consists independently of a hydrogen atom or may contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. Also, R 22 and R 23 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0067] R 24 It can be a halogen atom, hydroxyl group, cyano group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; or a hydrocarbon thio group or -N(R) group with 1 to 20 carbon atoms containing heteroatoms. 24A (R) 24B R 24A and R 24B Each is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. When b2 is 2 or more, each R 24 Multiple Rs can be the same or different. 24 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0068] 8. The polymer as in 6 or 7, further comprising at least one repeating unit selected from repeating units represented by formula (b1) and repeating units represented by formula (b2).

[0069] [Chemistry 6]

[0070]

[0071] In the formula, R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0072] Y 1 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain.

[0073] R 31 It is a hydrogen atom, or a group having 1 to 20 carbon atoms, selected from at least one of the following structures: hydroxyl group other than phenolic hydroxyl group, cyano group, carbonyl group, carboxyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulcinolone ring and carboxylic anhydride (-C(=O)-OC(=O)-).

[0074] R 32It can be a halogen atom, carboxyl group, nitro group, cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When c2 is 2, 3, or 4, each R 32 They can be the same or different.

[0075] c1 can be 1, 2, 3, or 4. c2 can be 0, 1, 2, 3, or 4. However, 1 ≤ c1 + c2 ≤ 5.

[0076] 9. A chemically amplified resist composition comprising (A) a base polymer comprising any one of the polymers described in 6 to 8.

[0077] 10. As in 9, the chemically amplified resist composition also contains (B) organic solvents.

[0078] 11. Chemically amplified resist compositions such as 9 or 10 also contain (C) quenchers.

[0079] 12. Any chemically amplified resist composition as described in any of 9. to 11, further contains (D) a photoacid generator.

[0080] 13. Any chemically amplified resist composition as described in any of 9 to 12, further contains (E) a surfactant.

[0081] 14. A method for forming a pattern, comprising the following steps:

[0082] A resist film is formed on a substrate using a chemically amplified resist composition as described in any of 9. to 13, and the resist film is exposed to high-energy radiation.

[0083] The previously exposed resist film was developed using a developer.

[0084] 15. The pattern forming method as in 14, wherein the aforementioned high-energy rays are KrF excimer lasers, ArF excimer lasers, EB, or EUV with a wavelength of 3 to 15 nm.

[0085] [The effects of the invention]

[0086] When patterning is performed using a chemically amplified resist composition containing a polymer that functions as a photoacid generator and includes repeating units of a polymer containing sulfonium salt-type monomers from the present invention, resist patterns with high contrast, good sensitivity, and excellent photolithographic properties such as EL, LWR, CDU, and DOF can be formed. Detailed Implementation

[0087] 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.

[0088] [Sulfonate type monomer]

[0089] The sulfonium salt type monomer of the present invention is represented by the following formula (A).

[0090] [Chemistry 7]

[0091]

[0092] In equation (A), p is 1, 2 or 3.

[0093] In formula (A), n1 is 0 or 1. When n1 is 0, it is a benzene ring; when n1 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with n1 = 0. n2 is 1 or 2. Considering the availability of raw materials, n2 is preferably 1. n3 is 0, 1, 2, or 3. Considering the availability of raw materials, n3 is preferably 0, 1, or 2. However, when n1 is 0, 1 ≤ n2 + n3 ≤ 5; when n1 is 1, 1 ≤ n2 + n3 ≤ 7.

[0094] In formula (A), R 1The halogen atom, nitro group, hydroxyl group, carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxycarbonyl group with 2 to 20 carbon atoms containing heteroatoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. The hydrocarbon group, hydrocarbon oxy group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl; alkenyl groups with 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclohexenyl; aryl groups with 6 to 20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7 to 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. When n3 is 2 or 3, each R... 1 They can be the same or different. Also, when n3 is 2 or 3, multiple R... 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings.

[0095] In formula (A), R 2 It is a hydrocarbon group with 1 to 30 carbon atoms, which may also contain heteroatoms. When p is 1, there are 2 R groups. 2 They can be the same or different.

[0096] R 2 Specific examples of halogen atoms that can be represented include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0097] R 2The 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, norcamphenyl, 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 may 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 may 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, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0098] Furthermore, the bond is to S + Two of the three substituents can also bond to each other and form a ring together with the sulfur atom they are bonded to. Specific examples of the aforementioned ring structure can be shown in the following formulas, etc.

[0099] [Chemistry 8]

[0100]

[0101] In the formula, the dashed lines represent atomic bonds.

[0102] The sulfonium salt type monomer represented by formula (A) should preferably be represented by the following formula (A1).

[0103] [Chemistry 9]

[0104]

[0105] In the formula, p, n1~n3 and R 1 Same as above. Z - As will be described later.

[0106] In formula (A1), n4 is 0 or 1. When n4 is 0, it is a benzene ring; when n4 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with n4 of 0. n5 is 0, 1, 2, 3, 4, or 5. Considering the availability of raw materials, n5 is preferably 0, 1, or 2.

[0107] In equation (A1), R 3The group may contain a halogen atom, nitro group, hydroxyl group, carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxycarbonyl group with 2 to 20 carbon atoms containing heteroatoms. The hydrocarbon group, hydrocarbon oxy group, and hydrocarbon thio group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 1 Examples of hydrocarbon groups are similar, but not limited to. When n5 is 2, 3, 4, or 5, each R 3 They can be the same or different, 2 Rs 3 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0108] Specific examples of cations of sulfonium salt type monomers represented by formula (A) are listed below, but are not limited thereto.

[0109] [Chemistry 10]

[0110]

[0111] [Chemistry 11]

[0112]

[0113] [Chemistry 12]

[0114]

[0115] [Chemistry 13]

[0116]

[0117] [Chemistry 14]

[0118]

[0119] [Chemistry 15]

[0120]

[0121] [Chemistry 16]

[0122]

[0123] [Chemistry 17]

[0124]

[0125] [Chemistry 18]

[0126]

[0127] [Chemistry 19]

[0128]

[0129] [Chemistry 20]

[0130]

[0131] [Chemistry 21]

[0132]

[0133] [Chemistry 22]

[0134]

[0135] [Chemistry 23]

[0136]

[0137] [Chemistry 24]

[0138]

[0139] [Chemistry 25]

[0140]

[0141] [Chemistry 26]

[0142]

[0143] [Chemistry 27]

[0144]

[0145] [Chemistry 28]

[0146]

[0147] [Chemistry 29]

[0148]

[0149] In formula (A), Z - It is an aromatic sulfonate anion having an aromatic vinyl structure. The aforementioned aromatic sulfonate anion is preferably represented by the following formula (Z).

[0150] [Chemistry 30]

[0151]

[0152] In formula (Z), 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, it is preferable to have a benzene ring with m1 = 0. m2 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, m2 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred, and 0 or 1 being even more preferred. m3 is 0, 1, 2, or 3.

[0153] In formula (Z), m4 is 0 or 1. When m4 is 0, it is a benzene ring; when m4 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with m4 of 0. m5 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, m5 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more desirable. m6 is 0, 1, 2, or 3.

[0154] In formula (Z), m7 is 0 or 1. When m7 is 0, it is a benzene ring; when m7 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with m7 = 0. m8 is 1, 2, 3, or 4. Considering the availability of raw materials, m8 is preferably 1, 2, or 3, with 1 or 2 being more desirable. m9 is 0, 1, 2, or 3.

[0155] In formula (Z), m10 is 0 or 1. When m10 is 0, it is a benzene ring; when m10 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with m10 of 0. m11 is 0, 1, 2, 3, or 4. m12 is 0, 1, 2, or 3.

[0156] In equation (Z), m13 is 0 or 1. m14 is 0 or 1.

[0157] In equation (Z), m15 is either 0 or 1. Considering the structural changes, m15 should ideally be 1.

[0158] However, when m1 is 0, the order is 0 ≤ m2 + m3 + m14 ≤ 4; when m1 is 1, the order is 0 ≤ m2 + m3 + m14 ≤ 6. When m4 is 0, the order is 0 ≤ m5 + m6 ≤ 4; when m4 is 1, the order is 0 ≤ m5 + m6 ≤ 6. When m7 is 0, the order is 0 ≤ m8 + m9 ≤ 5; when m7 is 1, the order is 0 ≤ m8 + m9 ≤ 7. When m10 is 0, the order is 0 ≤ m11 + m12 ≤ 4; when m10 is 1, the order is 0 ≤ m11 + m12 ≤ 6. Furthermore, regarding the number of iodine atoms in the anion, a higher number of iodine atoms results in higher absorption, especially for EUV. However, there is a concern that this may lead to reduced solvent solubility and precipitation in the resist composition; therefore, the order should ideally be 1 ≤ m2 + m5 + m8 ≤ 4.

[0159] In equation (Z), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R A It is preferable to have a hydrogen atom or a methyl group, with a hydrogen atom being better.

[0160] In equation (Z), R 11The halogen atom other than iodine, nitro, cyano, hydroxyl, carboxyl, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxycarbonyl group with 2 to 20 carbon atoms containing heteroatoms. The halogen atom other than iodine is preferably a fluorine, chlorine, or bromine atom, with fluorine being more preferred. The hydrocarbon group, hydrocarbon oxy group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclohexenyl; aryl groups with 6 to 20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them. 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 ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. When m3 is 2 or 3, each R... 11 They can be the same or different.

[0161] Furthermore, when m3 is 2 or 3, there are 2 R... 11 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 rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, adamantane rings, 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.

[0162] In equation (Z), R12 The halogen atom can be any halogen group other than iodine, such as nitro, cyano, hydroxyl, or carboxyl. It can also contain a hydrocarbon group with 1 to 20 carbon atoms (or a hydrocarbon oxy group with 1 to 20 carbon atoms), a hydrocarbon thio group with 1 to 20 carbon atoms (or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms), or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms. Specific examples of halogen atoms other than iodine include fluorine, chlorine, and bromine atoms. The hydrocarbon group, hydrocarbon oxy group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 11 Examples of hydrocarbon groups are similar, but not limited to. When m6 is 2 or 3, each R 12 They can be the same or different.

[0163] Also, when m6 is 2 or 3, there are 2 Rs. 12 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings.

[0164] In equation (Z), R 13 The halogen atom can be any halogen group other than iodine, such as nitro, cyano, hydroxyl, or carboxyl. It can also contain a hydrocarbon group with 1 to 20 carbon atoms (or a hydrocarbon oxy group with 1 to 20 carbon atoms), a hydrocarbon thio group with 1 to 20 carbon atoms (or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms), or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms. Specific examples of halogen atoms other than iodine include fluorine, chlorine, and bromine atoms. The hydrocarbon group, hydrocarbon oxy group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 11 Examples of hydrocarbon groups are similar, but not limited to. When m9 is 2 or 3, each R 13 They can be the same or different.

[0165] Also, when m9 is 2 or 3, there are 2 Rs. 13 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings.

[0166] In equation (Z), R 14 The halogen atom can be any halogen atom other than fluorine or iodine, a nitro group, a hydroxyl group, or 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. Specific examples of halogen atoms other than fluorine and iodine atoms include chlorine atoms, bromine atoms, etc. The hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 11Examples of hydrocarbon groups are similar, but not limited to. When m12 is 2 or 3, each R 14 They can be the same or different.

[0167] Furthermore, when m12 is 2 or 3, there are 2 R... 14 They can also bond to each other and form rings together with the carbon atoms they are bonded to. The aforementioned rings are preferably 5- to 8-membered rings.

[0168] In equation (Z), R F It can be a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, it is preferable to be a fluorine atom, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio, with fluorine being more preferred. When m11 is 2, 3, or 4, each R... F They can be the same or different.

[0169] In formula (Z), L A L B L C L D and L E These can be independently identified as single bonds, ether bonds, ester bonds, sulfonate bonds, amide 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 ether bonds, ester bonds, or sulfonate bonds being preferred. B The bonds should ideally be single bonds, ether bonds, ester bonds, amide bonds, sulfonamide bonds, or sulfonate bonds, with ester bonds or sulfonate bonds being more preferred. C The bonds should ideally be single bonds, ether bonds, ester bonds, amide bonds, or sulfonate bonds, with single bonds, ether bonds, or ester bonds being preferred. D The bonds should ideally be single bonds, ether bonds, ester bonds, amide bonds, or sulfonate bonds, with single bonds, ether bonds, or ester bonds being preferred. E It is preferable to have single bonds, ether bonds, ester bonds, or sulfonate bonds, with single bonds, ether bonds, or ester bonds being more preferred.

[0170] When m14 is 1, L A and L B It is advisable to bond to adjacent carbon atoms on the aromatic ring. In this case, the substituents containing the fluorosulfonate anion structure and the substituents containing the aromatic ring replaced by the iodine atom will be located closer in space, so higher sensitivity can be expected.

[0171] In formula (Z), X L1 and X L2 Each is an alkylene group consisting of 1 to 40 carbon atoms, which may be a single bond or contain heteroatoms. The aforementioned alkylene groups can be linear, branched, or cyclic; specific examples include alkyldiyl groups, cyclic saturated alkylene groups, and arylene groups. Specific examples of the aforementioned heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0172] X L1 and X L2 Specific examples of hydrocarbon groups containing 1 to 40 carbon atoms, which may also contain heteroatoms, are shown below, but are not limited to these. Additionally, in the following formula, * represents L and L respectively. A and L C or L B and L D Atomic bonds.

[0173] [Chemistry 31]

[0174]

[0175] [Chemistry 32]

[0176]

[0177] [Chemistry 33]

[0178]

[0179] [Chemistry 34]

[0180]

[0181] Among them, X is the most suitable. L -0~X L -22, X L -29~X L -34, and X L -47~X L -58.

[0182] However, in equation (Z), m13 and m14 will not both be 0 at the same time, L A L B L C L D X L1 and X L2 It cannot be a single key at the same time.

[0183] Z - Specific examples of anions can be listed below, but are not limited to. 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.

[0184] [Chemistry 35]

[0185]

[0186] [Chemistry 36]

[0187]

[0188] [Chemistry 37]

[0189]

[0190] [Chemistry 38]

[0191]

[0192] [Chemistry 39]

[0193]

[0194] [Chemistry 40]

[0195]

[0196] [Chemistry 41]

[0197]

[0198] [Chemistry 42]

[0199]

[0200] [Chemistry 43]

[0201]

[0202] [Chemistry 44]

[0203]

[0204] [Chemistry 45]

[0205]

[0206] [Chemistry 46]

[0207]

[0208] [Chemistry 47]

[0209]

[0210] [Chemistry 48]

[0211]

[0212] [Chemistry 49]

[0213]

[0214] [Transformation 50]

[0215]

[0216] [Chemistry 51]

[0217]

[0218] [Chemistry 52]

[0219]

[0220] [Chemistry 53]

[0221]

[0222] [Chemistry 54]

[0223]

[0224] [Chemistry 55]

[0225]

[0226] [Chemistry 56]

[0227]

[0228] [Chemistry 57]

[0229]

[0230] [Chem.58]

[0231]

[0232] [Chemistry 59]

[0233]

[0234] [Transformation 60]

[0235]

[0236] [Chemistry 61]

[0237]

[0238] [Chemistry 62]

[0239]

[0240] [Chemistry 63]

[0241]

[0242] [Chemistry 64]

[0243]

[0244] [Chemistry 65]

[0245]

[0246] [Chemistry 66]

[0247]

[0248] [Chemistry 67]

[0249]

[0250] [Chemistry 68]

[0251]

[0252] [Chemistry 69]

[0253]

[0254] [Chemistry 70]

[0255]

[0256] [Chemistry 71]

[0257]

[0258] [Chemistry 72]

[0259]

[0260] [Chemistry 73]

[0261]

[0262] [Chemistry 74]

[0263]

[0264] [Chemistry 75]

[0265]

[0266] [Chemistry 76]

[0267]

[0268] [Chemistry 77]

[0269]

[0270] [Chemistry 78]

[0271]

[0272] [Chemistry 79]

[0273]

[0274] [Chemistry 80]

[0275]

[0276] [Chemistry 81]

[0277]

[0278] [Chemistry 82]

[0279]

[0280] [Chemistry 83]

[0281]

[0282] [Chemistry 84]

[0283]

[0284] [Chemistry 85]

[0285]

[0286] [Chemistry 86]

[0287]

[0288] [Chemistry 87]

[0289]

[0290] [Chemistry 88]

[0291]

[0292] [Chemistry 89]

[0293]

[0294] [Chemistry 90]

[0295]

[0296] [Chemistry 91]

[0297]

[0298] [Chemistry 92]

[0299]

[0300] [Chemistry 93]

[0301]

[0302] [Chemistry 94]

[0303]

[0304] [Chem. 95]

[0305]

[0306] [Chemistry 96]

[0307]

[0308] [Chemistry 97]

[0309]

[0310] [Chem. 98]

[0311]

[0312] [Chemistry 99]

[0313]

[0314] [Chemistry 100]

[0315]

[0316] [Chemistry 101]

[0317]

[0318] [Chemistry 102]

[0319]

[0320] [Chemistry 103]

[0321]

[0322] [Chemistry 104]

[0323]

[0324] [Chemistry 105]

[0325]

[0326] [Chemistry 106]

[0327]

[0328] [Chemistry 107]

[0329]

[0330] [Chemistry 108]

[0331]

[0332] [Chemistry 109]

[0333]

[0334] [Chemical 110]

[0335]

[0336] [Chemistry 111]

[0337]

[0338] [Chemistry 112]

[0339]

[0340] [Chemistry 113]

[0341]

[0342] [Chemistry 114]

[0343]

[0344] [Chemistry 115]

[0345]

[0346] [Chemistry 116]

[0347]

[0348] [Chemistry 117]

[0349]

[0350] [Chemistry 118]

[0351]

[0352] [Chemistry 119]

[0353]

[0354] [Chemistry 120]

[0355]

[0356] [Chemistry 121]

[0357]

[0358] [Chemistry 122]

[0359]

[0360] [Chemistry 123]

[0361]

[0362] [Chemistry 124]

[0363]

[0364] [Chemistry 125]

[0365]

[0366] [Chemistry 126]

[0367]

[0368] [Chemistry 127]

[0369]

[0370] [Chemistry 128]

[0371]

[0372] [Chemistry 129]

[0373]

[0374] [Chemistry 130]

[0375]

[0376] [Chemistry 131]

[0377]

[0378] [Chemistry 132]

[0379]

[0380] [Chemistry 133]

[0381]

[0382] [Chemistry 134]

[0383]

[0384] [Chemistry 135]

[0385]

[0386] [Chemistry 136]

[0387]

[0388] [Chemistry 137]

[0389]

[0390] [Chemistry 138]

[0391]

[0392] [Chemistry 139]

[0393]

[0394] [Chemistry 140]

[0395]

[0396] [Chemistry 141]

[0397]

[0398] [Chemistry 142]

[0399]

[0400] [Chemistry 143]

[0401]

[0402] [Chemistry 144]

[0403]

[0404] [Chemistry 145]

[0405]

[0406] [Chemistry 146]

[0407]

[0408] [Chemistry 147]

[0409]

[0410] [Chemistry 148]

[0411]

[0412] [Chemistry 149]

[0413]

[0414] [Chemistry 150]

[0415]

[0416] [Chemistry 151]

[0417]

[0418] [Chemistry 152]

[0419]

[0420] [Chemistry 153]

[0421]

[0422] [Chemistry 154]

[0423]

[0424] [Chemistry 155]

[0425]

[0426] [Chemistry 156]

[0427]

[0428] [Chemistry 157]

[0429]

[0430] [Chemistry 158]

[0431]

[0432] [Chemistry 159]

[0433]

[0434] [Chemistry 160]

[0435]

[0436] [Chemistry 161]

[0437]

[0438] [Chemistry 162]

[0439]

[0440] [Chemistry 163]

[0441]

[0442] [Chemistry 164]

[0443]

[0444] [Chemistry 165]

[0445]

[0446] [Chemistry 166]

[0447]

[0448] [Chemistry 167]

[0449]

[0450] [Chemistry 168]

[0451]

[0452] [Chemistry 169]

[0453]

[0454] [Chemistry 170]

[0455]

[0456] [Chemistry 171]

[0457]

[0458] [Chemistry 172]

[0459]

[0460] [Chemistry 173]

[0461]

[0462] [Chemistry 174]

[0463]

[0464] [Chemistry 175]

[0465]

[0466] [Chemistry 176]

[0467]

[0468] [Chemistry 177]

[0469]

[0470] [Chemistry 178]

[0471]

[0472] [Chemistry 179]

[0473]

[0474] [Chemistry 180]

[0475]

[0476] [Chemistry 181]

[0477]

[0478] [Chemistry 182]

[0479]

[0480] [Chemistry 183]

[0481]

[0482] [Chemistry 184]

[0483]

[0484] [Chemistry 185]

[0485]

[0486] [Chemistry 186]

[0487]

[0488] [Chemistry 187]

[0489]

[0490] [Chem.188]

[0491]

[0492] [Chemistry 189]

[0493]

[0494] [Chemistry 190]

[0495]

[0496] [Chemistry 191]

[0497]

[0498] [Chemistry 192]

[0499]

[0500] [Chemistry 193]

[0501]

[0502] [Chemistry 194]

[0503]

[0504] [Chemistry 195]

[0505]

[0506] [Chemistry 196]

[0507]

[0508] [Chemistry 197]

[0509]

[0510] [Chemistry 198]

[0511]

[0512] [Chemistry 199]

[0513]

[0514] [Chem.200]

[0515]

[0516] [Chemical Engineering 201]

[0517]

[0518] [Chemical Engineering 202]

[0519]

[0520] [Chemical Engineering 203]

[0521]

[0522] [Chemical 204]

[0523]

[0524] [Chemical Engineering 205]

[0525]

[0526] [Chemical Engineering 206]

[0527]

[0528] [Chemical 207]

[0529]

[0530] [Chemical Engineering 208]

[0531]

[0532] [Chemical Engineering 209]

[0533]

[0534] [Chemical 210]

[0535]

[0536] [Chemistry 211]

[0537]

[0538] [Chemistry 212]

[0539]

[0540] [Chemistry 213]

[0541]

[0542] [Chemistry 214]

[0543]

[0544] [Chemical 215]

[0545]

[0546] [Chemistry 216]

[0547]

[0548] [Chemistry 217]

[0549]

[0550] [Chemistry 218]

[0551]

[0552] [Chemistry 219]

[0553]

[0554] [Chem.220]

[0555]

[0556] [Chemistry 221]

[0557]

[0558] [Chemistry 222]

[0559]

[0560] [Chemistry 223]

[0561]

[0562] [Chemistry 224]

[0563]

[0564] [Chemistry 225]

[0565]

[0566] [Chemistry 226]

[0567]

[0568] [Chemistry 227]

[0569]

[0570] [Chemistry 228]

[0571]

[0572] [Chemistry 229]

[0573]

[0574] [Chemistry 230]

[0575]

[0576] [Chemistry 231]

[0577]

[0578] [Chemistry 232]

[0579]

[0580] [Chemistry 233]

[0581]

[0582] [Chemistry 234]

[0583]

[0584] [Chemistry 235]

[0585]

[0586] [Chemistry 236]

[0587]

[0588] [Chemistry 237]

[0589]

[0590] [Chemistry 238]

[0591]

[0592] [Chemistry 239]

[0593]

[0594] [Chemistry 240]

[0595]

[0596] [Chemistry 241]

[0597]

[0598] [Chemistry 242]

[0599]

[0600] [Chemistry 243]

[0601]

[0602] [Chemistry 244]

[0603]

[0604] [Chemistry 245]

[0605]

[0606] [Chemistry 246]

[0607]

[0608] [Chemistry 247]

[0609]

[0610] [Chemistry 248]

[0611]

[0612] [Chemistry 249]

[0613]

[0614] [Chemistry 250]

[0615]

[0616] [Chemistry 251]

[0617]

[0618] [Chemistry 252]

[0619]

[0620] [Chemistry 253]

[0621]

[0622] [Chemistry 254]

[0623]

[0624] [Chemistry 255]

[0625]

[0626] [Chemistry 256]

[0627]

[0628] [Chemistry 257]

[0629]

[0630] [Chemistry 258]

[0631]

[0632] [Chemistry 259]

[0633]

[0634] [Chemistry 260]

[0635]

[0636] [Chemistry 261]

[0637]

[0638] [Chemistry 262]

[0639]

[0640] [Chemistry 263]

[0641]

[0642] [Chemistry 264]

[0643]

[0644] [Chemistry 265]

[0645]

[0646] [Chemistry 266]

[0647]

[0648] [Chemistry 267]

[0649]

[0650] [Chemistry 268]

[0651]

[0652] [Chemistry 269]

[0653]

[0654] [Chemistry 270]

[0655]

[0656] [Chemistry 271]

[0657]

[0658] [Chemistry 272]

[0659]

[0660] [Chemistry 273]

[0661]

[0662] [Chemistry 274]

[0663]

[0664] [Chemistry 275]

[0665]

[0666] [Chemistry 276]

[0667]

[0668] [Chemistry 277]

[0669]

[0670] [Chemistry 278]

[0671]

[0672] [Chemistry 279]

[0673]

[0674] The specific structure of the sulfonium salt type monomer of the present invention can be listed as any combination of the aforementioned anions and cations.

[0675] The sulfonium salt type monomer of the present invention can be synthesized using known methods. For example, a sulfonium salt containing the aforementioned sulfonium cation can first be synthesized using the synthesis method described in ARKIVOC (Gainesville, FL, United States) (2022), (7), 7-18. Then, the synthesized sulfonium salt can be converted into the desired sulfonium salt by performing a salt exchange reaction with the corresponding anion. The salt exchange with the corresponding anion can be easily carried out using known methods, for example, see Japanese Patent Application Publication No. 2007-145797.

[0676] Furthermore, the aforementioned manufacturing method is merely one example, and the manufacturing method of the matte salt of the present invention is not limited thereto.

[0677] The structural features of the sulfonate-type monomer of the present invention can be listed as follows: it has an aromatic vinyl structure as a polymerizable group and an aromatic sulfonate anion structure with an iodine atom, while the cyano group is bonded to the aromatic ring of the sulfonate cation. The aromatic sulfonate anion structure is more rigid and has less acid diffusion than the alkyl sulfonate anion structure. Regarding the iodine atom, especially in EUV lithography at a wavelength of 13.5 nm, the EUV absorption of the iodine atom is very large, thus generating secondary electrons from the iodine atom during exposure. Because the sulfonate-type monomer of the present invention has a polymerizable group in the anionic portion, the polymer of the present invention obtained using it becomes an anionic bonded acid generator with the anionic side bonded to the polymer backbone. That is, it generates acid bonded to the polymer backbone, thus suppressing the diffusion of the generated acid. Furthermore, the polymerizable groups, especially those composed of styrene and vinylnaphthalene structures, are more rigid than polymerizable groups such as methacrylates, and improve the glass transition temperature (Tg) of the polymer. It is believed that aromatic rings within or between polymers interact (π-π stacking effect), resulting in a regular arrangement of polymers. This arrangement also exhibits resistance to pattern collapse in the developer during the formation of fine patterns. Furthermore, the etching step following the formation of fine patterns also exhibits excellent etching resistance due to the aromatic rings directly bonded to the main chain. On the other hand, the cyano group substituted on the aromatic ring of the sulfonium cation is known as a strong electron-withdrawing group. Based on this, it is believed that the energy level of the lowest unoccupied molecular orbital in Frontier orbital theory is lowered. Therefore, it becomes easier to accept secondary electrons generated from the iodine atom in the anion, promoting the decomposition of the cation and efficiently generating acid. Moreover, since the nitrogen atom of the cyano group has a lone pair of electrons, it can interact with the protons of the generated acid and is expected to function as an acid diffusion inhibitor. These synergistic effects result in high sensitivity, prevent resolution degradation caused by acid diffusion, and improve LWR and CDU. Therefore, the polymer of the present invention is particularly ideal as a material for chemically amplified positive resist compositions.

[0678] [polymer]

[0679] The polymer of the present invention contains repeating units (hereinafter also referred to as repeating unit A) derived from sulfonium salt monomers represented by formula (A).

[0680] The aforementioned polymer may also contain repeating units represented by formula (a1) (hereinafter also referred to as repeating unit a1) or repeating units represented by formula (a2) (hereinafter also referred to as repeating unit a2).

[0681] [Chemistry 280]

[0682]

[0683] In equations (a1) and (a2), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0684] In equation (a1), X 1 It is a single bond, phenylene, naphthylene, or *-C(=O)-OX 11 - and the phenylene or naphthylene group may also be replaced by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, or a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom. X 11 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbon 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.

[0685] In equation (a2), X 2 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain. R 21 It can be a halogen atom, cyano group, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. a1 is 0, 1, 2, 3, or 4, and preferably 0 or 1. When a1 is 2, 3, or 4, each R... 21 They can be the same or different.

[0686] In equations (a1) and (a2), AL 1 and AL 2 Each of these groups is an acid-indestructible group independently. Specific examples of the aforementioned acid-indestructible groups can be cited, for example, those described in Japanese Patent Application Publication No. 2013-80033 and Japanese Patent Application Publication No. 2013-83821.

[0687] For representativeness, specific examples of the aforementioned acid-instable groups can be listed as those represented by formulas (AL-1) to (AL-3).

[0688] [Chemistry 281]

[0689]

[0690] In the formula, * represents an atomic bond.

[0691] In equations (AL-1) and (AL-2), R L1 and R L2Each hydrocarbon group is independently composed of 1 to 40 carbon atoms and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Preferably, the aforementioned hydrocarbon groups have 1 to 20 carbon atoms.

[0692] In formula (AL-1), a2 is an integer from 0 to 10, and preferably 1, 2, 3, 4 or 5.

[0693] In equation (AL-2), R L3 and R L4 Each group is independently composed of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Preferably, the aforementioned hydrocarbon groups have 1 to 20 carbon atoms. Furthermore, R... L2 R L3 and R L4 Any two atoms can also bond to each other and together with the carbon atoms they are bonded to, or carbon atoms and oxygen atoms, form a ring with 3 to 20 carbon atoms. The aforementioned ring is preferably a ring with 4 to 16 carbon atoms, and an alicyclic ring is particularly preferred.

[0694] In equation (AL-3), R L5 R L6 and R L7 Each hydrocarbon group is independently composed of 1 to 20 carbon atoms and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Preferably, the aforementioned hydrocarbon groups have 1 to 20 carbon atoms. Furthermore, R... L5 R L6 and R L7 Any two atoms can also bond to each other and together with the carbon atoms they are bonded to form a ring with 3 to 20 carbon atoms. The aforementioned ring is preferably a ring with 4 to 16 carbon atoms, and an alicyclic ring is particularly preferred.

[0695] Specific examples of repeated unit a1 can be listed below, but are not limited to these. Additionally, in the following formula, R... A and AL 1 Same as above.

[0696] [Chemistry 282]

[0697]

[0698] [Chemistry 283]

[0699]

[0700] [Chemistry 284]

[0701]

[0702] [Chemistry 285]

[0703]

[0704] Specific examples of repeated unit a2 can be listed below, but are not limited to these. Additionally, in the following formula, R... A and AL 2 Same as above.

[0705] [Chemistry 286]

[0706]

[0707] [Chemistry 287]

[0708]

[0709] [Chemistry 288]

[0710]

[0711] The aforementioned polymer may also contain repeating units represented by the following formula (a3) ​​(hereinafter also referred to as repeating unit a3).

[0712] [Chemistry 289]

[0713]

[0714] In formula (a3), b1 is 0 or 1. When b1 is 0, it is a benzene ring; when b1 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with b1 = 0. b2 is 0, 1, 2, or 3 when b1 is 0, and 0, 1, 2, 3, 4, or 5 when b1 is 1. Considering the availability of raw materials, b2 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more desirable.

[0715] In equation (a3), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Among these, hydrogen atom or methyl group are preferred, with hydrogen atom being even more desirable.

[0716] In equation (a3), X 3 The bonds are single bonds, *-C(=O)-O-, or *-C(=O)-NH-. * indicates an atomic bond with a carbon atom in the main chain. Among these, single bonds and *-C(=O)-O- are preferred, with single bonds being even better.

[0717] In equation (a3), X 4 It can be a single bond, an aliphatic alkylene group with 1 to 4 carbon atoms, a carbonyl group, a sulfonyl group, or a combination thereof. Among these, considering the availability of raw materials, a single bond, a carbonyl group, or a sulfonyl group is preferable; considering the polar groups generated after the reaction, a single bond or a carbonyl group is more preferred.

[0718] In equation (a3), X 5 and X 6 Each can be independently an oxygen atom or a sulfur atom. However, X 4 and X 6 Adjacent carbon atoms bonded to an aromatic ring. X 5 and X 6 They can be the same or different; considering the perspective of reactivity, X 5 and X 6 All of them should be oxygen atoms.

[0719] In equation (a3), R 22 and R 23 Each hydrocarbon group consists of 1 to 20 carbon atoms, which may be hydrogen atoms or may contain heteroatoms. The aforementioned hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclohexenyl; aryl groups with 6 to 20 carbon atoms, such as phenyl and naphthyl; aralkyl groups with 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them. 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, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0720] Also, R 22 and R 23They 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 rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, adamantane rings, 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.

[0721] In equation (a3), R 24 It can be a halogen atom, hydroxyl group, cyano group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; or a hydrocarbon thio group or -N(R) group with 1 to 20 carbon atoms containing heteroatoms. 24A (R) 24B R 24A and R 24B Each halogen atom is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The aforementioned halogen atom is preferably a fluorine, chlorine, bromine, or iodine atom, with fluorine or iodine being more preferred. The hydrocarbon group, as well as the hydrocarbon oxy group, hydrocarbon oxycarbonyl group, and hydrocarbon thio group, can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R. 22 and R 23 The same example applies to hydrocarbon groups. 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, or 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, or nitrogen atoms. This results in the possible inclusion of hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulopentazone, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. When b2 is 2 or more, each R... 24 They can be the same or different.

[0722] Furthermore, when b2 is 2 or more, multiple R 24They can also bond with each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. Specific examples of rings formed in this case include: cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, adamantane rings, 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.

[0723] Specific examples of repeated unit a3 can be listed below, but are not limited to these. 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.

[0724] [Chemistry 290]

[0725]

[0726] [Chemistry 291]

[0727]

[0728] [Chemistry 292]

[0729]

[0730] [Chemistry 293]

[0731]

[0732] [Chemistry 294]

[0733]

[0734] [Chemistry 295]

[0735]

[0736] [Chemistry 296]

[0737]

[0738] [Chemistry 297]

[0739]

[0740] [Chemistry 298]

[0741]

[0742] [Chemistry 299]

[0743]

[0744] [Chemical 300]

[0745]

[0746] [Chemical Engineering 301]

[0747]

[0748] [Chemical 302]

[0749]

[0750] [Chemical 303]

[0751]

[0752] [Chemical 304]

[0753]

[0754] [Chemical 305]

[0755]

[0756] [Chemical 306]

[0757]

[0758] [Chemical 307]

[0759]

[0760] [Chemical 308]

[0761]

[0762] [Chemical 309]

[0763]

[0764] [Chemical 310]

[0765]

[0766] [Chemistry 311]

[0767]

[0768] [Chemistry 312]

[0769]

[0770] [Chemistry 313]

[0771]

[0772] [Chemical 314]

[0773]

[0774] [Chemical 315]

[0775]

[0776] [Chemistry 316]

[0777]

[0778] [Chemistry 317]

[0779]

[0780] [Chemistry 318]

[0781]

[0782] [Chemistry 319]

[0783]

[0784] [Chem.320]

[0785]

[0786] [Chemistry 321]

[0787]

[0788] [Chemistry 322]

[0789]

[0790] [Chemistry 323]

[0791]

[0792] [Chemistry 324]

[0793]

[0794] [Chemistry 325]

[0795]

[0796] [Chemistry 326]

[0797]

[0798] [Chemistry 327]

[0799]

[0800] [Chemistry 328]

[0801]

[0802] [Chemistry 329]

[0803]

[0804] [Chemistry 330]

[0805]

[0806] [Chemistry 331]

[0807]

[0808] [Chemistry 332]

[0809]

[0810] [Chemistry 333]

[0811]

[0812] [Chemistry 334]

[0813]

[0814] [Chemistry 335]

[0815]

[0816] [Chemistry 336]

[0817]

[0818] [Chemistry 337]

[0819]

[0820] [Chemistry 338]

[0821]

[0822] [Chemistry 339]

[0823]

[0824] The aforementioned base polymer may also contain repeating units represented by formula (b1) (hereinafter also referred to as repeating unit b1) or repeating units represented by formula (b2) (hereinafter also referred to as repeating unit b2).

[0825] [Transformation 340]

[0826]

[0827] In equations (b1) and (b2), 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. R 31 It is a hydrogen atom, or a group containing at least one of the following structures: hydroxyl group (other than phenolic hydroxyl group), cyano group, carbonyl group, carboxyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulcinolone ring, and carboxylic anhydride (-C(=O)-OC(=O)-). R 32 It can be a halogen atom, carboxyl group, nitro group, cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. When c2 is 2, 3, or 4, each R 32 They can be the same or different. c1 can be 1, 2, 3 or 4. c2 can be 0, 1, 2, 3 or 4. However, 1 ≤ c1 + c2 ≤ 5.

[0828] Specific examples of repeating unit b1 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[0829] [Chemistry 341]

[0830]

[0831] [Chemistry 342]

[0832]

[0833] [Chemistry 343]

[0834]

[0835] [Chemistry 344]

[0836]

[0837] [Chemistry 345]

[0838]

[0839] [Chemistry 346]

[0840]

[0841] [Chemistry 347]

[0842]

[0843] [Chemistry 348]

[0844]

[0845] [Chemistry 349]

[0846]

[0847] [Chemical 350]

[0848]

[0849] [Chemistry 351]

[0850]

[0851] [Chemistry 352]

[0852]

[0853] [Chemistry 353]

[0854]

[0855] [Chemistry 354]

[0856]

[0857] [Chemistry 355]

[0858]

[0859] [Chemistry 356]

[0860]

[0861] Specific examples of repeated unit b2 can be listed below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[0862] [Chemistry 357]

[0863]

[0864] [Chemistry 358]

[0865]

[0866] [Chemistry 359]

[0867]

[0868] [Hua360]

[0869]

[0870] [Chemistry 361]

[0871]

[0872] Regarding repeating units b1 or b2, in ArF lithography, those with lactone rings as polar groups are particularly suitable, while in KrF lithography, EB lithography, and EUV lithography, those with phenolic sites are suitable.

[0873] The aforementioned basic polymer may also contain repeating units (hereinafter also referred to as repeating unit c) with a structure in which hydroxyl groups are protected by acid-instable groups. If repeating unit c has a structure with one or more hydroxyl groups protected, and the protecting groups decompose and generate hydroxyl groups due to the action of acid, there are no particular restrictions, and it is preferable to be represented by the following formula (c1).

[0874] [Chemistry 362]

[0875]

[0876] In equation (c1), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 41 It can also contain heteroatoms and be a (d+1) valence hydrocarbon group with 1 to 30 carbon atoms. R 42 It is an acid-labile group. d can be 1, 2, 3, or 4.

[0877] In equation (c1), R 42 The acid-unstable group indicated is one that has been deprotected by the acid, resulting in the formation of a hydroxyl group. R 42 There are no particular restrictions on the structure, and it is preferable to have an acetal structure, a ketal structure, an alkoxy carbonyl group, or an alkoxy methyl group represented by the following formula (c2), with an alkoxy methyl group represented by the following formula (c2) being particularly preferred.

[0878] [Chem.363]

[0879]

[0880] In the formula, * represents an atomic bond. R 43 It consists of hydrocarbon groups with 1 to 15 carbon atoms.

[0881] R 42Specific examples of the acid-labile group represented, the alkoxymethyl group represented by formula (c2), and the repeating unit c can be the same examples as those exemplified in the description of the repeating unit c described in JP-A-2020-111564.

[0882] The aforementioned base polymer may also contain a repeating unit d derived from indene, benzofuran, benzothiophene, acenaphthene, chromone, coumarin, norbornadiene, or their derivatives. Specific examples of the monomer providing the repeating unit d are as shown below, but are not limited thereto.

[0883] [Chemical formula 364]

[0884]

[0885] The aforementioned base polymer may also contain a repeating unit e derived from indan, vinylpyridine, or vinylcarbazole.

[0886] In the polymer of the present invention, the content ratios of the repeating units A, a1, a2, a3, b1, b2, c, d, and e are preferably 0 < A ≤ 0.4, 0 ≤ a1 ≤ 0.8, 0 ≤ a2 ≤ 0.8, 0 ≤ a3 ≤ 0.6, 0 < a1 + a2 + a3 ≤ 0.8, 0 ≤ b1 ≤ 0.6, 0 ≤ b2 ≤ 0.6, 0 ≤ c ≤ 0.5, 0 ≤ d ≤ 0.3, and 0 ≤ e ≤ 0.3, and more preferably 0 < A ≤ 0.3, 0 ≤ a1 ≤ 0.7, 0 ≤ a2 ≤ 0.7, 0 ≤ a3 ≤ 0.5, 0 < a1 + a2 + a3 ≤ 0.7, 0 ≤ b1 ≤ 0.5, 0 ≤ b2 ≤ 0.5, 0 ≤ c ≤ 0.3, 0 ≤ d ≤ 0.3, and 0 ≤ e ≤ 0.3. However, A + a1 + a2 + a3 + b1 + b2 + c + d + e ≤ 1.0.

[0887] The weight average molecular weight (Mw) of the aforementioned polymer is preferably 1000 to 500000, and more preferably 3000 to 100000. If Mw is within this range, sufficient etching resistance can be obtained, and there is no concern about a decrease in resolution due to 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 THF or N,N-dimethylformamide (DMF) as a solvent.

[0888] In addition, regarding the molecular weight distribution (Mw / Mn) of the aforementioned polymer, as the pattern rule is miniaturized, the influence of Mw / Mn tends to become larger. Therefore, in order to obtain a resist composition that can be ideally used for fine pattern sizes, Mw / Mn is preferably a narrow dispersion of 1.0 to 2.0. If it is within the above range, there are few low molecular weight and high molecular weight polymers, and there is no concern about observing foreign substances on the pattern or deterioration of the pattern shape after exposure.

[0889] When synthesizing the aforementioned polymer, for example, the monomer that provides the aforementioned repeating unit can be polymerized by adding a free radical polymerization initiator to an organic solvent and heating it.

[0890] Specific 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). Specific examples of polymerization initiators include: 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The amount of these initiators added relative to the total amount of monomers used in polymerization should preferably be 0.01–25 mol%. The reaction temperature should preferably be 50–150 °C, preferably 60–100 °C. The reaction time should preferably be 2–24 hours, but from a production efficiency perspective, 2–12 hours is preferred.

[0891] The aforementioned polymerization initiator can be added to the monomer solution to supply the reactor, or a different initiator solution can be prepared and supplied to the reactor separately. Since there is a possibility that free radicals generated from the initiator may cause the polymerization reaction to proceed and produce ultra-high molecular weight polymers during the waiting time, from a quality management perspective, the monomer solution and initiator solution should preferably be prepared separately and added dropwise. Acid-labile groups can be used directly introduced into the monomer, or they can be protected or partially protected after polymerization. Furthermore, to adjust the molecular weight, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can 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 0.01–20 mol%.

[0892] In the case of monomers containing hydroxyl groups, the hydroxyl groups can be replaced with acetal groups such as ethoxy-ethoxy, which are easily deprotected by acids, during polymerization. After polymerization, deprotection can be carried out using weak acids and water. Alternatively, acetyl groups, formyl groups, trimethylacetyl groups, etc., can be used for replacement first, and alkaline hydrolysis can be carried out after polymerization.

[0893] When copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, hydroxystyrene or hydroxyvinylnaphthalene can be copolymerized with other monomers in an organic solvent with the addition of a free radical polymerization initiator and heated. Alternatively, acetoxystyrene or acetoxyvinylnaphthalene can be used, and after polymerization, the acetoxy groups can be deprotected by alkaline hydrolysis to obtain polyhydroxystyrene or hydroxyvinylnaphthalene.

[0894] The alkali used in alkaline hydrolysis can be ammonia, triethylamine, etc. Furthermore, the reaction temperature should preferably be -20 to 100℃, with 0 to 60℃ being more ideal. The reaction time should preferably be 0.2 to 100 hours, with 0.5 to 20 hours being more ideal.

[0895] In addition, the amount of each monomer in the aforementioned monomer solution can be appropriately set, for example, in a manner that makes it an ideal content ratio for the aforementioned repeating units.

[0896] Regarding the polymer obtained by the aforementioned manufacturing method, the reaction solution obtained by the polymerization reaction can be used as the final product, or the powder obtained by purification steps such as adding the polymer solution to a poor solvent to obtain the powder can be used as the final product. Considering the viewpoints of work efficiency and quality stabilization, it is advisable to use the polymer solution obtained by dissolving the powder obtained by the purification step into a solvent as the final product.

[0897] Specific examples of solvents used at this time can be cited from paragraphs

[0144] to

[0145] of Japanese Patent Application Publication No. 2008-111103, including ketones such as 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; and propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, and propylene glycol dimethyl ether. Ethers such as 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; alcohols such as diacetone alcohol (DAA); high-boiling-point alcohol solvents such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, and 1,3-butanediol; and their mixed solvents.

[0898] In the aforementioned polymer solution, the polymer concentration is preferably 0.01–30% by mass, and more preferably 0.1–20% by mass.

[0899] The aforementioned reaction solutions and polymer solutions should be filtered. Filtering removes foreign matter and gels that could cause defects, effectively stabilizing the quality.

[0900] The materials used in the aforementioned filters include: fluorocarbon, cellulose, nylon, polyester, and hydrocarbon-based materials. For filtration steps involving corrosion inhibitors, filters made of fluorocarbons such as Teflon (a registered trademark), polyethylene, polypropylene, or nylon are preferable. The pore size of the filter can be appropriately selected according to the target cleanliness level, preferably below 100 nm, and even better, below 20 nm. Furthermore, these filters can be used individually or in combination. The filtration method can involve passing the solution only once, but circulating the solution and performing multiple filtrations is preferable. The filtration steps can be performed during the polymer manufacturing process, in any order and number of times, preferably filtering the reaction solution after the polymerization reaction, the polymer solution, or both.

[0901] [Chemical amplification resist composition]

[0902] [(A) Basic Polymer]

[0903] The chemically amplified resist composition of the present invention contains a base polymer comprising the aforementioned polymer as component (A).

[0904] The aforementioned polymers may be used alone or in combination of two or more with different composition ratios, Mw and / or Mw / Mn. Furthermore, (A) the base polymer may include, in addition to the aforementioned polymers, hydrides of ring-opening metathesis polymers, for which the polymers described in Japanese Patent Application Publication No. 2003-66612 may be used.

[0905] [(B) Organic solvents]

[0906] The chemically amplified resist composition of the present invention may also contain an organic solvent as component (B). There are no particular limitations on whether the organic solvent in (B) 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.

[0907] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, ethyl lactate, DAA, and mixtures thereof are particularly well-soluble as the base polymer of component (A).

[0908] In the chemically amplified resist composition of the present invention, the content of (B) organic solvent relative to 80 parts by mass of (A) base polymer is preferably 200 to 7000 parts by mass, and more preferably 400 to 5000 parts by mass. (B) Organic solvent may be used alone or in combination with two or more types.

[0909] [(C) Quenching agent]

[0910] The chemically amplified resist composition of the present invention may also contain a quencher as component (C). Furthermore, in the present invention, the 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.

[0911] (C) Specific examples of quenching agents can be listed as onion salts represented by formula (1) or (2).

[0912] [Chem365]

[0913]

[0914] In equation (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 formula (2), R q2 Hydrocarbon groups consisting of 1 to 40 carbon atoms, which may also contain heteroatoms.

[0915] 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] 2,6Cyclic saturated hydrocarbon groups having 3 to 40 carbon atoms such as decyl and adamantyl; aryl groups having 6 to 40 carbon atoms such as phenyl, naphthyl, and anthryl. Further, a part or all of the hydrogen atoms of the aforementioned hydrocarbon group may also be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and a part of -CH2- of the aforementioned hydrocarbon group may also be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, it may also contain a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-O-C(=O)-), a haloalkyl group, etc.

[0916] R q2 The hydrocarbon group represented by can be specifically exemplified as R q1 As substituents of specific examples, in addition, fluorinated saturated hydrocarbon groups such as trifluoromethyl and trifluoroethyl, and fluorinated aryl groups such as pentafluorophenyl and 4-trifluoromethylphenyl can also be listed.

[0917] Specific examples of the anion of the onium salt represented by formula (1) can be listed as those shown below, but are not limited thereto.

[0918] [Chemical formula 366]

[0919]

[0920] [Chemical formula 367]

[0921]

[0922] [Chemical formula 368]

[0923]

[0924] [Chemical formula 369]

[0925]

[0926] [Chemical formula 370]

[0927]

[0928] Specific examples of the anion of the onium salt represented by formula (2) can be listed as those shown below, but are not limited thereto.

[0929] [Chemical formula 371]

[0930]

[0931] [Chemical formula 372]

[0932] [[ID=�5]]

[0933] [Chemical formula 373]

[0934]

[0935] [Chemistry 374]

[0936]

[0937] [Chemistry 375]

[0938]

[0939] In equations (1) and (2), Mq + The cation is a sulfonium cation. Examples of the aforementioned sulfonium cations include: sulfonium cations, monium cations, ammonium cations, etc. Specific examples of the aforementioned sulfonium cations include: those exemplified as sulfonium cations in formula (A), those described in paragraphs

[0102] to

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

[0044] to

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

[0035] to

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

[0940] Furthermore, the aforementioned sulfonium cation should preferably be a sulfonium cation represented by the following formula (sulfo-1).

[0941] [Chemistry 376]

[0942]

[0943] In formula (sulfo-1), e1 is 0 or 1. When e1 is 0, it is a benzene ring; when e1 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with e1 = 0. e2 is 0 or 1. When e2 is 0, it is a benzene ring; when e2 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with e2 = 0. e3 is 0 or 1. When e3 is 0, it is a benzene ring; when e3 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with e3 = 0.

[0944] In formula (sulfo-1), e4 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption of EUV, but the solvent solubility becomes less and there is a concern about precipitation in the resist composition. Therefore, e4 should preferably be 0, 1, 2, or 3, with 0, 1, or 2 being better.

[0945] In formula (sulfo-1), e5 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, e5 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred. e6 is 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, e6 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred. e7 is 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, e7 is preferably 0, 1, 2, or 3, with 0, 1, or 2 being more preferred.

[0946] In formula (sulfo-1), e8 is 0, 1, or 2. From the perspective of raw material availability, e8 is preferably 0 or 1. e9 is 0, 1, or 2. From the perspective of raw material availability, e9 is preferably 0 or 1. e10 is 0, 1, or 2. From the perspective of raw material availability, e10 is preferably 0 or 1.

[0947] In formula (sulfo-1), e11 is 0 or 1. When e11 is 0, it is a benzene ring; when e11 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with e11 of 0.

[0948] In formula (sulfo-1), e12 is 0, 1, 2, 3, or 4. The more iodine atoms in the cationic structure, the higher the absorption of EUV, but the solvent solubility becomes less and there is a concern about precipitation in the resist composition. Therefore, e12 should preferably be 0, 1, 2, or 3, with 0, 1, or 2 being better.

[0949] In formula (sulfo-1), e13 is 0, 1, or 2. From the perspective of raw material availability, e13 is preferably 0 or 1. e14 is 0, 1, or 2. From a synthetic perspective, e14 is preferably 0 or 1.

[0950] However, when e1 is 0, the condition is 0 ≤ e6 + e9 ≤ 4; when e1 is 1, the condition is 0 ≤ e6 + e9 ≤ 6. When e2 is 0, the condition is 0 ≤ e7 + e10 ≤ 4; when e2 is 1, the condition is 0 ≤ e7 + e10 ≤ 6. When e3 is 0, the condition is 1 ≤ e4 + e5 + e8 + e14 ≤ 4; when e3 is 1, the condition is 1 ≤ e4 + e5 + e8 + e14 ≤ 6. When e11 is 0, the condition is 0 ≤ e12 + e13 ≤ 4; when e11 is 1, the condition is 0 ≤ e12 + e13 ≤ 6. Also, e4 + e12 ≥ 1.

[0951] In formula (sulfo-1), R F1 ~R F3 Each of these can be independently composed of a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, trifluoromethyl, trifluoromethoxy, and trifluorothiomethoxy are preferred. When e5 is 2, 3, or 4, each R... F1 They can be the same or different. When e6 is 2, 3, 4, 5 or 6, each R... F2They can be the same or different. When e7 is 2, 3, 4, 5 or 6, each R... F3 They can be the same or different.

[0952] In formula (sulfo-1), R q11 ~R q14 The group 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 (which may also contain heteroatoms), a hydrocarbon oxygen group with 1 to 20 carbon atoms (which may also contain heteroatoms), or a hydrocarbon thio group with 1 to 20 carbon atoms (which may also contain heteroatoms). The hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given and illustrated in the description of formula (A) as R. 1 The same example applies to the hydrocarbon group. Furthermore, some or all of the hydrogen atoms in the hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon sulfide 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 in 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.

[0953] Also, when e8 is 2, there are 2 Rs. q11 They can be the same or different, 2 Rs q11 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When e9 is 2, there are 2 R atoms. q12 They can be the same or different, 2 Rs q12 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When e10 is 2, the two R atoms... q13 They can be the same or different, 2 Rs q13 They can also bond to each other and form rings together with the carbon atoms they are bonded to. When e13 is 2, there are 2 R atoms. q14 They can be the same or different, 2 Rs q14They 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 rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, adamantane rings, 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.

[0954] Furthermore, S is directly bonded to the sulfonium cation represented by formula (sulfo-1). + 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 exemplified by the following formulas, etc.

[0955] [Chemistry 377]

[0956]

[0957] In the formula, the dashed lines represent atomic bonds.

[0958] In formula (sulfo-1), L F and L G 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... F The bonds should ideally be single bonds, ether bonds, ester bonds, or sulfonate bonds, with ester bonds or sulfonate bonds being preferred. G It is preferable to have a single bond, ether bond, or ester bond, with a single bond being better.

[0959] In formula (sulfo-1), X L3 It is a single-bonded, or possibly heteroatom-containing, 1-40 carbon-membered alkylene group. The aforementioned alkylene group can be linear, branched, or cyclic; specific examples include: alkyldiyl, cyclic saturated alkylene groups, arylene groups, etc. Specific examples of the aforementioned heteroatom include: oxygen atoms, nitrogen atoms, sulfur atoms, etc. L3 Specific examples of hydrocarbon groups with 1 to 40 carbon atoms that may also contain heteroatoms can be illustrated as X in the description of formula (Z). L1 and X L2 The example X may also contain a heteroatom-containing hydrocarbon group with 1 to 40 carbon atoms. L -0~X L -58. Among them, X L3 It is advisable to be X L -0~X L-22, X L -29~X L -34 and X L -47~X L -58.

[0960] The sulfonium cation represented by formula (sulfo-1) should preferably be represented by formula (sulfo-1-1).

[0961] [Chemistry 378]

[0962]

[0963] In the formula, e4~e10, e12~e14, R F1 ~R F3 R q11 ~R q14 L F L G and X L3 Same as above.

[0964] The sulfonium cation represented by formula (sulfo-1-1) should preferably be represented by formula (sulfo-1-2).

[0965] [Chemistry 379]

[0966]

[0967] In the formula, e4~e10, R F1 ~R F3 and R q11 ~R q13 Same as above.

[0968] Specific examples of sulfonium cations represented by formula (sulfo-1) are shown below, but are not limited thereto. Additionally, in the following formula, Me is a methyl group.

[0969] [Chemistry 380]

[0970]

[0971] [Chemistry 381]

[0972]

[0973] [Chemistry 382]

[0974]

[0975] [Chemistry 383]

[0976]

[0977] [Chem. 384]

[0978]

[0979] [Chem. 385]

[0980]

[0981] [Chemistry 386]

[0982]

[0983] [Chemistry 387]

[0984]

[0985] [Chem.388]

[0986]

[0987] [Chemistry 389]

[0988]

[0989] [Chemistry 390]

[0990]

[0991] [Chemistry 391]

[0992]

[0993] [Chemistry 392]

[0994]

[0995] [Chemistry 393]

[0996]

[0997] [Chemistry 394]

[0998]

[0999] [Chemistry 395]

[1000]

[1001] [Chemistry 396]

[1002]

[1003] [Chemistry 397]

[1004]

[1005] [Chem.398]

[1006]

[1007] [Chemistry 399]

[1008]

[1009] [Chemical 400]

[1010]

[1011] [Chemical Engineering 401]

[1012]

[1013] [Chemical 402]

[1014]

[1015] [Chemical 403]

[1016]

[1017] [Chemical 404]

[1018]

[1019] [Chemical 405]

[1020]

[1021] [Chemical 406]

[1022]

[1023] [Chemical 407]

[1024]

[1025] Specific examples of the aforementioned citric acid can be found in paragraph

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

[1026] Specific examples of the aforementioned ammonium cations can be represented by the following formula (am-1).

[1027] [Chemical 408]

[1028]

[1029] In equation (am-1), R q21 ~R q24 Each can be independently a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Also, R q21 and R q22They 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 formula (A) as R. 1 The same example represents hydrocarbon groups.

[1030] Specific examples of ammonium cations represented by formula (am-1) are listed below, but are not limited thereto.

[1031] [Chemical 409]

[1032]

[1033] Specific examples of onium salts represented by 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.

[1034] The onium salts represented by formula (1) or (2) function as quenchers in the chemically amplified resist composition of the present invention. This is because the relative anions of the aforementioned onium salts are conjugate bases of weak acids. Here, "weak acid" means an acidity that cannot deprotect the acid-instable groups of the units containing acid-instable groups used in the base polymer. The onium salts represented by 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 a relative anion. That is, when onium salts that produce strong acids, such as sulfonic acid with fluorinated α-position, are mixed with onium salts that produce weak acids, such as unfluorinated sulfonic acid or carboxylic acid, if the strong acid generated from the photoacid generator due to high-energy radiation irradiation collides with the unreacted onium salt with a weak acid anion, the weak acid is released through salt exchange, and an onium salt with a strong acid anion is generated. During this process, the strong acid is exchanged for a weak acid with low catalytic activity, so it appears as if the acid is deactivated, thus allowing for the control of acid diffusion.

[1035] Furthermore, (C) the quenching agent may also 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.

[1036] 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.

[1037] When the chemically amplified resist composition of the present invention contains an onium salt represented by formula (1) or (2) as a quencher in component (C), its content relative to 80 parts by mass of the base polymer in component (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 formula (1) or (2) can be used alone or in combination of two or more.

[1038] The chemically amplified resist composition of the present invention may also contain a nitrogen-containing compound as a (C) quencher. Specific examples of nitrogen-containing compounds as component (C) include: first-, second-, or third-order amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103, and particularly include: amine compounds having hydroxyl groups, ether bonds, ester bonds, lactone rings, cyano groups, or sulfonate bonds. Also, compounds formed by protecting a first- or second-order amine with a carbamate group, as described in Japanese Patent Publication No. 3790649, may also be included.

[1039] 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. 2012-46501 can be referenced for photodegrading bases.

[1040] When the chemically amplified resist composition of the present invention contains a nitrogen-containing compound as a (C) quencher, its content relative to 80 parts by mass of the (A) base polymer 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.

[1041] [(D) Photoacid generator]

[1042] The chemically amplified resist composition of the present invention may also contain a photoacid generator as component (D). There are no particular limitations on the aforementioned photoacid generator being a compound that generates acid upon irradiation by high-energy rays. Ideal photoacid generators may be represented by formulas (3) or (4).

[1043] [Chemical 410]

[1044]

[1045] In equation (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.

[1046] Specific examples of sulfonium salt cations represented by formula (3) can be listed as follows: examples of sulfonium cations in formula (A), those described in paragraphs

[0102] to

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

[0044] to

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

[0035] to

[0046] of Japanese Patent Application Publication No. 7491173, and examples of sulfonium cations represented by formula (sulfo-1), etc., but are not limited thereto. Specific examples of ferrous salt cations represented by formula (4) can be listed in paragraph

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

[1047] In equations (3) and (4), Xa - It is the anion of a strong acid. The anions of the aforementioned strong acids can be represented by any one of the following formulas (Xa-1) to (Xa-4).

[1048] [Chemistry 411]

[1049]

[1050] In 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 following formula (Xa-1-1). fa1 The same example represents hydrocarbon groups.

[1051] The anion represented by formula (Xa-1) should preferably be represented by the following formula (Xa-1-1).

[1052] [Chemistry 412]

[1053]

[1054] In equation (Xa-1-1), Q 1 and Q2 Each of the following is independently 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 is preferably trifluoromethyl. m is 0, 1, 2, 3, or 4, with 1 being particularly preferred. R fa1 It can also contain hydrocarbon groups with 1 to 35 carbon atoms that are heteroatoms. The aforementioned heteroatoms are preferably oxygen, nitrogen, sulfur, halogen, etc., with oxygen atoms being more preferred. Considering that the aforementioned hydrocarbon groups can obtain high resolution in the formation of fine patterns, those with 6 to 30 carbon atoms are particularly preferred.

[1055] In 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.

[1056] 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.

[1057] In equation (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.

[1058] Specific examples of anions represented by 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.

[1059] [Chemistry 413]

[1060]

[1061] [Chemistry 414]

[1062]

[1063] [Chemical 415]

[1064]

[1065] [Chemistry 416]

[1066]

[1067] [Chemistry 417]

[1068]

[1069] [Chemistry 418]

[1070]

[1071] [Chemistry 419]

[1072]

[1073] [Chemistry 420]

[1074]

[1075] [Chemistry 421]

[1076]

[1077] [Chemistry 422]

[1078]

[1079] In formula (Xa-2), R fb1 and R fb2 Each hydrocarbon group consists independently of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in formula (Xa-1-1). fa1 The same example represents a hydrocarbon group. R fb1 and R fb2It 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.

[1080] In formula (Xa-3), R fc1 R fc2 and R fc3 Each hydrocarbon group consists independently of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed and illustrated as R in 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 bases 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.

[1081] In formula (Xa-4), R fd It may also contain a hydrocarbon group with 1 to 40 carbon atoms and 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 formula (Xa-1-1). fa1 The same example represents hydrocarbon groups.

[1082] Specific examples of anions represented by formula (Xa-4) can be listed below, but are not limited to these.

[1083] [Chemistry 423]

[1084]

[1085] [Chemistry 424]

[1086]

[1087] The aforementioned examples of 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 formula (Xa-5).

[1088] [Chemical 425]

[1089]

[1090] In equation (Xa-5), x is 1, 2, or 3. y is 1, 2, 3, 4, or 5.

[1091] z can be 0, 1, 2, or 3. However, 1 ≤ y + z ≤ 5. y should ideally be 1, 2, or 3, with 2 or 3 being better. z should ideally be 0, 1, or 2.

[1092] In equation (Xa-5), X BI When the atoms are iodine or bromine atoms, and x and / or y are 2 or more, they can be the same or different.

[1093] In equation (Xa-5), L 1 It is a saturated hydrocarbon group with 1 to 6 carbon atoms, consisting of a single bond, ether bond, or ester bond, or may also contain ether or ester bonds. The aforementioned saturated hydrocarbon group can be linear, branched, or cyclic.

[1094] In equation (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, and the linker may also contain oxygen, sulfur or nitrogen atoms.

[1095] In 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 having 1 to 20 carbon atoms, a hydrocarbon oxy group having 1 to 20 carbon atoms, a hydrocarbon carbonyl group having 2 to 20 carbon atoms, a hydrocarbon oxycarbonyl group having 2 to 20 carbon atoms, or a hydrocarbon sulfonyl oxy group having 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 feB Each 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 group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms. R feDIt 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 hydrocarbon oxy group with 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group with 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl oxy group with 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group can be saturated or unsaturated, and can be straight-chain, branched, or cyclic. The aforementioned hydrocarbon group, hydrocarbon oxy group, hydrocarbon carbonyl group, hydrocarbon oxycarbonyl group, hydrocarbon carbonyl oxy group, and hydrocarbon sulfonyl oxy group can be straight-chain, branched, or cyclic. When x and / or z are 2 or more, each R fe They can be the same or different.

[1096] 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.

[1097] In equation (Xa-5), Rf 11 ~Rf 14 Each of these atoms can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of them must be a fluorine atom or a trifluoromethyl group. Also, Rf 11 With Rf 12 They can also combine to form carbonyl groups. Rf 13 and Rf 14 All of them are fluorine atoms, which is of excellent quality.

[1098] Specific examples of anions represented by equation (Xa-5) are shown below, but are not limited to these. Furthermore, in the following equation, X... BI Same as above.

[1099] [Chemistry 426]

[1100]

[1101] [Chemistry 427]

[1102]

[1103] [Chemistry 428]

[1104]

[1105] [Chemistry 429]

[1106]

[1107] [Chemistry 430]

[1108]

[1109] [Chemistry 431]

[1110]

[1111] [Chemistry 432]

[1112]

[1113] [Chemistry 433]

[1114]

[1115] [Chemistry 434]

[1116]

[1117] [Chemistry 435]

[1118]

[1119] [Chemistry 436]

[1120]

[1121] [Chemistry 437]

[1122]

[1123] [Chemistry 438]

[1124]

[1125] [Chemistry 439]

[1126]

[1127] [Chemistry 440]

[1128]

[1129] [Chemistry 441]

[1130]

[1131] [Chemistry 442]

[1132]

[1133] [Chemistry 443]

[1134]

[1135] [Chemistry 444]

[1136]

[1137] [Chemistry 445]

[1138]

[1139] [Chemistry 446]

[1140]

[1141] [Chemistry 447]

[1142]

[1143] [Chemistry 448]

[1144]

[1145] The aforementioned non-nucleophilic relative ions may also include the fluorobenzenesulfonate 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 or Japanese Patent Application Publication No. 2021-70692, the anion with a cyclic ether group as described in Japanese Patent Application Publication No. 2018-180525 or Japanese Patent Application Publication No. 2021-35935, and the anion described in Japanese Patent Application Publication No. 2018-92159.

[1146] The aforementioned non-nucleophilic relative ions can also be further described in Japanese Patent Application Publication Nos. 2006-276759, 2015-117200, 2016-65016 and 2019-202974 as bulky benzenesulfonic acid derivatives without fluorine atoms, or in Japanese Patent Application Publication No. 6645464 as benzenesulfonate anions and alkylsulfonate anions bonded to aromatic groups containing iodine atoms without fluorine atoms.

[1147] The aforementioned non-nucleophilic relative ions may also be the anions of disulfonic acid 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 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. 2015-24989.

[1148] Furthermore, the photoacid generator of component (D) should also be represented by the following formula (5).

[1149] [Chemistry 449]

[1150]

[1151] In equation (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, which may also contain heteroatoms. 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.

[1152] 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, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups.]

[1153] R 203The 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, and hexadecane-1,16-diyl. Alkyl groups with 1 to 30 carbon atoms, such as heptadecanyl-1,17-diyl; cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norcamphenediyl, and adamantanediyl; and aryl groups such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, isobutylphenylene, sec-butylphenylene, tert-butylphenylene, naphthylene, methylnaphthylene, ethylnaphthylene, n-propylnaphthylene, isopropylnaphthylene, n-butylnaphthylene, isobutylnaphthylene, sec-butylnaphthylene, 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 ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. The aforementioned heteroatoms should preferably be oxygen atoms.

[1154] In equation (5), L 11 It 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.

[1155] In equation (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.

[1156] The photoacid generator represented by formula (5) should preferably be represented by the following formula (5').

[1157] [Chemistry 450]

[1158]

[1159] In equation (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 formula (Xa-1-1). fa1 The same example represents hydrocarbon groups. s and t are independently 0, 1, 2, 3, 4 or 5, and u is 0, 1, 2, 3 or 4.

[1160] The photoacid generator represented by formula (5) can be exemplified by the same example as that shown in Japanese Patent Application Publication No. 2017-26980 as the photoacid generator represented by formula (2).

[1161] Among the aforementioned photoacid generators, those containing anions represented by formula (Xa-1-1) or (Xa-4) exhibit low acid diffusion and excellent solvent solubility, making them particularly ideal. Furthermore, those represented by formula (5') exhibit extremely low acid diffusion, making them particularly ideal.

[1162] When the chemically amplified resist composition of the present invention contains photoacid generating agent (D), its content relative to 80 parts by mass of the base polymer (A) is preferably 0.1 to 40 parts by mass, and more preferably 0.5 to 20 parts by mass. If the amount of photoacid generating agent (D) added is within the aforementioned range, the resolution is good, and there is no concern about foreign matter forming in the resist film after development or during peeling, which is therefore ideal. One type of photoacid generating agent (D) can be used alone, or two or more can be used in combination.

[1163] [(E) Surfactant]

[1164] The chemically amplified resist composition of the present invention may also contain a surfactant as component (E). The surfactant (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 2011-16746.

[1165] 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 formula (surf-1).

[1166] [Chemistry 451]

[1167]

[1168] Here, R, Rf, A, B, C, m, and n are irrelevant to the foregoing description and apply only to formula (surf-1). R is an aliphatic group with 2 to 5 carbon atoms, ranging from 2 to 4 valences. Examples of the aforementioned aliphatic groups, for those with a 2-valent valence, include: ethylene, 1,4-butylene, 1,2-propylene, 2,2-dimethyl-1,3-propylene, 1,5-pentane, etc.; examples of those with a 3- or 4-valent valence include the following.

[1169] [Chemistry 452]

[1170]

[1171] In the formula, the dashed lines represent atomic bonds, which are partial structures derived from glycerol, trimethylolethane, trimethylolpropane, and neopentyl tertrol, respectively.

[1172] Among them, 1,4-butylene, 2,2-dimethyl-1,3-propylene, etc. are preferred.

[1173] 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 formula (surf-1) is not specified; they can be block-bonded or randomly bonded. For details on the manufacture of surfactants based on partially fluorinated oxyheterocyclic butane ring-opening polymer systems, please refer to the specification in US Patent No. 5,650,483, etc.

[1174] 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 for development with alkaline solutions after exposure or post-exposure baking (PEB) and are soluble in water, thus minimizing their potential to cause 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.

[1175] Specific examples of such polymeric surfactants include those containing at least one repeating unit selected from any of the following formulas (6A) to (6E).

[1176] [Chemistry 453]

[1177]

[1178] In equations (6A) to (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 having 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 It is a (w+1) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 20 carbon atoms. w can be 1, 2, or 3. R s5 Each 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 it may also insert an ether bond or a carbonyl group between carbon bonds.

[1179] R s1The 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.

[1180] R s2 The alkylene group represented should preferably be a saturated alkylene group, and can be linear, branched, or cyclic. Specific examples include: methylene, ethylene, propylene, butylene, and pentylene.

[1181] R s3 Or R s6 The hydrocarbon group 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. The aforementioned saturated hydrocarbon groups can be exemplified as R... s1 In addition to those representing hydrocarbon groups, other examples include: undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc. R s3 Or R s6 The fluorinated hydrocarbon groups can be categorized as those in which some or all of the hydrogen atoms of the carbon atom bonded to the aforementioned hydrocarbon group are replaced by fluorine atoms. As mentioned above, ether bonds or carbonyl groups may also be inserted between their carbon-carbon bonds.

[1182] R s3 Specific examples of acid-instable groups can be listed as follows: groups represented by the aforementioned formulas (AL-3) to (AL-5), trialkylsilyl groups with alkyl groups having 1 to 6 carbon atoms, and alkyl groups containing oxygen groups having 4 to 20 carbon atoms.

[1183] R s4 The (w+1) valence hydrocarbon group or fluorinated hydrocarbon group 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.

[1184] R saThe fluorinated hydrocarbon group represented should preferably be saturated and can be linear, branched, or cyclic. Specific examples include those in which some or all of the hydrogen atoms of 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.

[1185] Specific examples of the repeating units represented in any of equations (6A) to (6E) can be listed below, but are not limited thereto. Additionally, in the following equation, R... B Same as above.

[1186] [Chemistry 454]

[1187]

[1188] [Chemistry 455]

[1189]

[1190] [Chemistry 456]

[1191]

[1192] [Chemistry 457]

[1193]

[1194] [Chemistry 458]

[1195]

[1196] [Chemistry 459]

[1197]

[1198] The aforementioned polymeric surfactants may also contain other repeating units besides those represented by formulas (6A) to (6E). 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 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.

[1199] 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.

[1200] Methods for synthesizing the aforementioned polymeric surfactants include: providing repeating units represented by formulas (6A) to (6E), and monomers containing unsaturated bonds as needed, in an organic solvent, adding a free radical initiator, and heating to polymerize them. Examples of organic solvents used in polymerization include: toluene, benzene, THF, diethyl ether, dioxane, etc. Examples of polymerization initiators include: AIBN, 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2-azobis(2-methylpropionic acid), benzoyl peroxide, lauroyl peroxide, etc. The reaction temperature should preferably be 50–100℃. The reaction time should preferably be 4–24 hours. Acid-unstable groups can be directly introduced into the monomer, or they can be protected or partially protected after polymerization.

[1201] 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 0.01–10 mol%.

[1202] When the chemically amplified resist composition of the present invention contains surfactant (E), its content relative to 80 parts by mass of the base polymer (A) is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 10 parts by mass. If the content of surfactant (E) is 0.1 parts by mass or more, it will sufficiently improve the receding contact angle between the resist film surface and water; if it is 50 parts by mass 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.

[1203] [(F) Other ingredients]

[1204] 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 3000 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 relative to 80 parts by mass of the base polymer in (A) is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass. Excessive content may sometimes make acid diffusion control difficult, leading to degradation of resolution and 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.

[1205] [Pattern Formation Method]

[1206] The pattern forming method of the present invention includes the following steps:

[1207] A resist film is formed on the substrate using the aforementioned chemically amplified resist composition.

[1208] The aforementioned resist film was exposed to high-energy rays, and

[1209] The previously exposed resist film was developed using a developer.

[1210] 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.).

[1211] The resist film can be formed, for example, by using spin coating or other methods to coat the aforementioned chemically amplified resist composition onto a substrate 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.

[1212] High-energy rays used for photoresist film exposure include: KrF excimer laser, ArF excimer laser, EB, and EUV with wavelengths of 3–15 nm. When using KrF excimer laser, ArF excimer laser, 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. 2 And preferably, it should be 10–100 mJ / cm 2The 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 10–200 μC / cm 2 Irradiation is performed in this manner.

[1213] 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.

[1214] The aforementioned water-insoluble protective film, used to prevent leaching from the resist film and improve the hydrophobicity of the film surface, 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 developing solution and removes the protective film while removing the soluble portion of the resist film. The latter is particularly preferred because it is based on a polymer containing 1,1,1,3,3,3-hexafluoro-2-propanol residues that is insoluble in water but soluble in alkaline developing solution, and is 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 developing solution-soluble surfactants in alcohol solvents with 4 or more carbon atoms, ether solvents with 8 to 12 carbon atoms, or mixtures thereof.

[1215] 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, more preferably at 80–140°C for 1–3 minutes.

[1216] For example, a developing solution containing 0.1 to 5% by mass, preferably 2 to 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 to 3 minutes, preferably 0.5 to 2 minutes. This allows the exposed areas to dissolve and form the desired pattern on the substrate.

[1217] 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.

[1218] 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.

[1219] 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.

[1220] In the aforementioned organic solvent development, the developing solution may include: 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. Ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, 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.

[1221] [Example]

[1222] The present invention will be specifically described below with examples of synthesis, embodiments, and comparative examples, but the present invention is not limited to the following embodiments. Furthermore, the apparatus used is described below.

[1223] • MALDITOF-MS: S3000 manufactured by Nippon Electronics Co., Ltd.

[1224] [1] Synthesis of sulfonium salt monomers

[1225] [Example 1-1] Synthesis of monomer PAG-1

[1226] (1) Synthesis of intermediate In-1

[1227] [Chemistry 460]

[1228]

[1229] Under nitrogen atmosphere, SM-1 (27.9 g), SM-2 (89.5 g), and copper acetate (8.24 g) were dissolved in dichloroethane (300 g). The reaction mixture was then heated to 100 °C and matured for 15 hours. After maturation, the reaction mixture was cooled, and water (150 g) was added to stop the reaction. The organic layer was then separated and washed with water, followed by concentration under reduced pressure to remove the solvent. The filter residue was purified by silica gel column chromatography, yielding 53.8 g of intermediate In-1 (82% yield) as a yellow, viscous oil.

[1230] (2) Synthesis of monomer PAG-1

[1231] [Chemistry 461]

[1232]

[1233] Under nitrogen atmosphere, intermediates In-1 (36.1 g), In-2 (76.7 g), dichloromethane (300 g), and water (150 g) were fed and stirred at room temperature for 30 minutes. The organic layer was separated and washed with water, followed by vacuum concentration. The filter residue was washed with diisopropyl ether and concentrated to obtain 83.6 g of monomer PAG-1 (96% yield) as an oil.

[1234] The TOF-MS results for PAG-1 are shown below.

[1235] MALDI TOF-MS: POSITIVE M + 288 (equivalent to C) 19 H 14 NS + )

[1236] NEGATIVE M - 873 (equivalent to C) 22 H8F4I7O7S - )

[1237] [Examples 1-2 to 1-9] Synthesis of monomers PAG-2 to PAG-9

[1238] Using the corresponding raw materials and various organic synthesis reactions, the sulfonate-type monomers PAG-2 to PAG-9 shown below were synthesized.

[1239] [Chemistry 462]

[1240]

[1241] [Chemistry 463]

[1242]

[1243] [Comparative Examples 1-1 to 1-6] Comparative Synthesis of Monomers PAG-A to PAG-F

[1244] Using the corresponding raw materials and various organic synthesis reactions, the comparative sulfonate monomers PAG-A to PAG-F were synthesized as shown below.

[1245] [Chemistry 464]

[1246]

[1247] [2] Synthesis of basic polymers

[1248] The monomers used in the synthesis of the basic polymer, other than PAG-1 to PAG-9 and PAG-A to PAG-F, are described below.

[1249] [Chemistry 465]

[1250]

[1251] [Chemistry 466]

[1252]

[1253] [Chemistry 467]

[1254]

[1255] [Example 2-1] Synthesis of Polymer P-1

[1256] Under nitrogen atmosphere, monomers a1-1 (18.5 g), b1-1 (5.4 g), PAG-1 (26.2 g), V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), and 70 g of MEK were measured in a flask to prepare a monomer-polymerization initiator solution. In another flask conditioned under nitrogen atmosphere, 23 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 polymerization solution was maintained at 80°C with continuous stirring for 2 hours, and then cooled to room temperature. The resulting polymerization solution was added dropwise to 1000 g of vigorously stirred hexane, and the precipitated polymer was filtered and separated. The obtained polymer was then washed twice with 300 g of hexane and dried under vacuum at 50°C for 20 hours to obtain a white powdered polymer P-1 (yield 49.1 g, 98% yield). The Mw of polymer P-1 is 9600, and the Mw / Mn ratio is 1.62. Additionally, Mw is the converted value of polystyrene obtained by GPC using DMF as a solvent.

[1257] [Chemistry 468]

[1258]

[1259] [Examples 2-2 to 2-26, Comparative Examples 2-1 to 2-18] Synthesis of polymers P-2 to P-26 and CP-1 to CP-18

[1260] By changing the type and blending ratio of each monomer, the polymers shown in Tables 1 and 2 were manufactured using the same method as in Example 2-1.

[1261] [Table 1]

[1262]

[1263]

[1264] [Table 2]

[1265]

[1266] [3] Preparation of chemically amplified resist composition

[1267] [Examples 3-1 to 3-26, Comparative Examples 3-1 to 3-18]

[1268] A solution was prepared by dissolving a base polymer (P-1 to P-26) containing the sulfonium salt monomers (PAG-1 to PAG-9) of the present invention, a base polymer (CP-1 to CP-18) containing the comparative sulfonium salt monomers (PAG-A to PAG-F), a photoacid generator (PAG-X, PAG-Y), and a quencher (Q-1 to Q-4) in a solvent containing 0.01% by mass of surfactant A (OMNOVA) as shown in Tables 3 and 4 below. The solution was then filtered through a 0.2 μm Teflon (registered trademark) filter to prepare chemically amplified resist compositions (R-1 to R-26, CR-1 to CR-18).

[1269] [Table 3]

[1270]

[1271]

[1272] [Table 4]

[1273]

[1274]

[1275] In Tables 3 and 4, the solvent, photoacid generators PAG-X and PAG-Y, quenchers Q-1 to Q-4, and surfactant A are described below.

[1276] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[1277] EL (ethyl lactate)

[1278] DAA (diacetone alcohol)

[1279] • Photoacid generators: PAG-X, PAG-Y

[1280] [Chemistry 469]

[1281]

[1282] Quenching agents: Q-1 to Q-4

[1283] [Chemistry 470]

[1284]

[1285] Surfactant A: 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane-tetrahydrofuran-2,2-dimethyl-1,3-propanediol copolymer (manufactured by OMNOVA).

[1286] [Chemistry 471]

[1287]

[1288] a : (b + b') : (c + c') = 1 : 4 ~ 7 : 0.01 ~ 1 (molar ratio)

[1289] Mw = 1500

[1290] [4] Evaluation of EUV lithography (1)

[1291] [Examples 4-1 to 4-26, Comparative Examples 4-1 to 4-18]

[1292] The chemically amplified resist compositions (R-1 to R-26, CR-1 to CR-18) shown in Tables 3 and 4 were spin-coated onto a Si substrate with a silicon-containing spin-coating hard mask SHB-A940 (43% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd., to a thickness of 20 nm. The substrate was pre-baked at 100°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 NXE3400 (NA 0.33, σ 0.9 / 0.6, dipole illumination), with variations in exposure amount and focus (exposure interval: 1 mJ / cm). 2An LS pattern with a size of 18 nm and a pitch of 36 nm was exposed on the wafer (focal spacing: 0.020 μm). After exposure, PEB was performed at the temperatures shown in Tables 5 and 6 for 60 seconds. 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.

[1293] The LS pattern was observed using a Hitachi Advanced Technology Co., Ltd. (HIT) CG6300 measuring SEM, and the sensitivity, EL, LWR, depth of focus (DOF), and collapse limit were evaluated according to the following methods. Furthermore, the development defects of the obtained LS pattern were evaluated. The results are shown in Tables 5 and 6.

[1294] [Sensitivity Evaluation]

[1295] Calculate the optimal exposure Eop (mJ / cm) for obtaining an LS pattern with a linewidth of 18nm and a pitch of 36nm. 2 ), and let it be the sensitivity. The smaller the value, the higher the sensitivity.

[1296] [EL Review]

[1297] The EL (in %) is calculated using the following formula, based on the exposure within ±10% (16.2–19.8 nm) of the 18 nm spacing width in the aforementioned LS pattern. The larger this value, the better the performance.

[1298] EL(%)=(|E1-E2| / Eop)×100

[1299] E1: Provides optimal exposure for LS patterns with a linewidth of 16.2nm and a pitch of 36nm.

[1300] E2: Provides optimal exposure for LS patterns with a linewidth of 19.8nm and a pitch of 36nm.

[1301] Eop: Provides optimal exposure for LS patterns with a linewidth of 18nm and a pitch of 36nm.

[1302] [LWR Evaluation]

[1303] The dimensions at 10 points along the length of the line obtained by Eop irradiation of the LS pattern are measured, and the standard deviation (σ) of the result is calculated as 3 times the value (3σ) as the LWR. The smaller this value, the more uniform the line width and roughness of the pattern can be obtained.

[1304] [DOF Rating]

[1305] The focal depth is evaluated by determining the focal range formed within ±10% (16.2–19.8 nm) of the 18 nm dimension in the aforementioned LS pattern. The larger this value, the wider the focal depth.

[1306] [Collapse Limit Assessment of Line Patterns]

[1307] The line dimensions of the aforementioned LS pattern at various exposures were measured 10 times along its length for the optimal focal point. The finest line dimension that could be obtained without collapse was taken as the collapse limit dimension. The smaller this value, the better the collapse limit.

[1308] [Evaluation of Development Defects]

[1309] An LS pattern with a linewidth of 18nm and a pitch of 36nm, formed using the aforementioned optimal exposure, was inspected using a KLA-Tencor KLA2360 defect inspection device (trade name). The pixel size of the defect inspection device was set to 0.16μm, and the threshold was set to 20. Defects (number / cm) extracted by comparing the differences between the superposition of the image and the pixel units were detected. 2 ), and calculate the number of defects per unit area (defects / cm²). 2 Subsequently, a defect inspection was conducted, and developing defects were extracted from all defects and the number of developing defects per unit area (defects / cm²) was calculated. 2 Values ​​below 0.5 are rated A, values ​​above 0.5 but below 1.0 are rated B, values ​​above 1.0 but below 5.0 are rated C, and values ​​above 5.0 are rated D. Lower values ​​indicate better performance.

[1310] [Table 5]

[1311]

[1312]

[1313] [Table 6]

[1314]

[1315] As shown in Tables 5 and 6, the chemically amplified resist composition containing polymers derived from the sulfonate monomers of this invention exhibits good sensitivity, as well as excellent EL, LWR, and DOF. Furthermore, a low collapse limit value was confirmed, demonstrating strong resistance to pattern collapse even during fine pattern formation. In addition, development defects were also confirmed to be suppressed. Therefore, it is evident that the chemically amplified resist composition of this invention is suitable as a material for EUV lithography.

[1316] [5] Evaluation of EUV lithography (2)

[1317] [Examples 5-1 to 5-26, Comparative Examples 5-1 to 5-18]

[1318] The chemically amplified resist compositions (R-1 to R-26, CR-1 to CR-18) shown in Tables 3 and 4 were spin-coated onto a Si substrate with a silicon-containing spin-coating hard mask SHB-A940 (43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., with a film thickness of 20 nm. The resist film was pre-baked at 105°C for 60 seconds using a hot plate to obtain a resist film with a thickness of 50 nm. The resist film was exposed using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, wafer-scale hole pattern with a pitch of 46 nm and a deviation of +20%). Then, PEB was performed for 60 seconds using a hot plate at the temperatures recorded in Tables 7 and 8, followed by development with a 2.38% by mass TMAH aqueous solution for 30 seconds to form a hole pattern with a size of 23 nm.

[1319] Using a Hitachi Advanced Technologies (AG) CG6300 length measuring SEM, the exposure was measured when the hole size was formed at 23 nm, and this was set as the sensitivity. Furthermore, the size of 50 holes at this time was measured, and the standard deviation (σ) obtained from the results was set to three times the value (3σ) as the CDU. The results are shown in Tables 7 and 8.

[1320] [Table 7]

[1321]

[1322]

[1323] [Table 8]

[1324]

[1325]

[1326] The results shown in Tables 7 and 8 confirm that chemically amplified resist compositions containing polymers composed of the sulfonate type monomers of the present invention exhibit good sensitivity and excellent CDU.

[1327] [6] Evaluation of dry etching resistance

[1328] [Examples 6-1 to 6-26, Comparative Examples 6-1 to 6-18]

[1329] 2g of each polymer (polymers P-1 to P-26, comparative polymers CP-1 to CP-18) shown in Tables 1 and 2 were dissolved in 10g of cyclohexanone and filtered through a 0.2μm filter. The filtered polymer solution was spin-coated onto a Si substrate and formed into a film with a thickness of 300nm. The film was then evaluated under the following conditions.

[1330] Etching experiments using CHF3 / CF4-based gases:

[1331] The thickness difference of the polymer film before and after etching was determined using the TE-8500P dry etching apparatus manufactured by Tokyo Power Technology Co., Ltd.

[1332] The etching conditions are as follows.

[1333]

[1334] In this evaluation, films with smaller thickness variations, i.e., smaller reductions, indicate higher etching resistance. The results for dry etching resistance are shown in Tables 9 and 10.

[1335] [Table 9]

[1336]

[1337] [Table 10]

[1338]

[1339]

[1340] The results shown in Tables 9 and 10 confirm that the polymer of the present invention has excellent dry etching resistance to CHF3 / CF4 gases.

Claims

1. A sulfonium salt type monomer, represented by the following formula (A); In the formula, p is 1, 2 or 3; n1 is 0 or 1; n2 is 1 or 2; n3 is 0, 1, 2 or 3; however, when n1 is 0, it is 1≤n2+n3≤5, and when n1 is 1, it is 1≤n2+n3≤7. R 1 It can be a halogen atom, nitro group, hydroxyl group, carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; when n3 is 2 or 3, each R 1 They can be the same or different, 2 Rs 1 They can also bond to each other and form rings together with the carbon atoms they are bonded to; R 2 It is a hydrocarbon group with 1 to 30 carbon atoms, which may also contain heteroatoms; when p is 1, there are 2 R 2 They can be the same or different; also, they are bonded to S. + Two of the three substituents can also bond to each other and form a ring together with the sulfur atom they are bonded to; Z - It is an aromatic sulfonate anion with an aromatic vinyl structure.

2. The sulfonium salt type monomer according to claim 1, which is represented by the following formula (A1); In the formula, p, n1~n3, R 1 and Z - Same as above; n4 is 0 or 1; n5 is 0, 1, 2, 3, 4 or 5; R 3 It can be a halogen atom, nitro group, hydroxyl group, carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; when n5 is 2, 3, 4, or 5, each R 3 They can be the same or different, 2 Rs 3 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

3. The sulfonium salt type monomer according to claim 1, wherein, Z - Z represents the anion. In the formula, m1 is 0 or 1; m2 is 0, 1, 2, 3 or 4; m3 is 0, 1, 2 or 3; m4 is 0 or 1; m5 is 0, 1, 2, 3 or 4; m6 is 0, 1, 2 or 3; m7 is 0 or 1; m8 is 1, 2, 3 or 4; m9 is 0, 1, 2 or 3; m10 is 0 or 1; m11 is 0, 1, 2, 3 or 4; m12 is 0, 1, 2 or 3; m13 is 0 or 1; m14 is 0 or 1; m15 is 0 or 1; however, m When 1 is 0, 0 ≤ m2 + m3 + m14 ≤ 4; when m1 is 1, 0 ≤ m2 + m3 + m14 ≤ 6; when m4 is 0, 0 ≤ m5 + m6 ≤ 4; when m4 is 1, 0 ≤ m5 + m6 ≤ 6; when m7 is 0, 0 ≤ m8 + m9 ≤ 5; when m7 is 1, 0 ≤ m8 + m9 ≤ 7; when m10 is 0, 0 ≤ m11 + m12 ≤ 4; when m10 is 1, 0 ≤ m11 + m12 ≤ 6; and 1 ≤ m2 + m5 + m8 ≤ 4. R A It consists of hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups; R 11 R 12 and R 13 Each R can be an independent halogen atom other than an iodine atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; or it can also be a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; when m3 is 2 or 3, each R 11 They can be the same or different, 2 Rs 11 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when m6 is 2 or 3, each R 12 They can be the same or different, 2 Rs 12 They can also bond to each other and form rings together with the carbon atoms they are bonded to; when m9 is 2 or 3, each R 13 They can be the same or different, 2 Rs 13 They can also bond to each other and form rings together with the carbon atoms they are bonded to; R 14 It can be a halogen atom other than fluorine and iodine atoms, a nitro group, a hydroxyl 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 m12 is 2 or 3, each R 14 They can be the same or different, 2 Rs 14 They can also bond to each other and form rings together with the carbon atoms they are bonded to; R F It consists of a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms; when m11 is 2, 3, or 4, each R F They can be the same or different; L A L B L C L D and L E Each bond can be independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond; X L1 and X L2 Each is an independent single bond or may contain a heteroatom and be a hydrocarbon group with 1 to 40 carbon atoms; However, m13 and m14 cannot both be 0 at the same time, L A L B L C L D X L1 and X L2 It cannot be a single key at the same time.

4. The sulfonium salt type monomer according to claim 3, wherein, m15 is 1.

5. A monomeric photoacid generator, comprising a sulfonium salt monomer according to any one of claims 1 to 4.

6. A polymer comprising repeating units from the monomeric photoacid generator according to claim 5.

7. The polymer according to claim 6 further comprises at least one repeating unit selected from the repeating unit represented by formula (a1), the repeating unit represented by formula (a2), and the repeating unit represented by formula (a3); In the formula, R A Each can be independently composed of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; X 1 Single bond, phenylene, naphthylene, *-C(=O)-OX 11 -or *-C(=O)-NH-X 11 - and the phenylene or naphthylene group may also be replaced by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, or a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom, or a halogen atom; X 11 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring; X 2 It is a single bond, *-C(=O)-O- or *-C(=O)-NH-; * indicates an atomic bond with a carbon atom in the main chain; R 21 It can be a halogen atom, cyano group, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; when a1 is 2, 3, or 4, each R 21 They can be the same or different; AL 1 and AL 2 Each is an acid-labile group; a1 can be 0, 1, 2, 3 or 4; In the formula, b1 is 0 or 1; b2 is 0, 1, 2 or 3 when b1 is 0, and 0, 1, 2, 3, 4 or 5 when b1 is 1; R A It consists of hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups; X 3 For single bonds, *-C(=O)-O- or *-C(=O)-NH-; * indicates an atomic bond with a carbon atom in the main chain; X 4 It is a single bond, an aliphatic alkylene group, a carbonyl group, a sulfonyl group, or a combination thereof, having 1 to 4 carbon atoms; X 5 and X 6 Each can be independently an oxygen atom or a sulfur atom; however, X 4 and X 6 Adjacent carbon atoms bonded to the aromatic ring; R 22 and R 23 Each is an independent hydrocarbon group consisting of 1 to 20 carbon atoms, or may contain heteroatoms; also, R 22 and R 23 They can also bond to each other and form rings together with the carbon atoms they are bonded to; R 24 It can be a halogen atom, hydroxyl group, cyano group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; it can also be a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; or a hydrocarbon thio group or -N(R) group with 1 to 20 carbon atoms containing heteroatoms. 24A (R) 24B ); R 24A and R 24B Each is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; when b2 is 2 or more, each R 24 Multiple Rs can be the same or different. 24 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

8. The polymer according to claim 6 further comprises at least one repeating unit selected from the repeating units represented by formula (b1) and formula (b2); In the formula, R A Each can be independently composed of 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 31 It is a hydrogen atom, or a group containing at least one of the following structures with 1 to 20 carbon atoms: hydroxyl group other than phenolic hydroxyl group, cyano group, carbonyl group, carboxyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulcinolone ring and carboxylic anhydride (-C(=O)-OC(=O)-); R 32 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 oxy 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 oxy group with 2 to 20 carbon atoms containing heteroatoms; or it can be a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; when c2 is 2, 3 or 4, each R 32 They can be the same or different; c1 can be 1, 2, 3 or 4; c2 can be 0, 1, 2, 3 or 4; however, 1≤c1+c2≤5.

9. A chemically amplified resist composition comprising (A) a base polymer comprising the polymer according to claim 6.

10. The chemically amplified resist composition according to claim 9, further comprising (B) an organic solvent.

11. The chemically amplified resist composition according to claim 9, further comprising (C) a quencher.

12. The chemically amplified resist composition according to claim 9 further comprises (D) a photoacid generator.

13. The chemically amplified resist composition according to claim 9 further comprises (E) a surfactant.

14. A method for forming a pattern, comprising the following steps: A resist film is formed on a substrate using the chemically amplified resist composition according to claim 9. The resist film was exposed to high-energy rays, and The exposed resist film was developed using a developer.

15. The pattern forming method according to claim 14, wherein, The high-energy rays are KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet rays with wavelengths of 3–15 nm.

Images