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

Abstract

This invention provides a strontium salt type monomer represented by formula (A), a polymer containing repeating units from the strontium salt type monomer, a chemical amplification inhibitor composition containing the polymer, and a patterning method using the chemical amplification inhibitor composition. (In the formula, Z- represents an aromatic sulfonic acid anion having a polymerizable group.)

Description

Technical Field

[0001] This invention relates to strontium salt monomers, polymers, chemical amplification inhibitor compositions, and patterns forming methods. Prior Technology

[0002] With the increasing integration and speed of LSI, the miniaturization of patterning is progressing rapidly. In particular, the expansion of the flash memory market and the increase in memory capacity are driving miniaturization. Regarding cutting-edge miniaturization technologies, mass production of 65nm node devices using ArF lithography is underway, and preparations are underway for mass production of the next-generation 45nm node devices using ArF immersion lithography. For the next-generation 32nm node devices, there are ongoing discussions regarding immersion lithography using ultra-high nanometer lenses with liquids having a higher refractive index than water and high-refractive-index lenses, high-refractive-index resist films, extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm, and double exposure (double patterning lithography) of ArF lithography.

[0003] As miniaturization progresses, the refractive limit of light is approached, resulting in a decrease in light contrast. This decrease in light contrast leads to a reduction in the resolution or focal margin of the hole or trench pattern in the positive resist film.

[0004] As patterns become more refined, the line width roughness (LWR) of the line pattern and the dimensional uniformity (CDU) of the hole pattern are considered problems. Points have been made to the uneven distribution or aggregation of the base polymer or acid-generating agent, or the effect of acid diffusion. Furthermore, due to the thinning of the resist film, the LWR tends to increase, and the deterioration of LWR caused by thinning along with the progress of miniaturization has become a significant problem.

[0005] In EUV lithography resist formulations, it is necessary to simultaneously achieve high sensitivity, high resolution, and low light-to-weight ratio (LWR). Shortening the acid diffusion distance reduces LWR and lowers sensitivity. For example, lowering the post-exposure baking (PEB) temperature reduces LWR but lowers sensitivity. Similarly, increasing the amount of quencher reduces LWR but lowers sensitivity. Therefore, it is necessary to break the trade-off between sensitivity and LWR.

[0006] To suppress acid diffusion, a proposed method involves an inhibitor compound containing repeating units from onium salts of sulfonic acids with polymerizable unsaturated bonds (Patent Document 1). Such polymer-bonded acid generators, by generating polymeric sulfonic acids upon exposure, exhibit very short acid diffusion. Furthermore, sensitivity can be improved by increasing the ratio of the acid generator. In additive acid generators, increasing the amount increases sensitivity, but also increases the acid diffusion distance. Because acids diffuse unevenly, increased acid diffusion degrades the level-reduction ratio (LWR) or concentration-reduction ratio (CDU). In terms of the balance between sensitivity, LWR, and CDU, polymeric acid generators can be considered to offer high performance.

[0007] Because iodine atoms have very high absorption at a wavelength of 13.5 nm in EUV, it has been confirmed that they generate secondary electrons from iodine atoms during exposure, making them noteworthy in EUV lithography. Patent Document 2 describes a photoacid generator in which iodine atoms are introduced into anions, and Patent Document 3 describes a photoacid generator containing polymeric groups in which iodine atoms are introduced into anions. This confirms a certain degree of improvement in lithography performance, but iodine-based organic solvents have low solubility, raising concerns about precipitation in the solvent.

[0008] To further suppress acid diffusion, it has been proposed to use polymers containing repeating units from strontium salts of weak acids with a pKa of -0.8 or higher that have polymeric groups as inhibitory components of polymer-bonded quenchers (Patent Documents 4-8). In Patent Document 4, examples of weak acids include carboxylic acids, sulfonamides, phenols, and hexafluoroethanol. [Previous Technical Documents] [Patent Literature]

[0009] [Patent Document 1] Japanese Patent No. 4425776 [Patent Document 2] Japanese Patent No. 6720926 [Patent Document 3] Japanese Patent No. 6973274 [Patent Document 4] International Publication No. 2019 / 167737 [Patent Document 5] International Publication No. 2022 / 264845 [Patent Document 6] Japanese Patent Application Publication No. 2022-115072 [Patent Document 7] Japanese Patent No. 7433394 [Patent Document 8] Japanese Patent Application Publication No. 2024-178693 Summary of the Invention

[0010] [The problem that the invention aims to solve] Among chemical amplification resist compositions that use acid as a catalyst, there is a prospect of developing resist compositions that offer higher sensitivity and improve lithography performance such as LWR, CDU, exposure margin (EL), and depth of focus (DOF), as well as excellent etch resistance after patterning.

[0011] This invention arose in light of the aforementioned circumstances, and aims to provide a chemical amplification inhibitor composition that exhibits excellent solvent solubility, high sensitivity, high contrast, and excellent lithography performance (LWR, CDU, EL, DOF, etc.) in photolithography, particularly in the use of high-energy rays such as KrF excimer lasers, ArF excimer lasers, electron beams (EB), and EUV. Furthermore, it demonstrates strong resistance to pattern collapse and excellent etching resistance even during fine pattern formation. The composition includes a strontium salt monomer, a polymer containing repeating units from the strontium salt monomer, a chemical amplification inhibitor composition containing the polymer, and a pattern formation method using the chemical amplification inhibitor composition. [Methods for solving problems]

[0012] The inventors of this invention, through repeated and in-depth research to achieve the aforementioned objectives, discovered that as a polymer-bonded quencher, a polymer containing repeating units derived from strontium salts is used. This strontium salt contains a carboxylic acid anion with a styrene or vinylnaphthalene structure as a polymerizable group and an iodine atom, and a triarylstrontium cation with an iodine atom on the same aromatic ring and an acid-unstable group having a tertiary / secondary ether structure, a tertiary / secondary ester structure, a tertiary / secondary carbonate structure, or an acetal structure. This allows for the production of a chemical amplification inhibitor composition with excellent solvent solubility, high sensitivity, improved imaging performance of LWR, CDU, EL, DOF, etc., high contrast and high resolution, and excellent etching resistance. Thus, this invention was completed.

[0013] That is, the present invention provides the following strontium salt type monomer, polymer, chemical amplification inhibitor composition and pattern formation method. 1. A strontium salt type monomer, which is represented by the following formula (a). [Chemistry 1] (In the formula, n1 is 0 or 1; n2 is 1, 2, 3 or 4; n3 is 1 or 2; n4 is 0, 1 or 2; however, when n1 is 0, it is 0 ≦ n2 + n3 + n4 ≦ 5, and when n1 is 1, it is 0 ≦ n2 + n3 + n4 ≦ 7; n5 is 0 or 1; n6 is 1, 2, 3 or 4; n7 is 0, 1 or 2; however, when n5 is 0, it is 0 ≦ n6 + n7 ≦ 5, and when n5 is 1, it is 0 ≦ n6 + n7 + ≦ 7; n8 is 1 or 2; RF consists of a fluorine atom, a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, or a pentafluorothio group; when n6 is 2, 3, or 4, each RF may be the same or different from the others; R1 and R2 are each independently a halogen atom other than fluorine, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or a hydrocarbon group with 1 to 20 carbon atoms (heteroatomic), a hydrocarbon oxygen group with 1 to 20 carbon atoms (heteroatomic), or a hydrocarbon thio group with 1 to 20 carbon atoms (heteroatomic); when n4 is 2, each R1 can be the same or different, and two R1s can also bond to each other to form a ring with the bonded carbon atoms; when n7 is 2, each R2 can be the same or different, and two R2s can also bond to each other to form a ring with the bonded carbon atoms. L1 series ether bonds, ester bonds, or carbonate bonds; RAL series acid unstable groups; Furthermore, two of the three aromatic rings bonded to S+ can also bond with each other to form a ring together with these bonded sulfur atoms; (Z-series carboxylic acid anions with aromatic vinyl structures and iodine atoms.) 2. As in 1, the strontium salt type monomer, wherein, is represented by the following formula (a1): [Chemistry 2] (In the formula, n2~n4, n6~n8, RF, R1, R2, L1, RAL and Z-series are the same as above.) 3. Sulphur salt type monomers such as 1 or 2, wherein the above-mentioned acid-instable group is represented by the following formula (AL-1) or (AL-2): [Chemistry 3] (In the formula, p1 and p2 are each independently 0 or 1; q1 and q2 are each independently 0, 1, 2, 3 or 4;) RL1 and RL2 are each independently a hydrocarbon group with 1 to 12 carbon atoms; RL3 is a hydrogen atom or a hydrocarbon group with 1 to 12 carbon atoms; the -CH2- portion of the hydrocarbon group represented by RL1, RL2, and RL3 can also be substituted by -O- or -S-. If the hydrocarbon group contains an aromatic ring, some or all of the hydrogen atoms in the aromatic ring can also be substituted by a halogen atom, a cyano group, a nitro group, an alkyl group with 1 to 4 carbon atoms containing a halogen atom, or an alkoxy group with 1 to 4 carbon atoms containing a halogen atom; furthermore, RL1 and RL2 can also bond together with these bonded carbon atoms to form a ring, and the -CH2- portion of this ring can also be substituted by -O- or -S-. However, if RL3 is a hydrogen atom, RL1 and RL2 are bonded together with these bonded carbon atoms to form an alicyclic ring containing multiple bonds; furthermore, a portion of the hydrogen atoms in this alicyclic ring can also be substituted by a halogen atom. RL4 and RL5 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; RL6 is a hydrocarbon group having 1 to 20 carbon atoms, and the -CH2- portion of this hydrocarbon group can also be substituted by -O- or -S-; in addition, RL5 and RL6 can also bond with each other to form a heterocyclic group having 3 to 20 carbon atoms together with the bonded carbon atoms and LB, and the -CH2- portion of this heterocyclic group can also be substituted by -O- or -S-; LB series -O- or -S-; The RLa~RLd series are each independently composed of hydrogen atoms, or may contain heteroatoms and hydrocarbon groups with 1 to 20 carbon atoms; * indicates an atomic bond with L1. 4. For any of the strontium salt type monomers in 1 to 3, the Z- group represents the anion of the following formula (Z): [Chemistry 4] (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 or 1; however, m1 is...) When m1 is 0, the system is 0 ≤ m2 + m3 + m1 ≤ 4; when m1 is 1, the system is 0 ≤ m2 + m3 + m1 ≤ 6. When m4 is 0, the system is 0 ≤ m5 + m6 ≤ 4; when m4 is 1, the system is 0 ≤ m5 + m6 ≤ 6. When m7 is 0, the system is 0 ≤ m8 + m9 ≤ 5; when m7 is 1, the system is 0 ≤ m8 + m9 ≤ 7. Furthermore, 1 ≤ m2 + m5 + m8 ≤ 4. RA series: hydrogen atom, fluorine atom, methyl or trifluoromethyl; R3, R4, and R5 are each independently a halogen atom other than iodine, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy carbonyl group with 1 to 20 carbon atoms containing heteroatoms; when m3 is 2 or 3, each R3 can be the same or different, and two R3s can also bond to each other to form a ring with the bonded carbon atoms; when m6 is 2 or 3, each R4 can be the same or different, and two R4s can also bond to each other to form a ring with the bonded carbon atoms; when m9 is 2 or 3, each R5 can be the same or different, and two R5s can also bond to each other to form a ring with the bonded carbon atoms; LA1, LA2, LB1, and LB2 are each independently composed of single bonds, ether bonds, carbonyl bonds, ester bonds, sulfonate bonds, amide bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds; XL1 and XL2 are each independently a single-bonded or, alternatively, a hydrocarbon group with 1 to 40 carbon atoms containing heteroatoms. 5. A strontium salt type quenching agent, which is composed of any one of the strontium salt type monomers as described in 1 to 4. 6. A polymer comprising repeating units from a strontium salt-type quencher such as 5. 7. The polymer of formula 6 further contains at least one of the repeating units selected from the following formula (b1), the following formula (b2), and the following formula (b3): [Chemistry 5] (In the formula, each of the RA series is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group;) X1 refers to single bonds, pendiphenyl, pendinaphthyl, *-C(=O)-O-X11- or *-C(=O)-N(H)-X11-, where the pendiphenyl or pendinaphthyl group can be substituted by hydroxyl, nitro, cyano, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, oxygen, or halogen atoms; X11 refers to saturated pendialkyl groups with 1 to 10 carbon atoms, pendiphenyl, or pendinaphthyl groups, where the saturated pendialkyl group can also contain hydroxyl, ether bonds, ester bonds, or lactone rings; X2-series single bonds, *-C(=O)-O- or *-C(=O)-N(H-); * indicates an atomic bond with a carbon atom in the main chain; R11 can be a halogen atom, cyano group, hydroxyl group, nitro group, pentafluorothio group, or may contain a hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbon oxy group with 1 to 20 carbon atoms, a hydrocarbon carbonyl group with 2 to 20 carbon atoms, a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms, or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms; when a1 is 2, 3, or 4, each R11 can be the same or different from the others; AL1 and AL2 are each independently acid-labile groups; a1 series 0, 1, 2, 3 or 4;) [Chemistry 6] (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;) RA series: hydrogen atom, fluorine atom, methyl or trifluoromethyl; X3 series single bonds, *-C(=O)-O- or *-C(=O)-N(H)-; * indicates an atomic bond with a carbon atom in the main chain; X4-series single bonds, aliphatic hydrocarbon groups with 1 to 4 carbon atoms, carbonyl groups, sulfonyl groups, or combinations thereof; The X5 and X6 series are each independently composed of oxygen or sulfur atoms; however, the X4 and X6 series are bonded to adjacent carbon atoms in the aromatic ring. R12 and R13 are each independently a hydrogen atom, or may contain heteroatoms and be hydrocarbon groups with 1 to 20 carbon atoms; furthermore, R12 and R13 can also bond with each other to form a ring with these bonded carbon atoms; R14 can be a halogen atom, hydroxyl group, cyano group, nitro group, pentafluorothio group, or a hydrocarbon group with 1-20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1-20 carbon atoms containing heteroatoms, a hydrocarbon oxy carbonyl group with 2-20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1-20 carbon atoms, or -N (R14A) (R14B); R14A and R14B are each independently a hydrogen atom or a hydrocarbon group with 1-6 carbon atoms; when b2 is 2 or more, each R14 can be the same or different from the others, and multiple R14s can also bond together with each other to form a ring with the carbon atoms of the aromatic rings. 8. Polymers such as 6 or 7 further contain repeating units represented by the following formula (c): [Chemistry 7] (In the formula, RA represents hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups;) Y1 series single bonds, *-C(=O)-O- or *-C(=O)-N(H)-; * indicates an atomic bond with a carbon atom in the main chain; R21 series halogen atoms, carboxyl, nitro, cyano, pentafluorothio, may also contain heteroatoms with 1 to 20 carbon atoms, may also contain heteroatoms with 1 to 20 carbon atoms, may also contain heteroatoms with 2 to 20 carbon atoms, may also contain heteroatoms with 2 to 20 carbon atoms, may also contain heteroatoms with 2 to 20 carbon atoms, or ... alkyloxycarbonyl groups; c1 represents 1, 2, 3, or 4; c2 represents 0, 1, 2, or 3; however, 1 ≤ c1 + c2 ≤ 5. 9. The polymer of any one of 6 to 8 further contains repeating units derived from a fluorosulfonic acid anion having a polymerizable group and at least one iodine atom, and a strontium cation. 10. The polymer of any one of 6 to 9 further contains a repeating unit represented by the following formula (e); [Chemistry 8] (In the formula, RA represents hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups;) Z1 series includes single bonds, pendiphenyl, pendinaphthyl, *-C(=O)-O-Z11- or *-C(=O)-N(H)-Z11-. The pendiphenyl or pendinaphthyl group can also be substituted by hydroxyl, nitro, cyano, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, or saturated hydrocarbon groups with 1 to 10 carbon atoms containing fluorine atoms, oxygen, or halogen atoms; * indicates an atomic bond with a carbon atom in the main chain; Z11 series includes saturated pendialkyl groups with 1 to 10 carbon atoms, pendiphenyl, or pendinaphthyl groups, which can also contain hydroxyl, ether, ester, or lactone rings. R51 refers to a hydrogen atom, or a group containing at least one of the following: hydroxyl group (other than phenolic hydroxyl group), cyano group, carbonyl group, carboxyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulopentalide ring, and carboxylic anhydride (-C(=O)-OC(=O)-). It has 1 to 20 carbon atoms. 11. A chemical amplification inhibitor composition comprising a base polymer containing (A) a polymer containing any one of 6 to 10. 12. As in 11, the chemical amplification inhibitor composition further contains (B) organic solvents. 13. Chemical amplification inhibitors such as those in 11 or 12 further contain (C) quenchers. 14. Any chemical amplification inhibitor composition such as those in 11 to 13 further contains (D) an acid generating agent. 15. Any chemical amplification inhibitor composition such as those in 11 to 14 further contains (E) surfactant. 16. A pattern forming method comprising the steps of: forming a resist film on a substrate using a chemical amplifying resist composition as described in any one of 11 to 15, exposing the resist film to high-energy rays, and developing the exposed resist film using a developing solution. 17. The pattern forming method of 16, wherein the high-energy ray is an ArF excimer laser with a wavelength of 193 nm or a KrF excimer laser with a wavelength of 248 nm, an electron beam or extreme ultraviolet light with a wavelength of 3 to 15 nm. [Effects of the Invention]

[0014] When patterning is performed using a chemically amplified resist composition containing a polymer comprising repeating units that function as quenchers, derived from the strontium salt monomers of the present invention, high contrast and good sensitivity are achieved, resulting in resist patterns with excellent lithography properties such as LWR, CDU, EL, and DOF. Implementation

[0015] [Sulphur salt type monomer] The strontium salt type single system of the present invention is represented by formula (a). [Chemistry 9]

[0016] 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, 2, 3, or 4. The more the number of iodine atoms increases, the more the absorption of EUV light is enhanced, thus contributing to higher sensitivity. However, considering solvent solubility, the total number of iodine atoms in the strontium cation should be 1, 2, or 3. n3 is 1 or 2. n4 is 0, 1, or 2. However, when n5 is 0, it is 0 ≤ n2 + n3 + n4 ≤ 5; when n5 is 1, it is 0 ≤ n2 + n3 + n4 ≤ 7. n5 is 0 or 1. When n5 is 0, it is a benzene ring; when n5 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with n5 = 0. n6 is 1, 2, 3, or 4. n7 is 0, 1, or 2. However, when n5 is 0, it is 0≦n6+n7≦5; when n5 is 1, it is 0≦n6+n7+≦7. n8 is 1 or 2.

[0017] In formula (a), RF refers to 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, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, or a pentafluorothio group. Among these, it is preferable to be a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, a trifluoromethylthio group, or a pentafluorothio group, and more preferably a fluorine atom. When n6 is 2, 3, or 4, the RFs may be the same or different from each other.

[0018] In formula (a), R1 and R2 are each independently a halogen atom other than fluorine, a nitro group, a cyano group, a hydroxyl group, a carboxyl 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. Examples of halogen atoms other than fluorine include chlorine, bromine, and iodine atoms. The hydrocarbon groups, hydrocarbon thio groups, and hydrocarbon oxy groups 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, dibutyl, tributyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; cyclosaturated 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; cyclounsaturated 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. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be substituted by a heteroatom group containing oxygen, sulfur, nitrogen, halogen, etc., and part of the -CH2- group in the aforementioned hydrocarbon group can also be substituted by a heteroatom group containing oxygen, sulfur, nitrogen, etc. As a result, it may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonate ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. When n4 is 2, each R1 can be the same or different. In addition, when n4 is 2, the two R1s can also bond to each other and form a ring together with the carbon atoms of such bonds. The aforementioned ring is preferably a 5- to 8-membered ring. When n7 is 2, each R2 can be the same or different. In addition, when n7 is 2, the two R2s can also bond to each other and form a ring together with the carbon atoms of such bonds. The aforementioned rings should ideally consist of 5 to 8 members.

[0019] In formula (a), L1 represents ether, ester, or carbonate bonds. Among these, ether or ester bonds are preferred.

[0020] In formula (a), RAL is an acid-indestructible group. The acid-indestructible group described above is preferably represented by formula (AL-1) or (AL-2). [Chemistry 10] (In the formula, * represents an atomic bond with L1.)

[0021] In formulas (AL-1) and (AL-2), p1 and p2 are each independently 0 or 1. q1 and q2 are each independently 0, 1, 2, 3, or 4. When L1 is an oxygen atom and a carbonate bond is formed with it, p1 or p2 is 1; otherwise, p1 or p2 should preferably be 0. Furthermore, when p1 is 1, q1 should preferably be 1 or 2; when p1 is 0, q1 is 0. When p2 is 1, q2 should preferably be 1 or 2; when p2 is 0, q2 is 0.

[0022] In formula (AL-1), RL1 and RL2 are each independently a hydrocarbon group having 1 to 12 carbon atoms. RL3 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. The -CH2- portion of the hydrocarbon group represented by RL1, RL2, and RL3 can also be substituted by -O- or -S-. In the case where the hydrocarbon group contains an aromatic ring, part or all of the hydrogen atoms of the aromatic ring can also be substituted by a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms containing a halogen atom, or an alkoxy group having 1 to 4 carbon atoms containing a halogen atom.

[0023] RL1, RL2, and RL3 represent hydrocarbon groups with 1 to 12 carbon atoms, which can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, tripentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, norcamphenylmethyl, adamantyl, adamantylmethyl, tricyclic [5.2.1.02,6]decyl, and tetracyclic [6.2.1.02,6]. [13,6.02,7] Cyclic saturated hydrocarbon groups having 3 to 12 carbon atoms, such as dodecyl; alkenyl groups having 2 to 12 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, pentenyl, and hexenyl; alkynyl groups having 2 to 12 carbon atoms, such as ethynyl, propynyl, butynyl, pentynyl, and hexynyl; cyclic unsaturated aliphatic hydrocarbon groups having 3 to 12 carbon atoms, such as cyclopentenyl and cyclohexenyl; aryl groups having 6 to 12 carbon atoms, such as phenyl, naphthyl, and dihydroindenyl; and aralkyl groups having 7 to 12 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl: and other groups obtained by combining these groups.

[0024] Furthermore, RL1 and RL2 can also bond together with the carbon atoms of these bonds to form a ring, and the -CH2- portion of this ring can be substituted by -O- or -S-. Specific examples of rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, norcamphene rings, adamantane rings, tricyclic [5.2.1.02,6]decane rings, and tetracyclic [6.2.1.13,6.02,7]dodecane rings. Furthermore, the -CH2- portion of the aforementioned rings can also be substituted by -O- or -S-. However, when RL3 is a hydrogen atom, RL1 and RL2 are bonded together with the carbon atoms of these bonds to form an alicyclic ring containing multiple bonds. Furthermore, the hydrogen atoms of this alicyclic ring can also be substituted by halogen atoms.

[0025] In formula (AL-2), RL4 and RL5 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon groups having 1 to 10 carbon atoms represented by RL4 and RL5 can be saturated or unsaturated, and can be linear, branched, or cyclic. As specific examples, those with the same number of carbon atoms as those exemplified as hydrocarbon groups represented by RL1, RL2, and RL3 can be listed.

[0026] In formula (AL-2), RL6 is a hydrocarbon group with 1 to 20 carbon atoms, and part of the -CH2- group can be substituted by -O- or -S-. The above hydrocarbon 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, dibutyl, tributyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, norbornelmethyl, adamantyl, adamantylmethyl, tricyclo[5.2.1.02,6]decyl, tetracyclo[6.2.1.13,6.02,7]dodecyl; vinyl, propenyl, butenyl, etc. Alkenyl groups with 2 to 20 carbon atoms, such as pentenyl and hexenyl; alkyne groups with 2 to 20 carbon atoms, such as ethynyl, propynyl, butynyl, pentynyl, and hexynyl; cyclopentenyl, cyclohexenyl, and norbornenyl; aryl groups with 6 to 20 carbon atoms, such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, dibutylphenyl, tributylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, dibutylnaphthyl, and tributylnaphthyl; aralkyl groups with 7 to 20 carbon atoms, such as benzyl and phenethyl; and other groups obtained by combining these. In addition, RL5 and RL6 can also bond with each other to form heterocyclic groups with 3 to 20 carbon atoms together with the carbon atoms of these bonds and L2. A portion of the -CH2- of the heterocyclic group can also be replaced by -O- or -S-.

[0027] In formulas (AL-1) and (AL-2), RLa~RLd are each independently a hydrogen atom, or may contain heteroatoms, and are hydrocarbon groups with 1 to 20 carbon atoms. These hydrocarbon groups with 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed that are the same as those exemplified as the hydrocarbon group represented by RL6, but are not limited to these.

[0028] In formula (AL-2), L2 is either -O- or -S-.

[0029] Specific examples of unstable acid groups represented by formula (AL-1) can be listed below, but are not limited to these. * indicates an atomic bond with L1. [Chemistry 11]

[0030] [Chemistry 12]

[0031] [Chemistry 13]

[0032] [Chemistry 14]

[0033] [Chemistry 15]

[0034] [Chemistry 16]

[0035] [Chemistry 17]

[0036] [Chemistry 18]

[0037] [Chemistry 19]

[0038] [Chemistry 20]

[0039] [Chemistry 21]

[0040] [Chemistry 22]

[0041] [Chemistry 23]

[0042] [Chemistry 24]

[0043] [Chemistry 25]

[0044] [Chemistry 26]

[0045] [Chemistry 27]

[0046] [Chemistry 28]

[0047] [Chemistry 29]

[0048] [Chemistry 30]

[0049] [Chemistry 31]

[0050] [Chemistry 32]

[0051] Specific examples of unstable acid groups represented by formula (AL-2) can be listed below, but are not limited to these. * indicates an atomic bond with L1. [Chemistry 33]

[0052] [Chemistry 34]

[0053] In formula (a), the iodine atom and -L1-RAL are preferably bonded to adjacent carbon atoms. Due to their proximity and the electron-withdrawing property of the iodine atom, the acidity of the phenols or carboxylic acids generated by deprotecting -RAL is increased, thus improving the solubility contrast.

[0054] Furthermore, two of the three aromatic rings bonded to S+ can also bond with each other to form a ring together with the sulfur atoms of these bonds. Specific examples of the aforementioned ring structures can be given by formulas such as the following. [Chemistry 35] (In the formula, the dashed lines represent atomic bonds.)

[0055] As a strontium salt type monomer represented by formula (a), it is preferable to be represented by the following formula (a1). [Chemistry 36] (In the formula, n2~n4, n6~n8, RF, R1, R2, L1, and RAL are the same as above. Z will be described later.)

[0056] Specific examples of cations of strontium salt-type monomers represented by formula (a) are shown below, but are not limited to these. Furthermore, in the following formula, Me is methyl. Moreover, the substitution positions of the substituents on the aromatic ring are not limited to these. [Chemistry 37]

[0057] [Chemistry 38]

[0058] [Chemistry 39]

[0059] [Chemistry 40]

[0060] [Chemistry 41]

[0061] [Chemistry 42]

[0062] [Chemistry 43]

[0063] [Chemistry 44]

[0064] [Chemistry 45]

[0065] [Chemistry 46]

[0066] [Chemistry 47]

[0067] [Chemistry 48]

[0068] [Chemistry 49]

[0069] [Transformation 50]

[0070] [Chemistry 51]

[0071] [Chemistry 52]

[0072] [Chemistry 53]

[0073] [Chemistry 54]

[0074] [Chemistry 55]

[0075] [Chemistry 56]

[0076] [Chemistry 57]

[0077] [Chem.58]

[0078] [Chemistry 59]

[0079] [Transformation 60]

[0080] [Chemistry 61]

[0081] [Chemistry 62]

[0082] [Chemistry 63]

[0083] [Chemistry 64]

[0084] [Chemistry 65]

[0085] [Chemistry 66]

[0086] [Chemistry 67]

[0087] [Chemistry 68]

[0088] [Chemistry 69]

[0089] [Chemistry 70]

[0090] [Chemistry 71]

[0091] [Chemistry 72]

[0092] [Chemistry 73]

[0093] [Chemistry 74]

[0094] [Chemistry 75]

[0095] [Chemistry 76]

[0096] [Chemistry 77]

[0097] [Chemistry 78]

[0098] [Chemistry 79]

[0099] [Chemistry 80]

[0100] [Chemistry 81]

[0101] [Chemistry 82]

[0102] [Chemistry 83]

[0103] [Chemistry 84]

[0104] [Chemistry 85]

[0105] [Chemistry 86]

[0106] [Chemistry 87]

[0107] [Chemistry 88]

[0108] [Chemistry 89]

[0109] [Chemistry 90]

[0110] [Chemistry 91]

[0111] [Chemistry 92]

[0112] [Chemistry 93]

[0113] [Chemistry 94]

[0114] [Chemistry 95]

[0115] [Chemistry 96]

[0116] [Chemistry 97]

[0117] [Chem. 98]

[0118] [Chemistry 99]

[0119] [Chemistry 100]

[0120] [Chemistry 101]

[0121] [Chemistry 102]

[0122] [Chemistry 103]

[0123] [Chemistry 104]

[0124] [Chemistry 105]

[0125] [Chemistry 106]

[0126] [Chemistry 107]

[0127] [Chemistry 108]

[0128] [Chemistry 109]

[0129] [Chemical 110]

[0130] [Chemistry 111]

[0131] [Chemistry 112]

[0132] [Chemistry 113]

[0133] [Chemistry 114]

[0134] [Chemistry 115]

[0135] [Chemistry 116]

[0136] [Chemistry 117]

[0137] [Chemistry 118]

[0138] [Chemistry 119]

[0139] [Chemistry 120]

[0140] [Chemistry 121]

[0141] [Chemistry 122]

[0142] [Chemistry 123]

[0143] [Chemistry 124]

[0144] [Chemistry 125]

[0145] [Chemistry 126]

[0146] [Chemistry 127]

[0147] [Chemistry 128]

[0148] [Chemistry 129]

[0149] [Chemistry 130]

[0150] [Chemistry 131]

[0151] [Chemistry 132]

[0152] [Chemistry 133]

[0153] [Chemistry 134]

[0154] [Chemistry 135]

[0155] [Chemistry 136]

[0156] [Chemistry 137]

[0157] [Chemistry 138]

[0158] [Chemistry 139]

[0159] [Chemistry 140]

[0160] [Chemistry 141]

[0161] [Chemistry 142]

[0162] [Chemistry 143]

[0163] [Chemistry 144]

[0164] [Chemistry 145]

[0165] [Chemistry 146]

[0166] [Chemistry 147]

[0167] [Chemistry 148]

[0168] [Chemistry 149]

[0169] [Chemistry 150]

[0170] [Chemistry 151]

[0171] [Chemistry 152]

[0172] [Chemistry 153]

[0173] [Chemistry 154]

[0174] [Chemistry 155]

[0175] [Chemistry 156]

[0176] [Chemistry 157]

[0177] [Chemistry 158]

[0178] [Chemistry 159]

[0179] [Chemistry 160]

[0180] [Chemistry 161]

[0181] [Chemistry 162]

[0182] [Chemistry 163]

[0183] [Chemistry 164]

[0184] [Chemistry 165]

[0185] [Chemistry 166]

[0186] [Chemistry 167]

[0187] [Chemistry 168]

[0188] [Chemistry 169]

[0189] [Chemistry 170]

[0190] [Chemistry 171]

[0191] [Chemistry 172]

[0192] [Chemistry 173]

[0193] [Chemistry 174]

[0194] [Chemistry 175]

[0195] [Chemistry 176]

[0196] [Chemistry 177]

[0197] [Chemistry 178]

[0198] [Chemistry 179]

[0199] [Chemistry 180]

[0200] [Chemistry 181]

[0201] [Chemistry 182]

[0202] [Chemistry 183]

[0203] [Chemistry 184]

[0204] [Chemistry 185]

[0205] [Chemistry 186]

[0206] [Chemistry 187]

[0207] [Chem.188]

[0208] [Chemistry 189]

[0209] [Chemistry 190]

[0210] [Chemistry 191]

[0211] [Chemistry 192]

[0212] [Chemistry 193]

[0213] [Chemistry 194]

[0214] [Chemistry 195]

[0215] [Chemistry 196]

[0216] [Chemistry 197]

[0217] [Chemistry 198]

[0218] [Chemistry 199]

[0219] [Chemistry 200]

[0220] [Chemical Engineering 201]

[0221] [Chemical Engineering 202]

[0222] [Chemical Engineering 203]

[0223] [Chemical 204]

[0224] [Chemical Engineering 205]

[0225] [Chemical Engineering 206]

[0226] [Chemical 207]

[0227] [Chemical Engineering 208]

[0228] [Chemical Engineering 209]

[0229] [Chemical 210]

[0230] [Chemistry 211]

[0231] [Chemistry 212]

[0232] [Chemistry 213]

[0233] [Chemistry 214]

[0234] [Chemical 215]

[0235] [Chemistry 216]

[0236] [Chemistry 217]

[0237] [Chemistry 218]

[0238] [Chemistry 219]

[0239] [Chem.220]

[0240] [Chemistry 221]

[0241] [Chemistry 222]

[0242] [Chemistry 223]

[0243] [Chemistry 224]

[0244] [Chemistry 225]

[0245] [Chemistry 226]

[0246] [Chemistry 227]

[0247] [Chemistry 228]

[0248] [Chemistry 229]

[0249] [Chemistry 230]

[0250] [Chemistry 231]

[0251] [Chemistry 232]

[0252] [Chemistry 233]

[0253] [Chemistry 234]

[0254] [Chemistry 235]

[0255] [Chemistry 236]

[0256] [Chemistry 237]

[0257] [Chemistry 238]

[0258] [Chemistry 239]

[0259] [Chemistry 240]

[0260] [Chemistry 241]

[0261] [Chemistry 242]

[0262] [Chemistry 243]

[0263] [Chemistry 244]

[0264] [Chemistry 245]

[0265] [Chemistry 246]

[0266] [Chemistry 247]

[0267] [Chemistry 248]

[0268] [Chemistry 249]

[0269] [Chemistry 250]

[0270] [Chemistry 251]

[0271] [Chemistry 252]

[0272] [Chemistry 253]

[0273] [Chemistry 254]

[0274] [Chemistry 255]

[0275] [Chemistry 256]

[0276] [Chemistry 257]

[0277] [Chemistry 258]

[0278] [Chemistry 259]

[0279] [Chemistry 260]

[0280] [Chemistry 261]

[0281] [Chemistry 262]

[0282] [Chemistry 263]

[0283] [Chemistry 264]

[0284] [Chemistry 265]

[0285] [Chemistry 266]

[0286] [Chemistry 267]

[0287] [Chemistry 268]

[0288] [Chemistry 269]

[0289] [Chemistry 270]

[0290] [Chemistry 271]

[0291] [Chemistry 272]

[0292] [Chemistry 273]

[0293] [Chemistry 274]

[0294] [Chemistry 275]

[0295] [Chemistry 276]

[0296] [Chemistry 277]

[0297] [Chemistry 278]

[0298] [Chemistry 279]

[0299] [Chemistry 280]

[0300] [Chemistry 281]

[0301] [Chemistry 282]

[0302] [Chemistry 283]

[0303] [Chemistry 284]

[0304] [Chemistry 285]

[0305] [Chemistry 286]

[0306] [Chemistry 287]

[0307] [Chemistry 288]

[0308] [Chemistry 289]

[0309] [Chemistry 290]

[0310] [Chemistry 291]

[0311] [Chemistry 292]

[0312] [Chemistry 293]

[0313] [Chemistry 294]

[0314] [Chemistry 295]

[0315] [Chemistry 296]

[0316] [Chemistry 297]

[0317] [Chemistry 298]

[0318] [Chemistry 299]

[0319] [Chemical 300]

[0320] [Chemical Engineering 301]

[0321] [Chemical 302]

[0322] [Chemical 303]

[0323] [Chemical 304]

[0324] [Chemical 305]

[0325] [Chemical 306]

[0326] [Chemical 307]

[0327] [Chemical 308]

[0328] [Chemical 309]

[0329] [Chemical 310]

[0330] [Chemistry 311]

[0331] In formulas (a) and (a1), Z- is a carboxylic acid anion having an aromatic vinyl structure and an iodine atom. As the above-mentioned carboxylic acid anion, it is preferable to be represented by the following formula (Z). [Chemistry 312]

[0332] 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, more preferably 0, 1, or 2, and even more preferably 0 or 1. m3 is 0, 1, 2, or 3.

[0333] In formula (Z), m4 is 0 or 1. When m4 is 0, it represents a benzene ring; when m4 is 1, it represents a naphthalene ring. Considering solvent solubility, it is preferable to have m4 as 0 (benzene ring). m5 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, m5 is preferably 0, 1, 2, or 3, and more preferably 0, 1, or 2. m6 is 0, 1, 2, or 3.

[0334] 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 m7 as 0 (benzene ring). m8 is 1, 2, 3, or 4. Considering the availability of raw materials, m8 is preferably 1, 2, or 3, and more preferably 1 or 2. m9 is 0, 1, 2, or 3.

[0335] In formula (Z), m10 is either 0 or 1. m11 is either 0 or 1.

[0336] However, when m1 is 0, it is 0≦m2+m3+m11≦4; when m1 is 1, it is 0≦m2+m3+m11≦6. When m4 is 0, it is 0≦m5+m6≦4; when m4 is 1, it is 0≦m5+m6≦6. When m7 is 0, it is 0≦m8+m9≦5; when m7 is 1, it is 0≦m8+m9≦7. Furthermore, regarding the number of iodine atoms in the anion, a higher number of iodine atoms results in higher absorption, especially for EUV, but there is a risk of decreased solvent solubility and precipitation in the inhibitor composition; therefore, 1≦m2+m5+m8≦4 is preferable.

[0337] In formula (Z), RA represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Among these, it is preferable to be a hydrogen atom, a methyl group, or more preferably a hydrogen atom.

[0338] In formula (Z), R3 represents a halogen atom other than iodine, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a pentafluorothio 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 1 to 20 carbon atoms containing heteroatoms. The halogen atom other than iodine is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom. 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, dibutyl, tributyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; cyclosaturated 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; cyclounsaturated 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. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups can be substituted by heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- group in the aforementioned hydrocarbon groups can be substituted by heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the hydrocarbon groups may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. When m3 is 2 or 3, each R3 group can be the same or different.

[0339] Furthermore, when m3 is 2 or 3, the two R3 atoms can also bond to each other and form a ring together with the carbon atoms of the aromatic rings in such bonding. Specific examples of rings formed in this way include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. In addition, some or all of the hydrogen atoms in the above-mentioned rings can be replaced by heteroatom groups containing oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and some of the -CH2- in the above-mentioned rings can also be replaced by heteroatom groups containing oxygen atoms, sulfur atoms, nitrogen atoms, etc. As a result, 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.

[0340] In formula (Z), R4 represents a halogen atom other than iodine, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a pentafluorothio group, or a hydrocarbon group containing 1 to 20 carbon atoms with heteroatoms, a hydrocarbon oxy group containing 1 to 20 carbon atoms with heteroatoms, a hydrocarbon thio group containing 1 to 20 carbon atoms with heteroatoms, or a hydrocarbon oxycarbonyl group containing 1 to 20 carbon atoms with heteroatoms. Specific examples of halogen atoms other than iodine atoms include fluorine atoms, chlorine atoms, and bromine atoms. The hydrocarbon groups of the aforementioned hydrocarbon groups, hydrocarbon oxy groups, and hydrocarbon thio groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be those identical to those exemplified as hydrocarbon groups represented by R3, but are not limited to these. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups can be replaced by heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- group in the aforementioned hydrocarbon groups can be replaced by heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the hydrocarbon groups may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. When m6 is 2 or 3, each R4 group can be the same or different.

[0341] Furthermore, when m6 is 2, the two R4 atoms can also bond to each other and form a ring together with the bonded carbon atoms. The aforementioned rings are preferably 5- to 8-membered rings.

[0342] In formula (Z), R5 represents a halogen atom other than iodine, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a pentafluorothio group, or a hydrocarbon group containing 1 to 20 carbon atoms with heteroatoms, a hydrocarbon oxygen group containing 1 to 20 carbon atoms with heteroatoms, a hydrocarbon thio group containing 1 to 20 carbon atoms with heteroatoms, or a hydrocarbon oxygen carbonyl group containing 1 to 20 carbon atoms with heteroatoms. Specific examples of halogen atoms other than iodine atoms include fluorine atoms, chlorine atoms, and bromine atoms. The hydrocarbon groups of the aforementioned hydrocarbon groups, hydrocarbon oxygen groups, and hydrocarbon thio groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be those identical to those exemplified as hydrocarbon groups represented by R3, but are not limited to these. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups can be substituted by heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- group in the aforementioned hydrocarbon groups can also be substituted by heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the hydrocarbon groups may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. When m9 is 2 or 3, each R5 group can be the same or different.

[0343] Furthermore, when m9 is 2, the two R5 atoms can also bond to each other and form a ring together with the bonded carbon atoms. The aforementioned rings are preferably 5- to 8-membered rings.

[0344] In formula (Z), LA1, LA2, LB1, and LB2 are each independently a single bond, ether bond, carbonyl bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. Of these, LA1 is preferably a single bond, ether bond, ester bond, or sulfonate bond, and more preferably an ether bond, ester bond, or sulfonate bond. LA2 is preferably a single bond, ether bond, ester bond, amide bond, sulfonamide bond, or sulfonate bond, and more preferably an ester bond or sulfonate bond. LB1 is preferably a single bond, ether bond, ester bond, amide bond, or sulfonate bond, and more preferably a single bond, ether bond, or ester bond. LB2 is preferably a single bond, ether bond, ester bond, amide bond, or sulfonate bond, and more preferably a single bond, ether bond, or ester bond.

[0345] When m11 is 1, LA1 and LA2 should ideally be bonded to adjacent carbon atoms of the aromatic ring. In this case, the substituents containing the fluorosulfonic acid anion structure and the substituents containing the aromatic ring substituted by the iodine atom are spatially closer, and higher sensitivity can be expected.

[0346] In formula (Z), XL1 and XL2 are each an independent single bond, or may contain heteroatoms and have 1 to 40 carbon atoms in an extended hydrocarbon group. These extended hydrocarbon groups can be linear, branched, or cyclic; specific examples include alkane dimethyl groups, cyclic saturated extended hydrocarbon groups, and extended aryl groups. Specific examples of the heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0347] Specific examples of XL1 and XL2 that may contain heteroatoms and carbon atoms of 1 to 40 carbon atoms are shown below, but are not limited to these. Furthermore, in the following formulas, * represents atomic bonds with LA1 and LB1, or with LA2 and LB2, respectively. [Chemistry 313]

[0348] [Chemical 314]

[0349] [Chemical 315]

[0350] [Chemistry 316]

[0351] Among these, the most suitable are XL-0~XL-22, XL-29~XL-34 and XL-47~XL-61.

[0352] Specific examples of anions of onium salt type monomers represented by formula (a) can be listed below, but are not limited to these. Furthermore, in the following formulas, RA refers to the same as above, and Me refers to methyl groups. In addition, the bonding positions of various substituents on the aromatic ring can also be interchanged on the aromatic ring. [Chemistry 317]

[0353] [Chemistry 318]

[0354] [Chemistry 319]

[0355] [Chemistry 320]

[0356] [Chemistry 321]

[0357] [Chemistry 322]

[0358] [Chemistry 323]

[0359] [Chemistry 324]

[0360] [Chemistry 325]

[0361] [Chemistry 326]

[0362] [Chemistry 327]

[0363] [Chemistry 328]

[0364] [Chemistry 329]

[0365] [Chemistry 330]

[0366] [Chemistry 331]

[0367] [Chemistry 332]

[0368] [Chemistry 333]

[0369] [Chemistry 334]

[0370] [Chemistry 335]

[0371] [Chemistry 336]

[0372] [Chemistry 337]

[0373] [Chemistry 338]

[0374] [Chemistry 339]

[0375] [Transformation 340]

[0376] [Chemistry 341]

[0377] [Chemistry 342]

[0378] [Chemistry 343]

[0379] [Chemistry 344]

[0380] [Chemistry 345]

[0381] [Chemistry 346]

[0382] [Chemistry 347]

[0383] [Chemistry 348]

[0384] [Chemistry 349]

[0385] [Chemical 350]

[0386] [Chemistry 351]

[0387] [Chemistry 352]

[0388] [Chemistry 353]

[0389] [Chemistry 354]

[0390] [Chemistry 355]

[0391] [Chemistry 356]

[0392] [Chemistry 357]

[0393] [Chemistry 358]

[0394] [Chemistry 359]

[0395] [Hua360]

[0396] [Chem 361]

[0397] [Chem 362]

[0398] [Chem 363]

[0399] [Chem 364]

[0400] [Chem 365]

[0401] [Chem 366]

[0402] [Chem 367]

[0403] [Chem 368]

[0404] [Chem 369]

[0405] [Chem 370]

[0406] [Chem 371]

[0407] [Chem 372]

[0408] [Chem 373]

[0409] [Chem 374]

[0410] [Chemistry 375]

[0411] [Chemistry 376]

[0412] [Chemistry 377]

[0413] [Chemistry 378]

[0414] [Chemistry 379]

[0415] [Chemistry 380]

[0416] [Chemistry 381]

[0417] [Chemistry 382]

[0418] [Chemistry 383]

[0419] [Chem. 384]

[0420] [Chem.385]

[0421] [Chemistry 386]

[0422] [Chemistry 387]

[0423] [Chem.388]

[0424] [Chemistry 389]

[0425] [Chemistry 390]

[0426] [Chemistry 391]

[0427] [Chemistry 392]

[0428] [Chemistry 393]

[0429] [Chemistry 394]

[0430] [Chemistry 395]

[0431] [Chemistry 396]

[0432] [Chemistry 397]

[0433] [Chem.398]

[0434] [Chemistry 399]

[0435] [Chemical 400]

[0436] [Chemical Engineering 401]

[0437] [Chemical 402]

[0438] [Chemical 403]

[0439] [Chemical 404]

[0440] [Chemical 405]

[0441] [Chemical 406]

[0442] [Chemical 407]

[0443] [Chemical 408]

[0444] [Chemical 409]

[0445] [Chemical 410]

[0446] [Chemistry 411]

[0447] [Chemistry 412]

[0448] [Chemistry 413]

[0449] [Chemistry 414]

[0450] [Chemical 415]

[0451] [Chemistry 416]

[0452] [Chemistry 417]

[0453] [Chemistry 418]

[0454] [Chemistry 419]

[0455] [Chem.420]

[0456] [Chemistry 421]

[0457] [Chemistry 422]

[0458] [Chemistry 423]

[0459] Other specific examples of anions of onium salt type monomers represented by formula (a) may be listed in paragraphs

[0049] ,

[0054] to

[0056] , and

[0062] to

[0064] of Japanese Patent No. 7433394, and paragraph

[0116] of Japanese Unexamined Patent Application Publication No. 2024-178693, but are not limited to these.

[0460] As specific examples of the strontium salt type monomers of this invention, any combination of the above-mentioned anions and cations can be listed.

[0461] The strontium salt type monomer of the present invention can be synthesized by known methods. Specifically, the method described in paragraphs

[0402] to

[0405] of Japanese Patent No. 7433394 can be cited, but the synthesis method is not limited to that method.

[0462] [polymer] The polymer system of the present invention contains repeating units (hereinafter also referred to as repeating unit a) derived from the strontium salt type monomer represented by formula (a).

[0463] The polymer of this invention functions as a quencher in a chemical amplification inhibitor composition while also functioning as a base polymer; it is a polymer-bonded quencher. Structural features of the polymer include repeating units from the strontium salt monomer of this invention. These repeating units have: a carboxylic acid anion with an iodine atom directly bonded to the main chain (benzene or naphthalene), and an acid-unstable triarylstrontium cation with an iodine atom on the same aromatic ring and an acid-unstable group having a tertiary / secondary ether, tertiary / secondary ester, tertiary / secondary carbonate, or acetal structure. The iodine atom has a large atomic weight, thus exhibiting low acid diffusion. This prevents the reduction in resolution caused by acid diffusion blurring, improving LWR and CDU. Furthermore, because EUV at a wavelength of 13.5 nm has extremely high absorption, secondary electrons are generated during exposure, and their energy moves towards the acid-generating agent, promoting decomposition and thereby achieving high sensitivity. Polymerizable groups composed of styrene or vinylnaphthalene structures are more rigid than those of methacrylates, thus increasing the glass transition temperature (Tg) of the polymer. It is believed that through the interaction of aromatic rings within or between polymers (π-π stacking effect), the polymers are regularly arranged, exhibiting resistance to pattern collapse even during the formation of fine patterns in the developer. Furthermore, even in the etching step after the formation of fine patterns, excellent etching resistance is exhibited due to the aromatic rings directly bonded to the main chain. On the other hand, it is known that iodine atoms bonded to aromatic rings of strontium cations exhibit very high EUV absorption, similar to those bonded to anions, thus generating secondary electrons from iodine atoms during exposure, and exhibiting electron-withdrawing properties due to their halogen nature. The acid-labile groups on the same aromatic ring of the strontium cation, possessing tertiary / secondary ether, tertiary / secondary ester, tertiary / secondary carbonate, or acetal structures, undergo deprotection reactions due to the acid generated during exposure, producing corresponding phenols or carboxylic acids. This transformation from lipophilic to hydrophilic structures improves the contrast between the exposed and unexposed areas. Furthermore, iodine atoms are bonded to adjacent carbon atoms of the phenolic hydroxyl or carboxyl groups generated during the deprotection reaction, increasing the acidity of the phenols and carboxylic acids through the electron-withdrawing property of the iodine atoms. When the deprotected exposed areas are developed with an alkaline developer, the increased acidity of the phenols improves their solubility in the alkaline developer, thus suppressing development residue. Additionally, the other aromatic rings in the triarylstrontium cation preferably contain substituents with fluorine atoms. It is believed that substituents containing fluorine atoms or fluorine atoms have strong electron-withdrawing properties, lowering the LUMO energy level in the front-end molecular orbital theory of triarylstrom cations. Therefore, they readily accept secondary electrons from iodine atoms in both cations and anions, promoting the decomposition of cations and efficiently generating acids.Furthermore, the carboxylic acid anion system has relatively high basicity, effectively capturing acids generated from strong acids. Through these additive effects, it improves the lithography properties of LWR, CDU, etc., while maintaining high sensitivity, and becomes capable of forming patterns that suppress development residues, making it particularly suitable as a material for chemical amplification positive resist components. In addition, the aromatic ring system functions as a good etching resistance group, making it suitable for the formation of fine patterns.

[0464] [polymer] The polymer system of the present invention contains repeating units (hereinafter also referred to as repeating unit a) derived from the strontium salt type monomer represented by formula (a).

[0465] The 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.). [Chemistry 424]

[0466] In formulas (b1) and (b2), each of the RA series is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0467] In formula (b1), X1 is a single bond, phenyl, naphthyl, *-C(=O)-O-X11-, or *-C(=O)-N(H)-X11-. This phenyl or naphthyl group can also be substituted by a hydroxyl, nitro, 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. X11 is a saturated hydrocarbon group with 1 to 10 carbon atoms, phenyl, or naphthyl. This saturated hydrocarbon group can also contain a hydroxyl, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0468] In formula (b2), X2 represents a single bond, *-C(=O)-O-, or *-C(=O)-N(H)-. * indicates an atomic bond with a carbon atom in the main chain. R11 represents a halogen atom, cyano group, hydroxyl group, nitro group, pentafluorosulfur group, or may contain a hydrocarbon group with 1-20 carbon atoms, a hydrocarbon oxygen group with 1-20 carbon atoms, a hydrocarbon carbonyl group with 2-20 carbon atoms, a hydrocarbon carbonyl oxygen group with 2-20 carbon atoms, or a hydrocarbon oxygen carbonyl group with 2-20 carbon atoms. a1 is 0, 1, 2, 3, or 4, preferably 0 or 1. When a1 is 2, 3, or 4, each R11 can be the same or different.

[0469] In formulas (b1) and (b2), AL1 and AL2 are each an acid-indestructible group. Specific examples of the aforementioned acid-indestructible groups can be found in Japanese Patent Application Publication No. 2013-80033 or Japanese Patent Application Publication No. 2013-83821.

[0470] Typically, specific examples of the aforementioned unstable acid groups can be represented by the following formulas (AL-3) to (AL-5). [Chemical 425] (In the formula, * represents an atomic bond.)

[0471] In formulas (AL-3) and (AL-4), RL11 and RL12 are each independently a hydrocarbon group with 1 to 40 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, fluorine, and iodine atoms. The aforementioned hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Preferably, the hydrocarbon group has 1 to 20 carbon atoms.

[0472] In formula (AL-3), a2 is an integer from 0 to 10, and should preferably be 1, 2, 3, 4 or 5.

[0473] In formula (AL-4), RL13 and RL14 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, fluorine, and iodine atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Furthermore, any two of RL12, RL13, and RL14 can bond together with these bonded carbon atoms or carbon and oxygen atoms to form a ring having 3 to 20 carbon atoms. The ring is preferably a ring having 4 to 16 carbon atoms, and especially preferably an alicyclic ring.

[0474] In formula (AL-5), RL15, RL16, and RL17 are each independently a hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, fluorine, and iodine atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Furthermore, any two of RL15, RL16, and RL17 can bond together to form a ring with 3 to 20 carbon atoms. The ring is preferably a ring with 4 to 16 carbon atoms, and especially preferably an alicyclic ring.

[0475] Other specific examples of the aforementioned acid-indestabilized groups include those described in paragraphs

[0064] to

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

[0013] to

[0014] of Japanese Patent Publication No. 7492842. In these cases, the formation of a conjugated olefin or acrylate derivative after the acid de-reaction is used as the driving force for the reaction.

[0476] Specific examples of repeating unit b1 can be listed below, but are not limited to these. Furthermore, in the following formula, RA and AL1 are the same as those described above. [Chemistry 426]

[0477] [Chemistry 427]

[0478] [Chemistry 428]

[0479] [Chemistry 429]

[0480] [Chemistry 430]

[0481] [Chemistry 431]

[0482] [Chemistry 432]

[0483] Specific examples of repeating unit b2 can be listed below, but are not limited to these. Furthermore, in the following formula, RA and AL2 are the same as described above. [Chemistry 433]

[0484] [Chemistry 434]

[0485] [Chemistry 435]

[0486] The polymers described above may also contain repeating units represented by the following formula (b3) (hereinafter also referred to as repeating unit b3). [Chemistry 436]

[0487] In formula (b3), 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 being 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, and more preferably 0, 1, or 2.

[0488] In formula (b3), RA refers to a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. RA is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0489] In formula (b3), X3 represents a single bond, *-C(=O)-O-, or *-C(=O)-N(H)-. * indicates an atomic bond with a carbon atom in the main chain. Among these, a single bond is preferable, and *-C(=O)-O- is even more preferable.

[0490] In formula (b3), X4 is a single bond, an aliphatic hydrocarbon 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 group generated after the reaction, a single bond or a carbonyl group is even more preferable.

[0491] In formula (b3), X5 and X6 are each independently oxygen or sulfur atoms. However, X4 and X6 are bonded to adjacent carbon atoms of the aromatic ring. X5 and X6 can be the same or different from each other; considering reactivity, it is advisable that X5 and X6 are both oxygen atoms.

[0492] In formula (b3), R12 and R13 are each independently a hydrogen atom, or may contain heteroatoms and have 1 to 20 carbon atoms as hydrocarbon groups. The above 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, dibutyl, tributyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; 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; cyclounsaturated alkyl 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 other alkyl groups obtained by combinations thereof. Furthermore, one or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by a heteroatom group containing oxygen, sulfur, nitrogen, halogen, etc., and one part of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by a heteroatom group containing oxygen, sulfur, nitrogen, etc. As a result, it may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc.

[0493] Furthermore, R12 and R13 can also bond with each other to form a ring together with the carbon atoms of these bonds. Specific examples of rings formed in this way include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. In addition, some or all of the hydrogen atoms in the above-mentioned rings can be replaced by heteroatom groups containing oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and some of the -CH2- in the above-mentioned rings can also be replaced by heteroatom groups containing oxygen atoms, sulfur atoms, nitrogen atoms, etc. As a result, 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.

[0494] In formula (b3), R14 can be a halogen atom, hydroxyl group, cyano group, nitro group, pentafluorothio 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 oxycarbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms, or -N(R14A)(R14B). R14A and R14B are each independently a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms. The aforementioned halogen atom is preferably a fluorine atom, chlorine atom, bromine atom, or iodine atom, and more preferably a fluorine atom or iodine atom. The hydrocarbon group and the hydrocarbon oxy group, hydrocarbon oxycarbonyl group, and hydrocarbon thio group can be saturated or unsaturated, and can be linear, branched, or cyclic. As specific examples, the hydrocarbon groups represented by R12 and R13 are the same. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups can be substituted by heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- group in the aforementioned hydrocarbon groups can also be substituted by heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the hydrocarbon groups may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. When b2 is 2 or more, each R14 group can be the same or different.

[0495] Furthermore, when b2 is 2 or more, the complex number of R14 atoms can also bond with each other to form a ring together with the carbon atoms of the aromatic rings formed in this way. Specific examples of rings formed in this way include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, adamantane rings, etc. In addition, some or all of the hydrogen atoms in the above-mentioned rings can be replaced by heteroatom groups containing oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and some of the -CH2- in the above-mentioned rings can also be replaced by heteroatom groups containing oxygen atoms, sulfur atoms, nitrogen atoms, etc. As a result, 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.

[0496] Specific examples of repeating unit b3 can be listed below, but are not limited to these. Furthermore, in the following formula, RA refers to the same as above, and Me refers to methyl groups. In addition, the bonding positions of various substituents on the aromatic ring can also be interchanged. [Chemistry 437]

[0497] [Chemistry 438]

[0498] [Chemistry 439]

[0499] [Chemistry 440]

[0500] [Chemistry 441]

[0501] [Chemistry 442]

[0502] [Chemistry 443]

[0503] [Chemistry 444]

[0504] [Chemistry 445]

[0505] [Chemistry 446]

[0506] [Chemistry 447]

[0507] [Chemistry 448]

[0508] [Chemistry 449]

[0509] [Chemistry 450]

[0510] [Chemistry 451]

[0511] [Chemistry 452]

[0512] [Chemistry 453]

[0513] [Chemistry 454]

[0514] [Chemistry 455]

[0515] [Chemistry 456]

[0516] [Chemistry 457]

[0517] [Chemistry 458]

[0518] [Chemistry 459]

[0519] [Chemistry 460]

[0520] [Chemistry 461]

[0521] [Chemistry 462]

[0522] [Chemistry 463]

[0523] [Chemistry 464]

[0524] [Chemistry 465]

[0525] [Chemistry 466]

[0526] [Chemistry 467]

[0527] [Chemistry 468]

[0528] [Chemistry 469]

[0529] [Chemistry 470]

[0530] [Chemistry 471]

[0531] [Chemistry 472]

[0532] [Chemistry 473]

[0533] [Chemistry 474]

[0534] [Chemistry 475]

[0535] [Chemistry 476]

[0536] [Chemistry 477]

[0537] [Chemistry 478]

[0538] [Chemistry 479]

[0539] [Chemistry 480]

[0540] [Chemistry 481]

[0541] [Chemistry 482]

[0542] [Chemistry 483]

[0543] [Chemistry 484]

[0544] [Chemistry 485]

[0545] [Chemistry 486]

[0546] The polymer described above preferably contains a repeating unit represented by the following formula (c) (hereinafter also referred to as repeating unit c). [Chemistry 487]

[0547] In formula (c), RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Y1 is a single bond, *-C(=O)-O-, or *-C(=O)-N(H)-. * indicates an atomic bond with a carbon atom in the main chain. R21 is a halogen atom, a carboxyl group, a nitro group, a cyano group, a pentafluorothio group, or may contain a heteroatom with 1 to 20 carbon atoms, a heteroatom with 1 to 20 carbon atoms, a heteroatom with 2 to 20 carbon atoms, a heteroatom with 2 to 20 carbon atoms, a heteroatom with 2 to 20 carbon atoms, or a heteroatom with 2 to 20 carbon atoms. c1 is 1, 2, 3, or 4. c2 is 0, 1, 2, or 3. However, 1 ≤ c1 + c2 ≤ 5.

[0548] Specific examples of repeating unit c can be listed below, but are not limited to these. Furthermore, in the following formula, RA is the same as described above. [Chemistry 488]

[0549] [Chemistry 489]

[0550] [Chemistry 490]

[0551] [Chemistry 491]

[0552] [Chemistry 492]

[0553] The polymers described above preferably contain repeating units (hereinafter also referred to as repeating units d) derived from onium salt monomers containing a fluorosulfonic acid anion and a strontium cation with a polymerizable group and at least one iodine atom.

[0554] Specific examples of the anion of the repeating unit d can be found in the structures described in Japanese Patent No. 6973274

[0023] to

[0029] , Japanese Patent Application Publication No. 2023-172928

[0032] to

[0038] , and Japanese Patent Application Publication No. 2024-043941

[0032] to

[0047] .

[0555] Furthermore, a specific example of the anion of the repeating unit d should be represented by the following formula (d1). [Chemistry 493]

[0556] In formula (d1), d1 is 0 or 1. When d1 is 0, it is a benzene ring; when d1 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with d1 = 0. d2 is 0 or 1. When d2 is 0, it is a benzene ring; when d2 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with d2 = 0. d3 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, d3 is preferably 0, 1, or 2, and more preferably 0 or 1. d4 is 0, 1, 2, 3, or 4. It is preferably 0, 1, 2, or 3, and more preferably 0, 1, or 2, and even more preferably 0 or 1. d5 is 1, 2, 3, 4, 5, or 6. The more iodine atoms in the anionic structure, the higher the absorption, especially for EUV, but there is a risk of decreased solvent solubility and precipitation in the inhibitor composition. Therefore, d5 is preferably 1, 2, or 3, and more preferably 1 or 2. However, when d2 is 0, it is 1≦d4+d5≦4, and when d2 is 1, it is 1≦d4+d5≦6. d6 can be 0, 1, 2, 3, or 4, and should preferably be 0, 1, 2, or 3, and even more preferably 1.

[0557] In formula (d1), RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Among these, it is preferable to be a hydrogen atom, a methyl group, or more preferably a hydrogen atom.

[0558] In formula (d1), the iodine atom in the aromatic ring of the anion should be bonded to the adjacent position of the carbon atom in the LB bond. Iodine atom is an element with a large atomic radius, so it inhibits the rotation of the bonding axis between the aromatic ring bonded by the polymerizable group and the aromatic ring bonded by the iodine atom, thereby improving the rigidity of the polymer.

[0559] In formula (d1), R31 is a halogen atom, or may contain a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms. The halogen atom is preferably a fluorine atom, chlorine atom, bromine atom, or iodine atom, and more preferably a fluorine atom or iodine atom. The hydrocarbon 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, dibutyl, tributyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; 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; cyclounsaturated alkyl 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 other alkyl groups obtained by combinations thereof. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups can be substituted by heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- group in the aforementioned hydrocarbon groups can also be substituted by heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the hydrocarbon groups may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. When d3 is 2, 3, or 4, each R31 can be the same or different from the others.

[0560] Furthermore, when d3 is 2, 3, or 4, the complex R31 can also bond with each other to form a ring together with the carbon atoms of the aromatic rings formed in this way. Specific examples of rings formed in this way include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. In addition, some or all of the hydrogen atoms in the above-mentioned rings can be replaced by heteroatom groups containing oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and some of the -CH2- in the above-mentioned rings can also be replaced by heteroatom groups containing oxygen atoms, sulfur atoms, nitrogen atoms, etc. As a result, 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.

[0561] In formula (d1), R32 is a halogen atom other than an iodine atom, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms. Specific examples of halogen atoms other than iodine atoms include fluorine atoms, chlorine atoms, bromine atoms, etc. The above-mentioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be those identical to those exemplified as hydrocarbon groups represented by R31, but are not limited to these. When d4 is 2, 3, or 4, each R32 can be the same or different from the others.

[0562] Furthermore, when d4 is 2, 3, or 4, complex R32 atoms can also bond with each other to form a ring together with these bonded carbon atoms. The aforementioned rings are preferably 5- to 8-membered rings.

[0563] In formula (d1), LC, LD, and LE are each independently a single bond, ether bond, ester bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Among these, LC is preferably a single bond, ether bond, ester bond, or sulfonate bond, and more preferably an ester bond or sulfonate bond. LD is preferably a single bond, ether bond, or ester bond, and more preferably a single bond. LE is preferably a single bond, ether bond, ester bond, or sulfonate bond, and more preferably an ether bond or ester bond.

[0564] In formula (d1), XL3 is a single bond, or may contain a heteroatom and be an extended hydrocarbon group with 1 to 40 carbon atoms. The extended hydrocarbon group can be linear, branched, or cyclic; specific examples include alkyldiyl, cyclic saturated extended hydrocarbon groups, and extended aryl groups. Specific examples of the heteroatom include oxygen, nitrogen, and sulfur atoms. Specific examples of extended hydrocarbon groups with 1 to 40 carbon atoms represented by XL3 include XL-0 to XL-61, as exemplified in the description of formula (Z) as XL1 and XL2, which may also contain heteroatoms. Among these, XL-0 to XL-22, XL-29 to XL-34, and XL-47 to XL-61 are preferred.

[0565] Considering the rigidity of the obtained polymer, XL3 should ideally be a single bond.

[0566] In formula (d1), Q1 and Q2 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. As a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, trifluoromethyl is preferred.

[0567] In formula (d1), Q3 and Q4 are each independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. As a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, trifluoromethyl is preferred. As Q3 and Q4, fluorine atoms are even more preferred.

[0568] In formula (d1), the specific example of the substructure represented by -[C(Q1)(Q2)]d6-C(Q3)(Q4)-SO3- is preferably as shown below, but is not limited to these. Furthermore, in the following formula, * denotes an atomic bond with LC. [Chemistry 494]

[0569] Of these, Acid-1 to Acid-7 are preferred, and Acid-1 to Acid-3, Acid-6 and Acid-7 are even more preferred.

[0570] The anion represented by formula (d1) should preferably be represented by the following formula (d1-1). [Chemistry 495] (In the formula, d1~d6, RA, R31, R32, LC, LE, Q1~Q4 and Z+ series are the same as above.)

[0571] The anion represented by formula (d1-1) should preferably be represented by formula (d1-2). [Chemistry 496] (In the formula, d1~d6, RA, R31, R32, LC, Q1, Q2 and Z+ are the same as above.)

[0572] Specific examples of anions represented by formula (d1) can be listed below, but are not limited to these. Furthermore, in the following formula, RA and Q1 are the same as above, and Me is a methyl group. In addition, the bonding positions of various substituents on the aromatic ring can also be interchanged. [Chemistry 497]

[0573] [Chemistry 498]

[0574] [Chemistry 499]

[0575] [Chemical 500]

[0576] [Chemical 501]

[0577] [Chemical 502]

[0578] [Chemical 503]

[0579] [Chemical 504]

[0580] [Chemical 505]

[0581] [Chemical 506]

[0582] [Chemical 507]

[0583] [Chemical 508]

[0584] [Chemical 509]

[0585] [Chem.510]

[0586] [Chem.511]

[0587] [Chem.512]

[0588] [Chem.513]

[0589] [Chem.514]

[0590] [Chem.515]

[0591] [Chem.516]

[0592] [Chem.517]

[0593] [Chem.518]

[0594] [Chem.519]

[0595] [Chem.520]

[0596] [Chem.521]

[0597] [Chem.522]

[0598] [Chem.523]

[0599] [Chem.524]

[0600] [Chem.525]

[0601] [Chem.526]

[0602] [Chem.527]

[0603] [Chem.528]

[0604] [Chem. 529]

[0605] [Chem.530]

[0606] [Chemistry 531]

[0607] [Chemistry 532]

[0608] [Chem.533]

[0609] [Chemistry 534]

[0610] [Chem.535]

[0611] [Chemistry 536]

[0612] [Chemistry 537]

[0613] [Chem.538]

[0614] [Chem.539]

[0615] [Chem.540]

[0616] [Chemistry 541]

[0617] [Chemistry 542]

[0618] [Chem.543]

[0619] [Chemistry 544]

[0620] [Chem.545]

[0621] [Chemistry 546]

[0622] [Chemistry 547]

[0623] [Chem.548]

[0624] [Chemistry 549]

[0625] [Chemical 550]

[0626] [Chemistry 551]

[0627] [Chem.552]

[0628] [Chem.553]

[0629] As the anion of the repeating unit d, it is also appropriate to represent it by the following formula (d2). [Chem.554]

[0630] In formula (d2), d11 is 0 or 1. When d11 is 0, it is a benzene ring; when d11 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with d11 of 0. d12 is 1, 2, 3, or 4. Considering the availability of raw materials, d12 is preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1. d13 is 0, 1, or 2. However, when d11 is 0, it is 1 ≤ d12 + d13 ≤ 4; when d11 is 1, it is 1 ≤ d12 + d13 ≤ 6.

[0631] In formula (d2), d14 is 0 or 1. When d14 is 0, it is a benzene ring; when d14 is 1, it is a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with d14 of 0. d15 is 1, 2, 3, or 4, preferably 1, 2, or 3. The more iodine atoms in the anionic structure, the higher the absorption, especially for EUV, but the solvent solubility decreases, and there is a risk of precipitation in the inhibitor composition. Therefore, the number of iodine atoms in the anion is preferably 2, 3, 4, or 5, and more preferably 2, 3, or 4. d16 is 0, 1, or 2. However, when d14 is 0, it is 1≦d15+d16≦4; when d14 is 1, it is 1≦d15+d16≦6.

[0632] In formula (d2), d17 is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 1, 2 or 3, and even more preferably 1.

[0633] In formula (d2), RA refers to a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Among these, it is preferable to be a hydrogen atom, a methyl group, or more preferably a hydrogen atom.

[0634] In formula (d2), R33 represents a halogen atom other than an iodine atom, a nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. The halogen atom other than the iodine atom mentioned above is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom. 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, dibutyl, tributyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; 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; cyclounsaturated alkyl 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 other alkyl groups obtained by combinations thereof. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups can be substituted by heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- group in the aforementioned hydrocarbon groups can also be substituted by heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the hydrocarbon groups may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. When d13 is 2, each R33 can be the same or different from the others.

[0635] Furthermore, when d13 is 2, the two R33 atoms can also bond with each other to form a ring together with the carbon atoms of the aromatic rings. Specific examples of rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornene rings, and adamantane rings. In addition, some or all of the hydrogen atoms in the above rings can be substituted by heteroatoms containing oxygen, sulfur, nitrogen, or halogen atoms, and some of the -CH2- atoms in the above rings can also be substituted by heteroatoms containing oxygen, sulfur, or nitrogen atoms. As a result, the rings 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.

[0636] In formula (d2), R34 can be a halogen atom other than iodine, a nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms. Specific examples of halogen atoms other than iodine include fluorine, chlorine, and bromine atoms. The hydrocarbon groups, hydrocarbon oxy groups, and hydrocarbon thio groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be those identical to those exemplified as hydrocarbon groups represented by R33, but are not limited to these. When d16 is 2, each R34 can be the same or different from the others.

[0637] Furthermore, when d16 is 2, the two R34 atoms can also bond to each other and form a ring together with the bonded carbon atoms. The aforementioned rings are preferably 5- to 8-membered rings.

[0638] In formula (d2), LF1, LF2, LG1, and LG2 are each independently a single bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, carbonate bond, or carbamate bond. Of these, LF1 is preferably a single bond, ether bond, ester bond, or sulfonate bond, and more preferably an ester bond or sulfonate bond. LF2 is preferably a single bond, ether bond, ester bond, or sulfonate bond, and more preferably an ester bond or sulfonate bond. LG1 is preferably a single bond, ether bond, ester bond, or sulfonate bond, and more preferably a single bond, ether bond, or ester bond. LG2 is preferably a single bond, ether bond, ester bond, or sulfonate bond, and more preferably a single bond, ether bond, or ester bond.

[0639] LF1 and LF2 should be bonded to adjacent carbon atoms of the aromatic ring. In this case, the substituents containing the fluorosulfonic acid anion structure and the substituents containing the iodine-substituted aromatic ring are located in closer spatial positions, thus higher sensitivity is expected.

[0640] In formula (d2), XL4 and XL5 are each independently a single bond, or may contain heteroatoms and have 1 to 40 carbon atoms in an extended hydrocarbon group. The aforementioned extended hydrocarbon group can be linear, branched, or cyclic; specific examples include alkyldiyl, cyclic saturated extended hydrocarbon group, and extended aryl. Specific examples of the aforementioned heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms. Specific examples of extended hydrocarbon groups with 1 to 40 carbon atoms, represented by XL4 and XL, that may also contain heteroatoms, as exemplified in the description of formula (Z) as XL1 and XL2, are XL-0 to XL-61. Among these, XL-0 to XL-22, XL-29 to XL-34, and XL-47 to XL-61 are preferred.

[0641] In formula (d2), Q11 and Q12 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. As the fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, trifluoromethyl is preferred.

[0642] In formula (d2), Q13 and Q14 are each independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. As the fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, trifluoromethyl is preferred. As Q13 and Q14, fluorine atoms are more preferred.

[0643] In formula (d2), specific examples of the substructure represented by -[C(Q11)(Q12)]d17-C(Q13)(Q14)-SO3- are preferably those shown below, but are not limited thereto. In addition, in the following formula, * represents an atomic bond to LG1. [Chem 555]

[0644] Among these, Acid-1 to Acid-7 are preferred, and Acid-1 to Acid-3, Acid-6 and Acid-7 are more preferred.

[0645] As the anion represented by formula (d2), those represented by the following formula (d2-1) are preferred. [Chem 556] (In the formula, RA, R33, R34, LF1, LF2, Q11 to Q14 and d11 to d17 are the same as defined above.)

[0646] As the anion represented by formula (d2-1), those represented by the following formula (d2-2) are preferred. [Chem 557] (In the formula, RA, R33, R34, LF2, Q11, Q12 and d11 to d17 are the same as defined above.)

[0647] Specific examples of the anion represented by formula (d2) include those shown below, but are not limited thereto. In addition, in the following formula, RA and Q11 are the same as defined above, and Me is a methyl group. Further, the bonding positions of various substituents on the aromatic ring may be mutually replaced. [Chem 558]

[0648] [Chem.559]

[0649] [Transformation 560]

[0650] [Chem.561]

[0651] [Chem.562]

[0652] [Chem.563]

[0653] [Chem.564]

[0654] [Chem.565]

[0655] [Chem.566]

[0656] [Chem.567]

[0657] [Chem.568]

[0658] [Chem.569]

[0659] [Chemistry 570]

[0660] [Chemistry 571]

[0661] [Chemistry 572]

[0662] [Chem.573]

[0663] [Chemistry 574]

[0664] [Chem.575]

[0665] [Chemistry 576]

[0666] [Chemistry 577]

[0667] [Chem.578]

[0668] [Chemistry 579]

[0669] [Chem.580]

[0670] [Chem.581]

[0671] [Chem.582]

[0672] [Chem.583]

[0673] [Chem.584]

[0674] [Chem.585]

[0675] [Chem. 586]

[0676] [Chem. 587]

[0677] [Chem. 588]

[0678] [Chem. 589]

[0679] [Chem. 590]

[0680] [Chem. 591]

[0681] [Chem. 592]

[0682] [Chem. 593]

[0683] [Chem. 594]

[0684] [Chem. 595]

[0685] [Chem. 596]

[0686] [Chem. 597]

[0687] [Chem. 598]

[0688] [Chem. 599]

[0689]

[600]

[0690] [Chemical 601]

[0691] [Chemical 602]

[0692] [Chemical 603]

[0693] [Chemical 604]

[0694] [Chemical 605]

[0695] [Chemical 606]

[0696] [Chem.607]

[0697] [Chemical 608]

[0698] [Chemical 609]

[0699] [Chemical 610]

[0700] [Chem.611]

[0701] [Chem.612]

[0702] [Chemistry 613]

[0703] [Chemical 614]

[0704] [Chemical 615]

[0705] [Chem.616]

[0706] Specific examples of strontium cations as repeating unit d may include those exemplified as strontium salt type monomers represented by 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 Publication No. 7491173, but are not limited to these.

[0707] Furthermore, the strontium cation that serves as the repeating unit d should preferably be represented by the following formula (d3). [Chemistry 617]

[0708] In formula (d3), d21 is either 0 or 1. When d21 is 0, it represents a benzene ring; when d21 is 1, it represents a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with d21 = 0. d22 is either 0 or 1. When d22 is 0, it represents a benzene ring; when d22 is 1, it represents a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with d21 = 0. d23 is either 0 or 1. When d23 is 0, it represents a benzene ring; when d23 is 1, it represents a naphthalene ring. Considering solvent solubility, it is preferable to have a benzene ring with d23 = 0.

[0709] In formula (d3), d24 is 0, 1, 2, 3, or 4. The more iodine atoms in the cation structure, the higher the absorption, especially for EUV. However, there is a risk of poor solvent solubility and precipitation in the inhibitor composition. Therefore, d24 should preferably be 0, 1, 2, or 3, and more preferably 0, 1, or 2.

[0710] In formula (d3), d25 is 0, 1, 2, 3, or 4. Considering the availability of raw materials, d25 should preferably be 0, 1, 2, or 3, and more preferably 0, 1, or 2. d26 is 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, d26 should preferably be 0, 1, 2, or 3, and more preferably 0, 1, or 2. d27 is 0, 1, 2, 3, 4, 5, or 6. Considering the availability of raw materials, d27 should preferably be 0, 1, 2, or 3, and more preferably 0, 1, or 2.

[0711] In formula (d3), d28 is 0, 1, or 2. Considering the availability of raw materials, d28 should ideally be 0 or 1. d29 is 0, 1, or 2. Considering the availability of raw materials, d29 should ideally be 0 or 1. d30 is 0, 1, or 2. Considering the availability of raw materials, d30 should ideally be 0 or 1.

[0712] In formula (d3), d31 is either 0 or 1. When d31 is 0, it is a benzene ring; when d31 is 1, it is a naphthalene ring. Considering the solubility of the solvent, it is preferable to have a benzene ring with d31 being 0.

[0713] In formula (d3), d32 is 0, 1, 2, 3, or 4. The more iodine atoms in the cation structure, the higher the absorption, especially for EUV. However, there is a risk of poor solvent solubility and precipitation in the inhibitor composition. Therefore, d32 should preferably be 0, 1, 2, or 3, and more preferably 0, 1, or 2.

[0714] In formula (d3), d33 is 0, 1, or 2. From the perspective of raw material acquisition, d33 should preferably be 0 or 1. d34 is 0, 1, or 2. From the perspective of synthesis, d34 should preferably be 0 or 1.

[0715] However, when d21 is 0, it is 0 ≤ d26 + d29 ≤ 4; when d21 is 1, it is 0 ≤ d26 + d29 ≤ 6. When d22 is 0, it is 0 ≤ d27 + d30 ≤ 4; when d22 is 1, it is 0 ≤ d27 + d30 ≤ 6. When d23 is 0, it is 1 ≤ d24 + d25 + d28 + d34 ≤ 4; when d23 is 1, it is 1 ≤ d24 + d25 + d28 + d34 ≤ 6. When d31 is 0, it is 0 ≤ d32 + d33 ≤ 4; when d31 is 1, it is 0 ≤ d32 + d33 ≤ 6. Furthermore, d24 + d32 ≥ 1.

[0716] In formula (d3), RF1 to RF3 are each independently 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 d25 is 2 or more, each RF1 may be the same or different from the others. When d26 is 2 or more, each RF2 may be the same or different from the others. When d27 is 2 or more, each RF3 may be the same or different from the others.

[0717] In formula (d3), R41 to R44 are halogen atoms other than iodine and fluorine atoms, nitro groups, cyano groups, and may also contain hydrocarbon groups with 1 to 20 carbon atoms, hydrocarbon oxygen groups with 1 to 20 carbon atoms, or hydrocarbon thio groups with 1 to 20 carbon atoms. The hydrocarbon groups, hydrocarbon oxygen groups, and hydrocarbon thio groups mentioned above may be saturated or unsaturated, and may be linear, branched, or cyclic. As specific examples, those exemplified by hydrocarbon groups represented as R1 and R2 in the explanation of formula (a) can be listed. Furthermore, some or all of the hydrogen atoms in the hydrocarbon group, hydrocarbon oxygen group, and hydrocarbon sulfur group can be replaced by a heteroatom group containing oxygen atom, sulfur atom, nitrogen atom, halogen atom, etc. The -CH2- part of the hydrocarbon group can also be replaced by a heteroatom group containing oxygen atom, sulfur atom, nitrogen atom, etc. As a result, it can also contain hydroxyl group, cyano group, fluorine atom, chlorine atom, bromine atom, iodine atom, carbonyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulfonolactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl group, etc.

[0718] Furthermore, when d28 is 2, the two R41 atoms can be the same or different, and they can also bond together to form a ring with the carbon atoms of these bonds. When d29 is 2, the two R42 atoms can be the same or different, and they can also bond together to form a ring with the carbon atoms of these bonds. When d30 is 2, the two R43 atoms can be the same or different, and they can also bond together to form a ring with the carbon atoms of these bonds. When d33 is 2, the two R44 atoms can be the same or different, and they can also bond together to form a ring with the carbon atoms of these bonds. Specific examples of rings formed in this case include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norcamphene rings, and adamantane rings. Furthermore, some or all of the hydrogen atoms in the aforementioned ring can be replaced by a heteroatom group containing oxygen, sulfur, nitrogen, halogen, etc., and some of the -CH2- in the aforementioned ring can also be replaced by a heteroatom group containing oxygen, sulfur, nitrogen, etc. As a result, it may also contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc.

[0719] Furthermore, the aromatic rings of S+ in the strontium cation represented by formula (d3) can also bond to each other to form a ring together with S+. Specific examples of the aforementioned ring structures can be given by formulas such as the following. [Chem.618] (In the formula, the dashed lines represent atomic bonds.)

[0720] In formula (d3), LH1 and LH2 are each independently a single bond, ether bond, ester bond, amide bond, sulfonate bond, sulfonamide bond, carbonate bond, or carbamate bond. Among these, LH1 is preferably a single bond, ether bond, ester bond, or sulfonate bond, and more preferably an ester bond or sulfonate bond. LH2 is preferably a single bond, ether bond, or ester bond, and more preferably a single bond.

[0721] In formula (d3), XL6 is a single bond, or may contain a heteroatom and be an extended hydrocarbon group with 1 to 40 carbon atoms. The extended hydrocarbon group can be linear, branched, or cyclic; specific examples include alkyldiyl, cyclic saturated extended hydrocarbon groups, and extended aryl groups. Specific examples of the heteroatom include oxygen, nitrogen, and sulfur atoms. Specific examples of extended hydrocarbon groups with 1 to 40 carbon atoms represented by XL6 include XL-0 to XL-61, as exemplified in the description of formula (Z) as XL1 and XL2, which may also contain heteroatoms. Among these, XL-0 to XL-22, XL-29 to XL-34, and XL-47 to XL-61 are preferred.

[0722] The strontium cation represented by formula (d3) should preferably be represented by formula (d3-1). [Chem.619] (In the formula, d24~d30, d32~d34, RF1~RF3, R41~R44, LH1, LH2 and XL6 are the same as above.)

[0723] The strontium cation represented by formula (d3-1) should preferably be represented by formula (d3-2). [Chem.620] (In the formula, d24~d30, RF1~RF3 and R41~R43 are the same as above.)

[0724] Specific examples of strontium cations represented by formula (d3) are shown below, but are not limited to these. Furthermore, in the following formula, Me is a methyl group. [Chemistry 621]

[0725] [Chemistry 622]

[0726] [Chemistry 623]

[0727] [Chemistry 624]

[0728] [Chemical 625]

[0729] [Chemistry 626]

[0730] [Chemistry 627]

[0731] [Chemistry 628]

[0732] [Chemistry 629]

[0733] [Chemistry 630]

[0734] [Chemistry 631]

[0735] [Chemistry 632]

[0736] [Chemistry 633]

[0737] [Chemistry 634]

[0738] [Chemistry 635]

[0739] [Transformation 636]

[0740] [Chemistry 637]

[0741] [Chemistry 638]

[0742] [Chemistry 639]

[0743] [Transformation 640]

[0744] [Chemistry 641]

[0745] [Chemistry 642]

[0746] [Chemistry 643]

[0747] [Chemistry 644]

[0748] [Chemistry 645]

[0749] [Transformation 646]

[0750] [Chemistry 647]

[0751] [Chemistry 648]

[0752] The polymers described above preferably contain repeating units represented by the following formula (e) (hereinafter also referred to as repeating units e). [Chemistry 649]

[0753] In formula (e), RA represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z1 represents a single bond, an phenyl group, a naphthyl group, *-C(=O)-O-Z11-, or *-C(=O)-N(H)-Z11-. This phenyl or naphthyl group may also be substituted by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group containing 1 to 10 carbon atoms with fluorine atoms, or a saturated hydrocarbon group containing 1 to 10 carbon atoms with fluorine atoms, an oxygen group, or a halogen atom. * indicates an atomic bond with a carbon atom in the main chain. Z11 represents a saturated hydrocarbon group containing 1 to 10 carbon atoms, an phenyl group, or a naphthyl group. This saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. R51 is a group consisting of a hydrogen atom or a carbon group having 1 to 20 carbon atoms, or a structure containing at least one of the following: 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)-).

[0754] Specific examples of the repeating unit e can be listed below, but are not limited to these. Furthermore, in the following formula, RA is the same as above. [Chemical 650]

[0755] [Chemistry 651]

[0756] [Chemistry 652]

[0757] [Chemistry 653]

[0758] [Chem. 654]

[0759] [Chemistry 655]

[0760] [Chemistry 656]

[0761] [Chemistry 657]

[0762] [Chemistry 658]

[0763] [Chem. 659]

[0764] [Chem. 660]

[0765] [Chem. 661]

[0766] [Chem. 662]

[0767] [Chem. 663]

[0768] [Chem. 664]

[0769] [Chem. 665]

[0770] As the repeating unit e, for ArF lithography, it is particularly preferably one having a lactone ring as a polar group, and for KrF lithography, EB lithography and EUV lithography, it is preferably one having a phenolic moiety.

[0771] The above polymer may further contain a repeating unit having a structure wherein a hydroxyl group is protected by an acid-labile group (hereinafter also referred to as repeating unit f). There is no particular limitation on the repeating unit f, as long as it has a structure in which one or two or more hydroxyl groups are protected, and the protecting group is decomposed by the action of an acid to generate a hydroxyl group, and it is preferably represented by the following formula (f). [Chem. 666]

[0772] In formula (f), RA represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R61 represents an (e+1)-valent hydrocarbon group having 1 to 30 carbon atoms which may also contain a heteroatom. R62 represents an acid-labile group. e is 1, 2, 3 or 4.

[0773] In formula (f), the acid-labile group represented by R62 is not particularly limited as long as it can be deprotected by the action of an acid to generate a hydroxyl group. The structure of R62 is not particularly limited, and is preferably an acetal structure, a ketal structure, a hydrocarbyloxycarbonyl group, a hydrocarbyloxymethyl group represented by the following formula (f1), and particularly preferably a hydrocarbyloxymethyl group represented by the following formula (f1). [Chem 667] (In the formula, * represents an atomic bond. R63 is a hydrocarbyl group having 1 to 15 carbon atoms.)

[0774] Specific examples of the acid-labile group represented by R62, the hydrocarbyloxymethyl group represented by formula (f1), and the repeating unit f are the same as those exemplified in the description of the repeating unit d described in Japanese Patent Application Laid-Open No. 2020-111564.

[0775] The above polymer may further contain a repeating unit g derived from indene, benzofuran, benzothiophene, vinylnaphthalene, chromone, coumarin, norbornadiene, or derivatives thereof. Specific examples of monomers that provide the repeating unit g include those shown below, but are not limited thereto. [Chem 668]

[0776] The above polymer may further contain a repeating unit h derived from styrene, indane, vinylpyridine or vinylcarbazole.

[0777] In the polymer of the present invention, the content ratios of repeating units a, b1, b2, b3, c, d, e, f, g and h are preferably 0 < a ≦ 0.4, 0 < b1 ≦ 0.8, 0 ≦ b2 ≦ 0.8, 0 ≦ b3 ≦ 0.6, 0 < c ≦ 0.6, 0 ≦ d ≦ 0.4, 0 ≦ e ≦ 0.6, 0 ≦ f ≦ 0.3, 0 ≦ g ≦ 0.3 and 0 ≦ h ≦ 0.3, more preferably 0 < a ≦ 0.3, 0 < b1 ≦ 0.7, 0 ≦ b2 ≦ 0.7, 0 ≦ b3 ≦ 0.5, 0 < c ≦ 0.5, 0 ≦ d ≦ 0.3, 0 ≦ e ≦ 0.5, 0 ≦ f ≦ 0.2, 0 ≦ g ≦ 0.2 and 0 ≦ h ≦ 0.2, provided that a+b1+b2+b3+c+d+e+f+g+h ≦ 1.0.

[0778] The weight-average molecular weight (Mw) of the aforementioned polymer is preferably between 1,000 and 500,000, and more preferably between 3,000 and 100,000. As long as Mw is within this range, sufficient etch resistance can be obtained without concerns about reduced resolution due to the difference in dissolution rates before and after exposure. Furthermore, the Mw in this invention is a polystyrene-converted value determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as solvents.

[0779] The molecular weight distribution (Mw / Mn) of the aforementioned polymers tends to increase with the refinement of the pattern. Therefore, to obtain a resist composition suitable for use in fine pattern sizes, the Mw / Mn ratio should ideally be a narrow dispersion of 1.0 to 2.0. Within this range, there are fewer low- or high-molecular-weight polymers, eliminating the risk of foreign matter being observed on the pattern or deterioration of the pattern shape after exposure.

[0780] As a method for synthesizing the above-mentioned polymer, one example is to polymerize the monomer of the repeating unit in an organic solvent, add a free radical polymerization initiator, and heat it.

[0781] Specific examples of organic solvents used in polymerization include toluene, benzene, THF, diethyl ether, dialkylene, 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 lauryl peroxide. The amount of these initiators added relative to the total amount of monomers to be polymerized should preferably be 0.01 to 25 moles. The reaction temperature should preferably be 50 to 150°C, more preferably 60 to 100°C. The reaction time should ideally be 2 to 24 hours, but from the perspective of production efficiency, it should ideally be 2 to 12 hours.

[0782] The aforementioned polymerization initiator can be added to the monomer solution and supplied to the reactor, or a separate initiator solution can be prepared in addition to the monomer solution and supplied to the reactor independently. Because there is a possibility that free radicals generated from the initiator during the standby time may cause polymerization and produce ultra-high molecular weight polymers, from a quality control perspective, the monomer solution and initiator solution should be prepared and added dropwise separately. Acid-labile groups can be used directly introduced into the monomer, or post-polymerization protection or partial protection can be performed. Furthermore, to adjust the molecular weight, known chain transfer agents such as dodecyl mercaptan or 2-mercaptoethanol can be used. In this case, the amount of such chain transfer agents added relative to the total amount of monomers polymerized should preferably be 0.01 to 20 mol.

[0783] In the case of monomers containing hydroxyl groups, the hydroxyl groups can be replaced by acetal groups such as ethoxy-ethoxy, which are easily deprotected by acids, during polymerization, and then deprotected by weak acids and water after polymerization. Alternatively, they can be replaced by acetyl, methyl, trimethylacetyl, etc., and then subjected to alkaline hydrolysis after polymerization.

[0784] In the case of copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, hydroxystyrene or hydroxyvinylnaphthalene can also be polymerized 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 group can be deprotected by alkaline hydrolysis to obtain polyhydroxystyrene or hydroxypolyvinylnaphthalene.

[0785] Specific examples of alkalis used in alkaline hydrolysis include ammonia and triethylamine. Furthermore, the reaction temperature should preferably be -20 to 100°C, and more preferably 0 to 60°C. The reaction time should preferably be 0.2 to 100 hours, and more preferably 0.5 to 20 hours.

[0786] Furthermore, the amount of each monomer in the aforementioned monomer solution can be appropriately set, for example, in a manner that forms a preferred content ratio for the aforementioned repeating units.

[0787] The polymer obtained by the above manufacturing method can be regarded as the final product by the reaction solution obtained by polymerization reaction, or the powder obtained by refining steps such as adding the polymer liquid to a poor solvent to obtain the powder and then reprecipitating it. Considering the point of view of work efficiency or quality stability, it is better to regard the polymer solution obtained by dissolving the powder obtained by refining steps into a solvent as the final product.

[0788] As specific examples of solvents used at this time, ketones such as cyclohexanone and methyl-2-n-pentyl ketone described in paragraphs

[0144] to

[0145] of Japanese Patent Application Publication No. 2008-111103 can be cited; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and dimethyl propylene glycol dimethyl ether, etc. Ethers such as ethylene glycol dimethyl ether; esters such as PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tributyl acetate, tributyl propionate, propylene glycol monobutyl ether acetate, etc.; 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, 1,3-butanediol, etc.; and mixed solvents thereof.

[0789] In the above polymer solution, the concentration of the polymer should preferably be 0.01~30% by mass, and more preferably 0.1~20% by mass.

[0790] The above-mentioned reaction solutions or polymer solutions should be filtered. Filtering removes foreign matter or gel that could cause defects, thus effectively stabilizing the quality.

[0791] Regarding the materials used in the aforementioned filters, examples include fluorocarbon-based, cellulose-based, nylon-based, polyester-based, and hydrocarbon-based materials. In the filtration step involving inhibitor components, filters made of fluorocarbon-based, polyethylene, polypropylene, or nylon materials, often referred to as Teflon (registered trademark), are preferred. The filter pore size should be appropriately selected to match the target cleanliness level, preferably below 100 nm, and more preferably below 20 nm. Furthermore, these filters can be used individually or in combination. The filtration method can involve passing the solution through only once, or more preferably, circulating the solution for multiple filtrations. The filtration steps can be performed in any order and number of times during the polymer manufacturing process, preferably filtering the reaction solution after polymerization, the polymer solution, or both.

[0792] [Chemical Amplification Inhibitor Composition] [(A) Basic Polymer] The chemical amplification inhibitor composition of the present invention contains a base polymer containing the above-mentioned polymer as component (A).

[0793] The above-mentioned polymers can be used alone or in combination with two or more polymers having different composition ratios, Mw and / or Mw / Mn. In addition, (A) the base polymer may contain hydrides of ring-opening metathesis polymers in addition to the above-mentioned polymers, and the polymers described in Japanese Patent Application Publication No. 2003-66612 may be used.

[0794] [(B) Organic solvents] The chemical amplification inhibitor composition of the present invention may also contain an organic solvent as component (B). There are no particular limitations on the organic solvent as long as it can dissolve the above-mentioned 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, tributyl acetate, tributyl propionate, and propylene glycol monobutyl ether acetate; lactones such as GBL; and mixed solvents of these.

[0795] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, ethyl lactate, DAA, and mixed solvents thereof are particularly suitable for dissolving the base polymer of component (A).

[0796] In the chemical amplification inhibitor composition of the present invention, the content of (B) organic solvent is preferably 200-5000 parts by mass relative to 80 parts by mass of (A) base polymer, and more preferably 400-3500 parts by mass. (B) Organic solvent can be used alone or in combination with two or more.

[0797] [(C) Quenching agent] The chemical amplification inhibitor composition of the present invention may also contain a quencher as component (C). Furthermore, the quencher in the present invention is a material used to form a desired pattern by capturing strong acids generated from the photoacid generator in the chemical amplification inhibitor composition, preventing diffusion to unexposed areas. Additionally, "strong acid" refers to an acid with sufficient acidity to cause deprotection reactions of unstable acid groups.

[0798] As a specific example of (C) quenching agent, onium salts represented by formula (1) or (2) can be listed below. [Chem.669]

[0799] In formula (1), Rq1 is a hydrogen atom, or may contain a hydrocarbon group with 1 to 40 carbon atoms of heteroatoms, but excludes hydrogen atoms bonded to the α-position of the sulfonyl group that are replaced by fluorine atoms or fluoroalkyl groups. In formula (2), Rq2 is a hydrogen atom, or may contain a hydrocarbon group with 1 to 40 carbon atoms of heteroatoms.

[0800] Rq1 represents hydrocarbon groups with 1 to 40 carbon atoms. Specifically, examples include alkyl groups with 1 to 40 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, tripentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclo[5.2.1.02,6]decyl, and adamantylalkyl; and aryl groups with 6 to 40 carbon atoms such as phenyl, naphthyl, and anthracene. Furthermore, one or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by a heteroatom group containing oxygen, sulfur, nitrogen, halogen, etc., and one part of the -CH2- in the aforementioned hydrocarbon group can also be replaced by a heteroatom group containing oxygen, sulfur, nitrogen, etc. As a result, it may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc.

[0801] As for the hydrocarbon group represented by Rq2, in addition to the substituents exemplified as specific examples of Rq1, fluorinated saturated hydrocarbon groups such as trifluoromethyl and trifluoroethyl, or fluorinated aryl groups such as pentafluorophenyl and 4-trifluoromethylphenyl can also be listed.

[0802] Specific examples of onium salt anions represented by formula (1) can be listed below, but are not limited to these. [Transformation 670]

[0803] [Chemistry 671]

[0804] [Chemistry 672]

[0805] [Chemistry 673]

[0806] [Chemistry 674]

[0807] Specific examples of onium salt anions represented by equation (2) can be listed below, but are not limited to these. [Chemistry 675]

[0808] [Transformation 676]

[0809] [Chemistry 677]

[0810] [Transformation 678]

[0811] [Chemistry 679]

[0812] In formulas (1) and (2), Mq+ is a ium cation. The aforementioned ium cation is preferably a strontium cation, a monium cation, or an ammonium cation. Specific examples of the aforementioned strontium cation may include those that are the same as those exemplified as specific examples of strontium salt type monomer cations represented by 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 those represented by formula (d3), but are not limited to these.

[0813] As specific examples of the aforementioned citric acid, those described in paragraph

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

[0814] As a specific example of the aforementioned ammonium cation, the following formula (am-1) can be cited. [Transformation 680]

[0815] In formula (am-1), Rq11 to Rq14 are each an independent hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. Furthermore, Rq11 and Rq12 may bond to each other to form a ring with the nitrogen atoms in these bonds. Specific examples of the aforementioned hydrocarbon groups can be listed that are identical to those exemplified by the hydrocarbon groups represented by R1 and R2 in the explanation of formula (a).

[0816] Specific examples of ammonium cations represented by formula (am-1) can be listed below, but are not limited to these. [Chemistry 681]

[0817] As specific examples of onium salts represented by formula (1) or (2), any combination of the aforementioned anions and cations can be listed. Furthermore, these onium salts are readily prepared by ion exchange reactions using known organic chemical methods. For example, Japanese Patent Application Publication No. 2007-145797 can be consulted regarding ion exchange reactions.

[0818] The onium salts represented by formula (1) or (2) function as quenchers in the chemical amplification inhibitor composition of the present invention. This is due to the conjugate base of each of the aforementioned onium salts relative to anionic weak acids. The weak acid referred to here means that it exhibits an acidity that cannot deprotect the acid unstable group containing the acid unstable group unit used in the base polymer. The onium salts represented by formula (1) or (2) function as quenchers when used in combination with the conjugate base of a strong acid such as sulfonic acid with α-fluorination as a relative anionic onium salt-type photoacid generator. In other words, when using onium salts that produce strong acids like α-fluorinated sulfonic acids and weak acids like unfluorinated sulfonic acids or carboxylic acids, if the strong acid generated from the photoacid generator by high-energy radiation irradiation collides with the onium salt containing unreacted weak acid anions, the weak acid is released through salt exchange, producing an onium salt containing strong acid anions. In this process, the strong acid is exchanged for a weak acid with a lower catalytic energy; therefore, overall, the acid system is deactivated, and acid diffusion can be controlled.

[0819] In addition, as the quencher (C), the onium salt having strontium cation and benzene oxide anion sites in the same molecule as described in Japanese Patent No. 6848776, and further, the onium salt having strontium cation and carboxylate anion sites in the same molecule as described in Japanese Patent No. 6583136, Japanese Patent Application Publication No. 2020-200311, and the onium salt having monium cation and carboxylate anion sites in the same molecule as described in Japanese Patent No. 6274755, can also be used.

[0820] Here, when the photoacid generator that produces a strong acid is an onium salt, as mentioned above, the strong acid produced by high-energy ray irradiation can be exchanged for a weak acid. However, it is believed that the weak acid produced by high-energy ray irradiation is difficult to exchange with the unreacted onium salt that produces the strong acid. This is because onium cations are more likely to form ion pairs with the anions of strong acids.

[0821] In the case where the chemical amplification inhibitor composition of the present invention contains an onium salt represented by formula (1) or (2) as a quencher in (C), its content is preferably 0.1 to 20 parts by mass relative to 80 parts by mass of the base polymer in (A), and more preferably 0.1 to 10 parts by mass. As long as the content of the onium salt-type quencher is within the above range, the resolution is good and the sensitivity is not significantly reduced, which is preferable. The onium salt represented by formula (1) or (2) can be used alone or in combination of two or more.

[0822] The chemical amplification inhibitor composition of the present invention may also contain a nitrogen-containing compound as a (C) quencher. Specific examples of such nitrogen-containing compounds include first-, second-, or third-order amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103, particularly amine compounds having hydroxyl groups, ether bonds, ester bonds, lactone rings, cyano groups, or sulfonate bonds. Furthermore, compounds in which a first- or second-order amine is protected by a carbamate group, as described in Japanese Patent Publication No. 3790649, may also be cited.

[0823] Furthermore, strontium sulfonate salts with nitrogen-containing substituents can also be used as nitrogen-containing compounds. In such compounds, the unexposed portion functions as a quencher, while the exposed portion loses its quencher properties through neutralization with the acid it generates, thus functioning as a so-called photodegrading base. By using a photodegrading base, the contrast between the exposed and unexposed portions can be further enhanced. For examples of photodegrading bases, see, for instance, Japanese Patent Application Publication Nos. 2009-109595 and 2012-46501.

[0824] In the case where the chemical amplification inhibitor composition of the present invention contains a nitrogen-containing compound as a (C) quencher, its content is preferably 0.001 to 12 parts by mass, more preferably 0.01 to 8 parts by mass, relative to 80 parts by mass of the (A) base polymer. The aforementioned nitrogen-containing compound may be used alone or in combination of two or more. [(D) Acid generating agent] The chemical amplification inhibitor composition of the present invention may also contain an acid-generating agent, provided that the effect of the present invention is not impaired. Examples of such acid-generating agents include compounds that generate acid by sensing active light or radiation (photoacid generators). There is no particular limitation on the type of photoacid generator; it is suitable as long as the compound generates acid by high-energy radiation, such as those that generate sulfonic acid, amide acid, or methyl acid. Suitable photoacid generators include strontium salts, ferric salts, sulfonyldiazomethane, N-sulfonyloxyamide, and oxime-O-sulfonate type acid generators. Specific examples of acid generators can be found in paragraphs

[0122] to

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

[0825] In addition, suitable photoacid generators can be represented by formulas (3) or (4). [Chem. 682]

[0826] In formula (3), R101 to R105 are halogen atoms or hydrocarbon groups with 1 to 20 carbon atoms that may contain heteroatoms. In addition, any two of R101, R102 and R103 may bond to each other to form a ring with the sulfur atoms of these bonds. As specific examples of the above hydrocarbon groups, those that are the same as those exemplified by the hydrocarbon groups represented by R1 and R2 in the explanation of formula (a) can be listed. Furthermore, one or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by a heteroatom group containing oxygen, sulfur, nitrogen, halogen, etc., and one part of the -CH2- in the aforementioned hydrocarbon group can also be replaced by a heteroatom group containing oxygen, sulfur, nitrogen, etc. As a result, it may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc.

[0827] Specific examples of strontium salt cations represented by formula (3) may include those exemplified as strontium salt type monomer cations represented by 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 Patent Publication No. 2024 / 128017, those described in paragraphs

[0035] to

[0046] of Japanese Patent Publication No. 7491173, and those exemplified as strontium cations represented by formula (d3), but are not limited to these examples. Specific examples of ferrous salt cations represented by formula (4) may include those described in paragraph

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

[0828] In equations (3) and (4), Xa- is the anion of a strong acid. As the anion of the aforementioned strong acid, any one of the following equations (Xa-1) to (Xa-4) can be listed. [Chem.683]

[0829] In formula (Xa-1), Rfa is a fluorine atom, or may contain heteroatoms and is a hydrocarbon group with 1 to 60 carbon atoms. The above hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. As specific examples, those identical to the hydrocarbon group represented by Rfa1 in formula (Xa-1-1) described later can be listed.

[0830] The anion represented by formula (Xa-1) should preferably be represented by the following formula (Xa-1-1). [Chem.684]

[0831] In formula (Xa-1-1), QA and QB are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms. To improve solvent solubility, at least one of them should preferably be trifluoromethyl. k is 0, 1, 2, 3, or 4, and is particularly preferably 1. Rfa1 may also contain a hydrocarbon group with 1 to 40 carbon atoms that is a heteroatom. The heteroatoms mentioned above are preferably oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, etc., and are more preferably oxygen atoms. Considering that high resolution can be obtained in the formation of fine patterns, the hydrocarbon groups mentioned above are particularly preferably those with 6 to 30 carbon atoms.

[0832] In formula (Xa-1-1), Rfa1 represents a hydrocarbon group with 1 to 40 carbon atoms, which can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 40 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecanyl, and eicosyl; cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornel, norbornelmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl; unsaturated aliphatic hydrocarbon groups with 2 to 40 carbon atoms, such as 2-propenyl and 3-cyclohexenyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, and 9-enyl; and aralkyl groups with 7 to 40 carbon atoms, such as benzyl and diphenylmethyl. Polycyclic hydrocarbon groups with 7 to 40 carbon atoms containing an aromatic ring, such as 9,10-dihydro-9,10-ethbridged anthraceneyl and 6,13-dihydro-6,13-ethbridged pentaphenyl; hydrocarbon groups with 17 to 40 carbon atoms having a steroid skeleton; and other groups obtained by combining these.

[0833] Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups can be substituted by heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, the -CH2- group in the aforementioned hydrocarbon groups can be substituted by heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the hydrocarbon groups may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulopentalide, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. Specific examples of hydrocarbon groups containing heteroatoms include tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetaminomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-sideoxypropyl, 4-sideoxy-1-adamantyl, and 3-sideoxycyclohexyl.

[0834] In formula (Xa-1-1), the La1 group consists of 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 more suitable.

[0835] Specific examples of anions represented by formula (Xa-1) can be listed below, but are not limited to these. Furthermore, in the following formula, Q1 is the same as above, and Ac is acetyl. [Chem.685]

[0836] [Chem 686]

[0837] [Chem 687]

[0838] [Chem 688]

[0839] [Chem 689]

[0840] [Chem 690]

[0841] [Chem 691]

[0842] [Chem 692]

[0843] [Chem 693]

[0844] [Chem 694]

[0845] [Chem 695]

[0846] [Chem 696]

[0847] In formula (Xa-2), Rfb1 and Rfb2 are each independently a fluorine atom, or may contain heteroatoms, and are hydrocarbon groups with 1 to 40 carbon atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed that are the same as those exemplified as the hydrocarbon group represented by Rfa1 in formula (Xa-1-1). Rfb1 and Rfb2 are preferably fluorine atoms or linear fluorinated alkyl groups with 1 to 4 carbon atoms. Furthermore, Rfb1 and Rfb2 can also bond to each other to form a ring with such bonded groups (-CF2-SO2-N--SO2-CF2-). In this case, the group obtained by the mutual bonding of Rfb1 and Rfb2 is preferably fluorinated ethyl or fluorinated propyl.

[0848] In formula (Xa-3), Rfc1, Rfc2, and Rfc3 are each independently a fluorine atom, or may contain heteroatoms, and are hydrocarbon groups with 1 to 40 carbon atoms. These hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be listed that are the same as those exemplified as Rfa1 in formula (Xa-1-1). Rfc1, Rfc2, and Rfc3 are preferably fluorine atoms or linear fluorinated alkyl groups with 1 to 4 carbon atoms. Furthermore, Rfc1 and Rfc2 can also bond to each other to form a ring with these bonded groups (-CF2-SO2-C--SO2-CF2-). In this case, the group obtained by the mutual bonding of Rfc1 and Rfc2 is preferably fluorinated ethyl or fluorinated propyl.

[0849] In formula (Xa-4), the Rfd group may also contain hydrocarbon groups with 1 to 40 carbon atoms of heteroatoms. These hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples can be listed that are identical to those exemplified by the hydrocarbon group represented as Rfa1 in formula (Xa-1-1). Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be substituted by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, some of the -CH2- group in the aforementioned hydrocarbon groups may be substituted by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the hydrocarbon group may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonate ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups.

[0850] Specific examples of anions represented by formula (Xa-4) can be listed below, but are not limited to these. [Chemistry 697]

[0851] [Transformation 698]

[0852] As an example of anion represented by Xa-, we can further cite anions having aromatic rings substituted by iodine or bromine atoms. A specific example of such anion is represented by the following formula (Xa-5). [Transformation 699]

[0853] In equation (Xa-5), x is 1, 2, or 3. y is 1, 2, 3, 4, or 5. z can be 0, 1, 2, or 3. However, 1 ≤ y + z ≤ 5. y should ideally be 1, 2, or 3, and more preferably 2 or 3. z should ideally be 0, 1, or 2.

[0854] In formula (Xa-5), XBI represents an iodine atom or a bromine atom. When x and / or y are 2 or more, each XBI may be the same or different from the others.

[0855] In formula (Xa-5), L11 is a single bond, ether bond, ester bond, sulfonate bond, carbonate bond, carbamate bond, or a saturated alkyl group with 1 to 6 carbon atoms. The -CH2- portion of this alkyl group can also be substituted by an ether bond or an ester bond. The above-mentioned saturated alkyl group can be any of the following: linear, branched, or cyclic.

[0856] In formula (Xa-5), for the L12 system, when x is 1, it is a single bond or may contain a heteroatom of a carbon group with 1 to 20 carbon atoms; when x is 2 or 3, it is a (x+1) valence hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms.

[0857] L12 represents an extended hydrocarbon group with 1 to 20 carbon atoms, which 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, and dodecane-1, Alkyl groups with 1 to 20 carbon atoms, such as 12-diyl; cyclopentanediyl, cyclohexanediyl, norcamphenediyl, adamantanediyl, tricyclo[5.2.1.02,6]decanediyl, etc., cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms; unsaturated aliphatic hydrocarbon groups with 2 to 20 carbon atoms, such as vinylene, propene-1,3-diyl; aryl groups with 6 to 20 carbon atoms, such as phenylene, naphthyl, anthracenediyl; polycyclic hydrocarbon groups containing aromatic rings with 7 to 20 carbon atoms, such as 9,10-dihydro-9,10-ethbridged anthracenediyl, 6,13-dihydro-6,13-ethbridged pentaphenyl; and other groups obtained by combining these groups. The (x+1) valence hydrocarbon group with 1 to 20 carbon atoms represented by L12 can be saturated or unsaturated, and can be linear, branched, or cyclic. As a specific example, examples of the hydrocarbon groups with 1 to 20 carbon atoms mentioned above can be cited, which are obtained by removing one or two hydrogen atoms.

[0858] Furthermore, some or all of the hydrogen atoms in the aforementioned extended hydrocarbon group and (x+1) valence hydrocarbon group can be replaced by a heteroatom group containing oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and some of the -CH2- in the aforementioned extended hydrocarbon group and (x+1) valence hydrocarbon group can also be replaced by a heteroatom group containing oxygen atoms, sulfur atoms, nitrogen atoms, etc. As a result, it may also 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.

[0859] In formula (Xa-5), L13 series single bonds, ether bonds, ester bonds, sulfonate bonds, carbonate bonds or carbamate bonds.

[0860] In formula (Xa-5), Rfe refers to hydroxyl, carboxyl, fluorine, chlorine, bromine, amino, hydrocarbon group with 1 to 20 carbon atoms, hydrocarbon oxy group with 1 to 20 carbon atoms, hydrocarbon thio group with 1 to 20 carbon atoms, hydrocarbon carbonyl group with 2 to 20 carbon atoms, hydrocarbon oxycarbonyl group with 2 to 20 carbon atoms, hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms, or hydrocarbon sulfonyl oxy group with 1 to 20 carbon atoms, -N(RfeA)(RfeB), -N(RfeC)-C(=O)-RfeD or -N(RfeC)-C(=O)-O-RfeD. The hydrocarbon group, hydrocarbon oxy group, hydrocarbon thio group, hydrocarbon carbonyl group, hydrocarbon oxycarbonyl group, hydrocarbon carbonyl oxy group, and hydrocarbon sulfonyl oxy group may also contain at least one selected from fluorine, chlorine, bromine, iodine, hydroxyl, amino, ester bond and ether bond. RfeA and RfeB are each independently composed of a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. RfeC is composed of 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 oxy group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl oxy group having 2 to 6 carbon atoms. RfeD is composed of an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxy group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl oxy group having 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned hydrocarbon group, hydrocarbon oxy group, hydrocarbon carbonyl group, hydrocarbon oxy carbonyl group, hydrocarbon carbonyl oxy group, and hydrocarbon sulfonyl oxy group can be any of the following: linear, branched, or cyclic. When x and / or z are 2 or more, each Rfe can be the same or different from the others.

[0861] Among these, Rfe should preferably be a hydroxyl group, -N(RfeC)-C(=O)-RfeD, -N(RfeC)-C(=O)-O-RfeD, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group, etc.

[0862] In formula (Xa-5), Rf11 to Rf14 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, at least one of which is a fluorine atom or a trifluoromethyl group. Furthermore, Rf11 and Rf12 can also combine to form a carbonyl group. In particular, it is preferable that both Rf13 and Rf14 are fluorine atoms.

[0863] Specific examples of anions represented by formula (Xa-5) can be listed below, but are not limited to these. Furthermore, in the following formula, XBI is the same as above. [Chemical 700]

[0864] [Chemical 701]

[0865] [Chemical 702]

[0866] [Chemical 703]

[0867] [Chemical 704]

[0868] [Chemical 705]

[0869] [Chemical 706]

[0870] [Chem.707]

[0871] [Chem.708]

[0872] [Chem. 709]

[0873] [Chem.710]

[0874] [Chem.711]

[0875] [Chem.712]

[0876] [Chem.713]

[0877] [Chem.714]

[0878] [Chem 715]

[0879] [Chem 716]

[0880] [Chem 717]

[0881] [Chem 718]

[0882] [Chem 719]

[0883] [Chem 720]

[0884] [Chem 721]

[0885] [Chem 722]

[0886] [Chem 723]

[0887] Other examples of anions represented by Xa- include paragraphs

[0076] and

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

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

[0253] to

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

[0044] to

[0045] of International Publication No. 2024 / 122423, paragraphs

[0205] to

[0220] of Japanese Patent Application Publication No. 2023-123183, and paragraphs

[0170] to

[0178] of Japanese Patent Application Publication No. 2024-62406,

[0026] . ~

[0028] , Paragraphs from Japanese Patent Application Publication No. 2024-62407

[0022] ~

[0025] , Paragraphs from Japanese Patent Application Publication No. 2024-62408

[0026] ~

[0028] , Paragraphs from Japanese Patent Application Publication No. 2024-68156

[0028] ~

[0030] , Paragraphs from Japanese Patent Application Publication No. 2024-68157

[0026] ~

[0028] , Paragraphs from Japanese Patent Application Publication No. 2024-68158

[0028] ~

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

[0028] ~

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

[0031] ~

[0032] 3] Paragraphs from Japanese Patent Application Publication No. 2024-72281

[0023] ~

[0025] , Japanese Patent Application Publication No. 2024-77618

[0026] ~

[0029] , Japanese Patent Application Publication No. 2024-77619

[0020] ~

[0021] , Japanese Patent Application Publication No. 2024-80672

[0140] ~

[0143] , Japanese Patent Application Publication No. 2024-83303

[0023] ~

[0025] , Japanese Patent Application Publication No. 2024-83304

[0028] ~

[0031] , Japanese Patent Application Publication No. 2024-99500

[0030] ~

[0033] , Japan Paragraphs

[0028] to

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

[0030] to

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

[0025] to

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

[0033] to

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

[0021] to

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

[0169] to

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

[0178] to

[0181] of Japanese Patent Application Publication No. 2024-144356.The following are descriptions in paragraphs

[0040] to

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

[0157] to

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

[0227] to

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

[0253] to

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

[0309] to

[0312] of Japanese Patent Publication No. 7466782.

[0888] As the anion represented by Xa-, the following can also be used: the fluorobenzenesulfonic acid anion bonded to an aromatic group containing an iodine atom as described in Japanese Patent No. 6648726; the anion with a mechanism of decomposition by 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.

[0889] As the anion represented by Xa-, further, the anions of bulky benzenesulfonic acid derivatives without fluorine atoms described in Japanese Patent Application Publication Nos. 2006-276759, 2015-117200, 2016-65016, 2019-202974, and 2024-104830, as well as the benzenesulfonic acid anions or alkylsulfonic acid anions bonded to an aromatic group containing iodine atoms without fluorine atoms described in Japanese Patent No. 6645464, can also be used. In addition, the anions described in Japanese Patent Application Publication Nos. 2024-77330

[0229] to

[0231] and Japanese Patent Application Publication Nos. 2024-140135

[0033] to

[0093] can also be used.

[0890] As the anion represented by Xa-, the anion of disulfonic acid described in Japanese Patent Application Publication No. 2015-206932, the anion of sulfonic acid on one side and sulfenamide or sulfenimide on the other side as described in International Patent Application Publication No. 2020 / 158366, and the anion of sulfonic acid on one side and carboxylic acid on the other side as described in Japanese Patent Application Publication No. 2015-24989, can also be used.

[0891] Furthermore, the photoacid generator, which is the component of (D), should also be represented by the following formula (5). [Chem. 724]

[0892] In formula (5), R201 and R202 are each independently a hydrocarbon group with 1 to 30 carbon atoms, which may also contain heteroatoms. R203 is also a hydrocarbon group with 1 to 30 carbon atoms, which may contain heteroatoms. In addition, any two of R201, R202 and R203 may bond to each other to form a ring together with the sulfur atoms of these bonds.

[0893] R201 and R202 represent hydrocarbon groups with 1 to 30 carbon atoms, which 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, dibutyl, tributyl, tripentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, oxanorbornel, tricyclic [5.2.1.02, 6] Cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, such as decyl and adamantyl; aryl groups having 6 to 30 carbon atoms, such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, dibutylphenyl, tributylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, dibutylnaphthyl, tributylnaphthyl, anthracene, etc.; and other groups obtained by such combinations. Furthermore, one or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by a heteroatom group containing oxygen, sulfur, nitrogen, halogen, etc., and one part of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by a heteroatom group containing oxygen, sulfur, nitrogen, etc. As a result, it may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc.

[0894] R203 indicates that the hydrocarbon group with 1 to 30 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, decadecane, and so on. Alkyl groups with 1 to 30 carbon atoms, such as heptadecyl-1,17-diyl; cyclopentanediyl, cyclohexanediyl, norcamphenediyl, adamantanediyl, etc., with 3 to 30 carbon atoms, and cyclic saturated alkyl groups; alkyl phenyl, methyl alkyl phenyl, ethyl alkyl phenyl, n-propyl alkyl phenyl, isopropyl alkyl phenyl, n-butyl alkyl phenyl, isobutyl alkyl phenyl, dibutyl alkyl phenyl, tributyl alkyl phenyl, naphthyl, methyl naphthyl, ethyl naphthyl, n-propyl naphthyl, isopropyl naphthyl, n-butyl naphthyl, isobutyl naphthyl, dibutyl naphthyl, tributyl naphthyl, etc., and aryl groups, etc. Furthermore, one or all of the hydrogen atoms in the aforementioned alkyl group can be substituted by a heteroatom group containing oxygen, sulfur, nitrogen, halogen, etc., and one part of the -CH2- group in the aforementioned alkyl group can also be substituted by a heteroatom group containing oxygen, sulfur, nitrogen, etc. As a result, it may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonate ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. The aforementioned heteroatom is preferably an oxygen atom.

[0895] In formula (5), L21 is a single bond, an ether bond, or may contain a heteroatom with 1 to 20 carbon atoms in an extended hydrocarbon group. The above extended hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. As a specific example, those that are the same as those exemplified as extended hydrocarbon group represented by R203 can be listed.

[0896] In formula (5), Xa, Xb, Xc and Xd are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl atom. However, at least one of Xa, Xb, Xc and Xd is a fluorine atom or a trifluoromethyl atom.

[0897] As the photoacid generating agent represented by formula (5), it is preferable to be represented by the following formula (5'). [Chem. 725]

[0898] In formula (5'), L21 is the same as above. Xe is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. R301, R302, and R303 are each independently a hydrogen atom, or may contain a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms. The above hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. As specific examples, those that are the same as those exemplified by the hydrocarbon group represented by Rfa1 in formula (Xa-1-1) can be listed. p and q are each independently 0, 1, 2, 3, 4, or 5, and r is 0, 1, 2, 3, or 4.

[0899] As a specific example of a photoacid generating agent represented by formula (5), the same as that exemplified in Japanese Patent Application Publication No. 2017-26980 as a photoacid generating agent represented by formula (2) can be listed.

[0900] Among the above-mentioned photoacid generators, those containing anions represented by formula (Xa-1-1) or (Xa-4) exhibit low acid diffusion and excellent solubility in solvents, which is particularly good. In addition, those represented by formula (5') exhibit extremely low acid diffusion, which is particularly good.

[0901] In the case where the chemical amplification inhibitor composition of the present invention contains a photoacid generating agent (D), its content is preferably 0.1 to 40 parts by mass relative to 80 parts by mass of the base polymer (A), and more preferably 0.5 to 20 parts by mass. As long as the amount of photoacid generating agent (D) added is within the above range, the resolution is good, and there is no concern about the generation of foreign matter after the inhibitor film is developed or during peeling, which is preferable. The photoacid generating agent (D) can be used alone or in combination of two or more.

[0902] (E) Surfactants The chemical amplification inhibitor composition of the present invention may further 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 No. 2010-215608 or Japanese Patent Application Publication No. 2011-16746.

[0903] As surfactants that are insoluble or poorly soluble in water and alkaline developing solutions, the surfactants described in the above-mentioned publication are preferably FC-4430 (manufactured by 3M), Surflon (registered trademark) S-381 (manufactured by AGC SEIMI CHEMICAL CO., LTD.), OLFINE (registered trademark) E1004 (manufactured by Nissin Chemical Industry Co., Ltd.), KH-20, KH-30 (manufactured by AGC SEIMI CHEMICAL CO., LTD.), and oxetane ring-opening polymers represented by the following formula (surf-1). [Chemistry 726]

[0904] Here, R, Rf, A, B, C, m, and n are irrelevant to the aforementioned descriptions and apply only to formula (surf-1). R refers to an aliphatic group with 2 to 5 carbon atoms, ranging from 2 to 4 valences. Examples of these aliphatic groups that are divalent include ethyl, 1,4-butyl, 1,2-propyl, 2,2-dimethyl-1,3-propyl, and 1,5-pentyl; examples of those that are trivalent or tetravalent include the following. [Chem.727] (In the formula, the dashed lines represent atomic bonds, each a substructure derived from glycerol, trimethylolethane, trimethylolpropane, and neopentyl tertrol.)

[0905] Among these, 1,4-endobutyl, 2,2-dimethyl-1,3-endopropyl, etc. are preferred.

[0906] Rf is trifluoromethyl or pentafluoroethyl, preferably trifluoromethyl. m is an integer from 0 to 3, n is an integer from 1 to 4, and the sum of n and m is the valence of R, which 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 polymers, please refer to the specification of US Patent No. 5,650,483, etc.

[0907] Surfactants that are insoluble or sparingly soluble in water but soluble in alkaline developing solutions, when no resist protective film is used in ArF immersion lithography, can reduce water penetration or leaching by aligning with the surface of the resist film. Therefore, they are useful for reducing damage to the exposure equipment by inhibiting the leaching of water-soluble components from the resist film. Furthermore, because they are soluble in alkaline aqueous solutions after exposure or post-exposure baking (PEB), they are less likely to become foreign substances causing defects, which is also useful. Such surfactants are polymeric surfactants with properties that are insoluble or sparingly soluble in water but soluble in alkaline developing solutions; they are also known as hydrophobic resins, and those with high water-repellent properties that enhance hydrophobicity are particularly desirable.

[0908] Specific examples of such polymeric surfactants include polymeric surfactants containing at least one of the repeating units represented by formula (6A) (hereinafter also referred to as repeating unit 6A.), repeating units represented by formula (6B) (hereinafter also referred to as repeating unit 6B.), repeating units represented by formula (6C) (hereinafter also referred to as repeating unit 6C.), repeating units represented by formula (6D) (hereinafter also referred to as repeating unit 6D.), and repeating units represented by formula (6E) (hereinafter also referred to as repeating unit 6E.). [Chem.728]

[0909] In formulas (6A) to (6E), RB represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. W1 represents -CH2-, -CH2CH2-, -O-, or two separate -H groups. Rs1 represents a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms. Rs2 represents a single bond or a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms. Rs3 represents a hydrogen atom, a hydrocarbon group or a fluorinated hydrocarbon group with 1 to 15 carbon atoms, or an acid-labile group. In the case where Rs3 is a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group may be inserted between the carbon-carbon bonds. Rs4 represents a hydrocarbon group or a fluorinated hydrocarbon group with a (u+1) valence of 1 to 20 carbon atoms. u represents 1, 2, or 3. Rs5 represents a hydrogen atom or a group represented by -C(=O)-O-Rsa. Rsa represents a fluorinated hydrocarbon group with 1 to 20 carbon atoms. Rs6 series hydrocarbon groups or fluorinated hydrocarbon groups with 1 to 15 carbon atoms may also have ether bonds or carbonyl groups inserted between their carbon-carbon bonds.

[0910] Rs1 represents a hydrocarbon group with 1 to 10 carbon atoms, which 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, dibutyl, tributyl, 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.

[0911] The alkyl group represented by Rs2 should preferably be a saturated alkyl group, which can be linear, branched, or cyclic. Specific examples include methylene, ethyl alkyl, propyl alkyl, butyl alkyl, and pentyl alkyl.

[0912] The hydrocarbon group represented by Rs3 or Rs6 can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include aliphatic unsaturated hydrocarbon groups such as saturated hydrocarbon groups, alkenyl groups, and alkynyl groups, which are preferably saturated hydrocarbon groups. Specific examples of the aforementioned saturated hydrocarbon groups, in addition to those exemplified by hydrocarbon groups represented by Rs1, include undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl groups. Specific examples of fluorinated hydrocarbon groups represented by Rs3 or Rs6 include groups formed by replacing one or all of the hydrogen atoms bonded to the carbon atom with fluorine atoms. As described above, ether bonds or carbonyl groups can also be inserted between these carbon-carbon bonds.

[0913] Specific examples of acid-instable groups represented by Rs3 include groups represented by formulas (AL-3) to (AL-5), trialkylsilyl groups in which each alkyl group has 1 to 6 carbon atoms, and alkyl groups containing side oxygen atoms in which each alkyl group has 4 to 20 carbon atoms.

[0914] The (u+1) valence hydrocarbon group or fluorinated hydrocarbon group represented by Rs4 can be any of the following: linear, branched, or cyclic. As specific examples, groups obtained by removing u hydrogen atoms from the above-mentioned hydrocarbon group or fluorinated hydrocarbon group can be listed.

[0915] The fluorinated hydrocarbon group represented by Rsa should preferably be saturated and can be linear, branched, or cyclic. Specific examples include hydrocarbon groups in which some or all of the hydrogen atoms are replaced by fluorine atoms. Examples include 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-dodecylheptyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, etc.

[0916] Specific examples of repeating units 6A to 6E can be listed below, but are not limited to these. Furthermore, in the following formula, RB refers to the same units as described above. [Chemistry 729]

[0917] [Chemistry 730]

[0918] [Chemistry 731]

[0919] [Chemistry 732]

[0920] [Chemistry 733]

[0921] [Chemistry 734]

[0922] The aforementioned polymeric surfactants may also contain other repeating units besides repeating units 6A to 6E. Specific examples of other repeating units include repeating units obtained from methacrylic acid or α-trifluoromethacrylic acid derivatives. In the polymeric surfactant, the content of repeating units 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.

[0923] The Mw of the above-mentioned polymeric surfactants should preferably be 1,000 to 500,000, more preferably 3,000 to 100,000. The Mw / Mn ratio should preferably be 1.0 to 2.0, more preferably 1.0 to 1.6.

[0924] As a method for synthesizing the above-mentioned polymeric surfactants, one method is to polymerize a monomer containing an unsaturated bond, selected from at least one of repeating units 6A to 6E and other repeating units as needed, in an organic solvent by adding a free radical initiator and heating. Specific examples of organic solvents used in polymerization include toluene, benzene, THF, diethyl ether, and dialkylene. Specific examples of polymerization initiators include AIBN, 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauryl peroxide. The reaction temperature is preferably 50–100°C. The reaction time is preferably 4–24 hours. Acid-labile groups can be directly introduced into the monomer, or post-polymerization protection or partial protection can be performed.

[0925] In the synthesis of the aforementioned polymeric surfactants, known chain transfer agents such as dodecyl mercaptan or 2-mercaptoethanol can be used to adjust the molecular weight. In this case, the amount of such chain transfer agent added should preferably be 0.01 to 10 mol relative to the total moles of the monomers being polymerized.

[0926] In the case where the chemical amplification inhibitor composition of the present invention contains surfactant (E), its content is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 10 parts by mass, relative to 80 parts by mass of the base polymer (A). As long as the content of surfactant (E) is 0.1 parts by mass or more, the receding contact angle between the inhibitor film surface and water is sufficiently improved; as long as it is 50 parts by mass or less, the dissolution rate of the developer on the inhibitor film surface is low, thus sufficiently maintaining the height of the formed fine pattern. Surfactant (E) can be used alone or in combination of two or more.

[0927] [(F) Dissolution Inhibitor] The chemical amplification inhibitor composition of the present invention may further contain a dissolution inhibitor as component (F). In the case where the chemical amplification inhibitor composition of the present invention is positive, by incorporating a dissolution inhibitor, the difference in dissolution rate between the exposed and unexposed areas can be further increased, thereby further improving resolution.

[0928] Specific examples of the aforementioned dissolution inhibitors include compounds with a molecular weight preferably between 100 and 1000, more preferably between 150 and 800, in which the hydrogen atoms of the phenolic hydroxyl groups of a compound containing two or more phenolic hydroxyl groups are replaced by acid-instable groups at a ratio of 0 to 100 mol% in all respects; or compounds in which the hydrogen atoms of the carboxyl groups of a compound containing carboxyl groups are replaced by acid-instable groups at an average ratio of 50 to 100 mol% in all respects. Specifically, examples include compounds in which the hydrogen atoms of the hydroxyl and carboxyl groups of bisphenol A, phenolphthalein, phenolphthalein, cresol phenolic varnish, naphtholic acid, adamantane carboxylic acid, and cholic acid are replaced by acid-instable groups. Examples of such compounds include those described in paragraphs

[0155] to

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

[0929] In the case where the chemical amplification inhibitor composition of the present invention contains a dissolution inhibitor (F), its content is preferably 0 to 50 parts by mass relative to 80 parts by mass of the base polymer (A), and more preferably 5 to 40 parts by mass. The dissolution inhibitor (F) can be used alone or in combination of two or more.

[0930] [(G) Other ingredients] The chemical amplification inhibitor composition of the present invention, as other components (G), may also contain compounds that generate acid through acid decomposition (acid-increasing compounds), organic acid derivatives, fluorinated alcohols, water-repellent improvers, etc. For the aforementioned acid-increasing compounds, refer to the compounds described in Japanese Patent Application Publication No. 2009-269953 or Japanese Patent Application Publication No. 2010-215608. When containing the aforementioned acid-increasing compounds, the content is preferably 0 to 5 parts by mass relative to 80 parts by mass of the base polymer (A), and more preferably 0 to 3 parts by mass. If the content is too high, it may be difficult to control acid diffusion, leading to deterioration of resolution and pattern shape. For the aforementioned organic acid derivatives and fluorinated alcohols, refer to the compounds described in Japanese Patent Application Publication No. 2009-269953 or Japanese Patent Application Publication No. 2010-215608.

[0931] The aforementioned water-repellent improver can be used in immersion photography without a top coat. As such water-repellent improvers, polymers containing fluorinated alkyl groups, polymers containing 1,1,1,3,3,3-hexafluoro-2-propanol residues with a specific structure, and preferably those exemplified in Japanese Patent Application Publication Nos. 2007-297590 and 2008-111103 are preferred. The aforementioned water-repellent improvers need to be soluble in alkaline or organic solvent developing solutions. The aforementioned water-repellent improvers containing specific 1,1,1,3,3,3-hexafluoro-2-propanol residues exhibit good solubility in developing solutions. As water-repellent improvers, polymers containing repeating units containing amine groups or amine salts are highly effective in preventing the evaporation of acid in PEB and in preventing poor opening of the hole pattern after development. In the case where the chemical amplification inhibitor composition of the present invention contains the above-mentioned water-repellent improver, its content is preferably 0 to 20 parts by mass relative to 80 parts by mass of the (A) base polymer, and more preferably 0.5 to 10 parts by mass.

[0932] [Pattern Formation Method] When the chemically amplified resist composition of the present invention is used in the manufacture of various integrated circuits, known lithography techniques can be applied. For example, as a patterning method, a method comprising the following steps can be listed: forming a resist film on a substrate using the above-mentioned chemically amplified resist composition, exposing the above-mentioned resist film to high-energy rays, and developing the above-mentioned exposed resist film using a developer.

[0933] First, the chemically amplified resist composition of the present invention is coated onto a substrate for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective film, etc.) or a substrate for mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.) with a film thickness of 0.01~2.0 μm using appropriate coating methods such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor blade coating. The substrate is then pre-baked on a hot plate, preferably at 60~150°C for 10 seconds~30 minutes, more preferably at 80~120°C for 30 seconds~20 minutes, to form a resist film.

[0934] Then, the resist film is exposed using high-energy rays. Examples of such high-energy rays include ultraviolet light, far-ultraviolet light, EB, EUV with wavelengths of 3-15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation. When using ultraviolet light, far-ultraviolet light, EUV, X-rays, soft X-rays, excimer laser light, gamma rays, or synchrotron radiation as high-energy rays, irradiation is performed directly or using a mask to form the desired pattern, with an exposure dose preferably of about 1-200 mJ / cm², and more preferably about 10-100 mJ / cm². When using EB as high-energy rays, the pattern is drawn directly or using a mask to form the desired pattern, with an exposure dose preferably of about 0.1-100 μC / cm², and more preferably about 0.5-50 μC / cm². The chemical amplification inhibitor composition of the present invention is particularly suitable for micro-patterning using ArF excimer laser light with a wavelength of 193 nm, KrF excimer laser light with a wavelength of 248 nm, EB or EUV, X-rays, soft X-rays, gamma rays or synchrotron radiation with a wavelength of 3~15 nm, especially in high-energy rays.

[0935] After exposure, PEB can also be applied on a hot plate at a temperature of 60-150°C for 10-30 seconds, or more preferably at 80-120°C for 30-20 seconds.

[0936] After exposure or PEB, use a developing solution containing 0.1-10% by mass, preferably 2-5% by mass, of an alkaline aqueous solution of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc., and develop it for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes, using conventional methods such as dip, immersion, or spray. In this way, the exposed areas dissolve in the developing solution, while the unexposed areas do not dissolve, forming the desired positive pattern on the substrate.

[0937] Organic solvent developers can also be used instead of the aforementioned alkaline aqueous solutions to obtain negative patterns. Specific examples of developers used in this context 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, etc. Ethyl soybean ester, 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, benzyl formate, ethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, etc. These organic solvents can be used alone or in mixtures of two or more.

[0938] Rinsing may also be performed at the end of development. The rinsing solution should preferably be miscible with the developer and should not dissolve the resist film. Such a solvent is preferably an alcohol with 3 to 10 carbon atoms, an ether compound with 8 to 12 carbon atoms, an alkanes with 6 to 12 carbon atoms, an alkene, an alkyne, or an aromatic solvent.

[0939] Specific examples of alcohols with 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tributyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tripentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, and 2,3-dimethyl-2- Butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 1-octanol, etc.

[0940] Specific examples of the aforementioned ether compounds with 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, didi-second butyl ether, di-n-pentyl ether, diisopentyl ether, didi-second pentyl ether, di-third pentyl ether, and di-n-hexyl ether.

[0941] Specific examples of alkanes with 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. Specific examples of alkenes with 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Specific examples of alkynes with 6 to 12 carbon atoms include hexyne, heptyne, and octyne.

[0942] Specific examples of solvents in the aforementioned aromatic systems include toluene, xylene, ethylbenzene, isopropylbenzene, tributylbenzene, and mesitylene.

[0943] Rinsing can reduce the collapse or defects of the resist pattern. However, rinsing is not always necessary; omitting it can reduce solvent usage.

[0944] Alternatively, the developed hole or groove pattern can be shrunk using heat transfer, RELACS, or DSA techniques. A shrinking agent is applied to the hole pattern, and during baking, the diffusion of the acid catalyst from the resist film causes cross-linking of the shrinking agent on the surface of the resist film. The shrinking agent adheres to the sidewalls of the hole pattern. The baking temperature should be 70~180℃, more preferably 80~170℃, and the baking time should be 10~300 seconds to remove excess shrinking agent and reduce the size of the hole pattern. [Example]

[0945] 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 embodiments described below. Furthermore, the apparatus used is as described below. MALDI TOF-MS: S3000 manufactured by Nippon Electronics Co., Ltd.

[0946] [1] Synthesis of strontium salt type monomers [Example 1-1] Synthesis of strontium salt type monomer a-1 [Chemistry 735]

[0947] Under nitrogen atmosphere, compounds SM-1 (63.7 g), SM-2 (57.8 g), methyl isobutyl ketone (300 g), and water (150 g) were added, and the mixture was stirred at room temperature for 30 minutes. The organic layer was separated, washed with water, and then concentrated under reduced pressure. The residue was purified by silicone column chromatography to obtain 101.8 g of monomer a-1 as an oil (yield 88%).

[0948] The TOF-MS results of strontium salt type monomer a-1 are shown below. MALDI TOF-MS: POSITIVE M+601 (equivalent to C26H22F4IO2S+) NEGATIVE M-555 (equivalent to C15H9I2O5S-)

[0949] [Examples 1-2~1-7] Synthesis of strontium salt type monomers a-2~a-7 Using the corresponding raw materials and known organic synthesis reactions, the strontium salt type monomers a-2 to a-7 in the following formula table were synthesized. [Chemistry 736]

[0950] [Comparative Examples 1-1 to 1-5] Comparison of the synthesis of onium salt type monomers Ca-1 to Ca-5 Using the corresponding raw materials and known organic synthesis reactions, comparative onium salt monomers ca-1 to ca-5 represented by the following formulas were synthesized. [Chemistry 737]

[0951] [2] Synthesis of basic polymers The monomers used in the synthesis of the basic polymer, other than monomers a-1 to a-7 and comparative monomers ca-1 to ca-5, are as follows. [Chemistry 738]

[0952] [Chemistry 739]

[0953] [Chemistry 740]

[0954] [Chemistry 741]

[0955] [Chemistry 742]

[0956] [Example 2-1] Synthesis of Polymer P-1 Under nitrogen atmosphere, monomer-polymerization initiator solution was prepared in a flask by taking 14.0 g of monomer a-1, 27.0 g of monomer b1-1, 8.7 g of monomer c-1, 50.3 g of monomer d-1, 2.79 g of V-601 (manufactured by Fujifilm and Koei Tecmo Chemicals), and 140 g of MEK. In another flask under nitrogen atmosphere, 46 g of MEK was taken and heated to 80°C with stirring. The monomer-polymerization initiator solution was then added dropwise over 4 hours. After the addition was complete, the polymerization solution was maintained at 80°C and stirred for 2 hours, then cooled to room temperature. The obtained polymerization solution was added dropwise to 3000 g of vigorously stirred hexane, and the precipitated polymer was separated by filtration. The obtained polymer was washed twice with 600 g of hexane and then vacuum dried at 50°C for 20 hours to obtain a white powder polymer P-1 (yield 96.1 g, 96% yield). The Mw ratio of polymer P-1 is 10300, and the Mw / Mn ratio is 1.54. Furthermore, the Mw ratio is a polystyrene conversion value determined by GPC using DMF as a solvent. [Chemistry 743]

[0957] [Examples 2-2~2-50, Comparative Examples 2-1~2-38] Synthesis of polymers P-2~P-50 and comparative polymers CP-1~CP-38 By changing the type and blending ratio of each monomer, the polymers shown in Tables 1-3 are manufactured in the same manner as in Synthesis Example 2-1.

[0958] [Table 1] polymer Unit 1 Import ratio (mol%) Unit 2 Import ratio (mol%) Unit 3 Import ratio (mol%) Unit 4 Import ratio (mol%) Unit 5 Import ratio (mol%) Mw Mw / Mn P-1 a-1 5 b1-1 50 c-1 30 d-1 15 - - 10300 1.54 P-2 a-2 5 b1-1 50 c-1 30 d-1 15 - - 10400 1.52 P-3 a-3 5 b1-1 50 c-1 30 d-1 15 - - 10200 1.53 P-4 a-4 5 b1-1 50 c-1 30 d-1 15 - - 10000 1.54 P-5 a-5 5 b1-1 50 c-1 30 d-1 15 - - 10300 1.55 P-6 a-6 5 b1-1 50 c-1 30 d-1 15 - - 10100 1.55 P-7 a-7 5 b1-1 50 c-1 30 d-1 15 - - 10400 1.54 P-8 a-1 5 b1-2 50 c-1 30 d-1 15 - - 10300 1.53 P-9 a-2 5 b1-2 50 c-1 30 d-1 15 - - 10500 1.52 P-10 a-3 5 b1-2 50 c-1 30 d-1 15 - - 10300 1.56 P-11 a-4 5 b1-2 50 c-1 30 d-1 15 - - 10200 1.53 P-12 a-5 5 b1-2 50 c-1 30 d-1 15 - - 10400 1.53 P-13 a-6 5 b1-2 50 c-1 30 d-1 15 - - 10500 1.55 P-14 a-7 5 b1-2 50 c-1 30 d-1 15 - - 10600 1.56 P-15 a-1 5 b1-3 50 c-1 30 d-1 15 - - 10400 1.55 P-16 a-2 5 b1-3 50 c-1 30 d-1 15 - - 10300 1.54 P-17 a-3 5 b1-3 50 c-1 30 d-1 15 - - 10200 1.52 P-18 a-4 5 b1-3 50 c-1 30 d-1 15 - - 10300 1.51 P-19 a-5 5 b1-3 50 c-1 30 d-1 15 - - 10400 1.54 P-20 a-6 5 b1-3 50 c-1 30 d-1 15 - - 10500 1.55 P-21 a-7 5 b1-3 50 c-1 30 d-1 15 - - 10600 1.53 P-22 a-1 5 b1-4 50 c-1 30 d-1 15 - - 10300 1.54 P-23 a-2 5 b1-4 50 c-1 30 d-1 15 - - 10400 1.55 P-24 a-3 5 b1-4 50 c-1 30 d-1 15 - - 10100 1.55 P-25 a-4 5 b1-4 50 c-1 30 d-1 15 - - 10400 1.56 P-26 a-5 5 b1-4 50 c-1 30 d-1 15 - - 10200 1.53 P-27 a-6 5 b1-4 50 c-1 30 d-1 15 - - 10300 1.52 P-28 a-7 5 b1-4 50 c-1 30 d-1 15 - - 10400 1.54 P-29 a-1 5 b1-1 25 b2-1 25 c-2 30 d-1 15 10500 1.55 P-30 a-1 5 b1-2 25 b2-1 25 c-2 30 d-1 15 10600 1.53

[0959] [Table 2] polymer Unit 1 Import ratio (mol%) Unit 2 Import ratio (mol%) Unit 3 Import ratio (mol%) Unit 4 Import ratio (mol%) Unit 5 Import ratio (mol%) Mw Mw / Mn P-31 a-1 5 b1-3 25 b2-1 25 c-2 30 d-1 8 10500 1.53 P-32 a-1 5 b1-3 30 b2-1 25 c-3 25 d-1 15 10300 1.55 P-33 a-1 5 b1-1 25 b2-1 25 c-4 30 d-2 15 10400 1.54 P-34 a-2 5 b1-1 30 b3-1 15 c-1 30 d-2 15 10400 1.53 P-35 a-2 5 b1-1 25 b1-4 25 c-2 30 d-1 15 10500 1.52 P-36 a-1 5 b1-1 50 c-1 30 d-2 15 - - 10300 1.54 P-37 a-1 5 b1-1 50 c-1 30 d-3 15 - - 10200 1.55 P-38 a-2 5 b1-1 50 c-1 30 d-4 15 - - 10100 1.56 P-39 a-3 5 b1-1 50 c-1 30 d-5 15 - - 10600 1.55 P-40 a-4 5 b1-1 50 c-1 30 d-6 15 - - 10400 1.55 P-41 a-2 5 b1-1 45 c-2 25 d-1 15 e-1 10 10200 1.54 P-42 a-3 5 b1-3 45 c-4 25 d-2 15 e-2 10 10100 1.53 P-43 a-4 5 b1-3 45 c-2 25 d-3 10 e-3 5 10200 1.52 P-44 a-1 7 b1-1 58 c-1 35 - - - - 10400 1.54 P-45 a-2 7 b1-1 58 c-1 35 - - - - 10200 1.51 P-46 a-3 7 b1-1 58 c-2 35 - - - - 10500 1.55 P-47 a-4 7 b1-3 58 c-3 35 - - - - 10300 1.54 P-48 a-5 7 b1-4 58 c-4 35 - - - - 10100 1.56 P-49 a-6 7 b1-1 29 b2-1 29 c-1 35 - - 10400 1.54 P-50 a-7 7 b1-1 29 b3-1 29 c-2 35 - - 10200 1.52

[0960] [Table 3] polymer Unit 1 Import ratio (mol%) Unit 2 Import ratio (mol%) Unit 3 Import ratio (mol%) Unit 4 Import ratio (mol%) Unit 5 Import ratio (mol%) Mw Mw / Mn CP-1 ca-1 5 b1-1 50 c-1 30 d-1 15 - - 10200 1.53 CP-2 as-2 5 b1-1 50 c-1 30 d-1 15 - - 10200 1.55 CP-3 as-3 5 b1-1 50 c-1 30 d-1 15 - - 10500 1.52 CP-4 as-4 5 b1-1 50 c-1 30 d-1 15 - - 10400 1.53 CP-5 as-5 5 b1-1 50 c-1 30 d-1 15 - - 10400 1.54 CP-6 as-1 5 b1-2 50 c-1 30 d-1 15 - - 10200 1.55 CP-7 as-2 5 b1-2 50 c-1 30 d-1 15 - - 10200 1.54 CP-8 as-3 5 b1-2 50 c-1 30 d-1 15 - - 10600 1.55 CP-9 as-4 5 b1-2 50 c-1 30 d-1 15 - - 10600 1.53 CP-10 as-5 5 b1-2 50 c-1 30 d-1 15 - - 10300 1.54 CP-11 as-1 5 b1-3 50 c-1 30 d-1 15 - - 10400 1.56 CP-12 as-2 5 b1-3 50 c-1 30 d-1 15 - - 10300 1.52 CP-13 as-3 5 b1-3 50 c-1 30 d-1 15 - - 10200 1.51 CP-14 as-4 5 b1-3 50 c-1 30 d-1 15 - - 10100 1.55 CP-15 as-5 5 b1-3 50 c-1 30 d-1 15 - - 10200 1.55 CP-16 as-1 5 b1-4 50 c-1 30 d-1 15 - - 10400 1.54 CP-17 as-2 5 b1-4 50 c-1 30 d-1 15 - - 10300 1.54 CP-18 as-3 5 b1-4 50 c-1 30 d-1 15 - - 10400 1.55 CP-19 as-4 5 b1-4 50 c-1 30 d-1 15 - - 10300 1.53 CP-20 as-5 5 b1-4 50 c-1 30 d-1 15 - - 10100 1.52 CP-21 ca-1 5 b1-1 25 b2-1 25 c-2 30 d-1 15 10400 1.52 CP-22 ca-2 5 b1-2 25 b2-1 25 c-2 30 d-2 15 10000 1.53 CP-23 ca-4 5 b1-3 25 b2-1 25 c-2 30 d-4 8 10300 1.51 CP-24 ca-1 5 b1-1 25 b2-1 25 c-2 30 cd-1 15 10200 1.53 CP-25 ca-2 5 b1-2 25 b2-1 25 c-2 30 cd-2 15 10300 1.54 CP-26 ca-5 5 b1-3 25 b2-1 25 c-2 30 CD-3 15 10300 1.56 CP-27 ca-1 5 b1-1 50 c-1 30 CD-1 15 But But 10400 1.53 CP-28 ca-1 5 b1-1 50 c-1 30 cd-2 15 But But 10300 1.52 CP-29 ca-2 5 b1-1 50 c-1 30 cd-3 15 - - 10100 1.54 CP-30 as-1 5 b1-1 45 c-2 25 d-1 15 e-1 10 10400 1.55 CP-31 as-2 5 b1-3 45 c-4 25 cd-1 15 e-2 10 10300 1.56 CP-32 as-4 5 b1-3 45 c-2 25 cd-2 10 e-3 5 10200 1.55 CP-33 as-1 7 b1-1 58 c-1 35 - - - - 10200 1.53 CP-34 ca-2 7 b1-1 58 c-2 35 But But But But 10400 1.55 CP-35 ca-4 7 b1-2 58 c-2 35 But But But But 10400 1.54 CP-36 ca-1 7 b1-1 29 b2-1 29 c-1 35 But But 10500 1.52 CP-37 b1-1 55 c-1 30 CD-1 15 But But But But 10300 1.54 CP-38 b1-2 50 c-2 50 But But - - - - 10300 1.53

[0961] [3] Preparation of chemical amplification inhibitor composition [Examples 3-1 to 3-53, Comparative Examples 3-1 to 3-40] A solution was prepared by dissolving the predetermined components selected from the basic polymers of this invention (P-1 to P-50), the comparative basic polymers (CP-1 to CP-38), the acid generators (PAG-1, PAG-2), and the quenchers (SQ-1, AQ-1) as shown in Tables 4 to 6 in a solvent containing 0.01% by mass of 3M FC-4430 as a surfactant. The solution was then filtered through a 0.2 μm Teflon (registered trademark) filter to prepare chemical amplification inhibitor compositions (R-1 to R-53, CR-1 to CR-40).

[0962] [Table 4] inhibitor Composition Basic polymers (parts by weight) Quenching agent (parts by weight) Acid generating agent (parts by weight) solvent (parts by weight) Solvent 2 (parts by weight) Solvent 3 (parts by weight) Example 3-1 R-1 P-1(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-2 R-2 P-2(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-3 R-3 P-3(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-4 R-4 P-4(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-5 R-5 P-5(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-6 R-6 P-6(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-7 R-7 P-7(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-8 R-8 P-8(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-9 R-9 P-9(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-10 R-10 P-10(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-11 R-11 P-11(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-12 R-12 P-12(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-13 R-13 P-13(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-14 R-14 P-14(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-15 R-15 P-15(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-16 R-16 P-16(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-17 R-17 P-17(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-18 R-18 P-18(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-19 R-19 P-19(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-20 R-20 P-20(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-21 R-21 P-21(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-22 R-22 P-22(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-23 R-23 P-23(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-24 R-24 P-24(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-25 R-25 P-25(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-26 R-26 P-26(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-27 R-27 P-27(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-28 R-28 P-28(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-29 R-29 P-29(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-30 R-30 P-30(80) - - PGMEA(2250) EL(2800) DAA(550)

[0963] [Table 5] inhibitor Composition Basic polymers (parts by weight) Quenching agent (parts by weight) Acid generating agent (parts by weight) solvent (parts by weight) Solvent 2 (parts by weight) Solvent 3 (parts by weight) Example 3-31 R-31 P-31(80) - PAG-1(10) PGMEA(2250) EL(2800) DAA(550) Example 3-32 R-32 P-32(80) - - PGMEA(2250) EL(2800) DAA(550) Example 3-33 R-33 P-33(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-34 R-34 P-34(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-35 R-35 P-35(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-36 R-36 P-36(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-37 R-37 P-37(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-38 R-38 P-38(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-39 R-39 P-39(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-40 R-40 P-40(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-41 R-41 P-41(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-42 R-42 P-42(80) - - PGMEA(2250) EL(2800) DAA(550) Examples 3-43 R-43 P-43(80) - PAG-2(10) PGMEA(2250) EL(2800) DAA(550) Examples 3-44 R-44 P-44(80) - PAG-1(20) PGMEA(2250) EL(2800) DAA(550) Examples 3-45 R-45 P-45(80) - PAG-1(20) PGMEA(2250) EL(2800) DAA(550) Examples 3-46 R-46 P-46(80) - PAG-1(15) PAG-3(5) PGMEA(2250) EL(2800) DAA(550) Examples 3-47 R-47 P-47(80) - PAG-2(20) PGMEA(2250) EL(2800) DAA(550) Examples 3-48 R-48 P-48(80) - PAG-1(20) PGMEA(2250) EL(2800) DAA(550) Examples 3-49 R-49 P-49(80) - PAG-2(15) PAG-3(5) PGMEA(2250) EL(2800) DAA(550) Examples 3-50 R-50 P-50(80) - PAG-1(20) PGMEA(2250) EL(2800) DAA(550) Examples 3-51 R-51 P-1(80) SQ-1(4) - PGMEA(2250) EL(2800) DAA(550) Example 3-52 R-52 P-1(80) AQ-1(4) - PGMEA(2250) EL(2800) DAA(550) Examples 3-53 R-53 P-1(80) SQ-1(2) AQ-1(2) - PGMEA(2250) EL(2800) DAA(550)

[0964] [Table 6] inhibitor Composition Basic polymers (parts by weight) Quenching agent (parts by weight) Acid generating agent (parts by weight) Solvent 1 (parts by weight) Solvent 2 (parts by weight) Solvent 3 (parts by weight) Comparative Example 3-1 CR-1 CP-1(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-2 CR-2 CP-2(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-3 CR-3 CP-3(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Examples 3-4 CR-4 CP-4(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Examples 3-5 CR-5 CP-5(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Examples 3-6 CR-6 CP-6(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Examples 3-7 CR-7 CP-7(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Examples 3-8 CR-8 CP-8(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Examples 3-9 CR-9 CP-9(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-10 CR-10 CP-10(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-11 CR-11 CP-11(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-12 CR-12 CP-12(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-13 CR-13 CP-13(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-14 CR-14 CP-14(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-15 CR-15 CP-15(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-16 CR-16 CP-16(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-17 CR-17 CP-17(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-18 CR-18 CP-18(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-19 CR-19 CP-19(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-20 CR-20 CP-20(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-21 CR-21 CP-21(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-22 CR-22 CP-22(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-23 CR-23 CP-23(80) - PAG-1(10) PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-24 CR-24 CP-24(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-25 CR-25 CP-25(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-26 CR-26 CP-26(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-27 CR-27 CP-27(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-28 CR-28 CP-28(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-29 CR-29 CP-29(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-30 CR-30 CP-30(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-31 CR-31 CP-31(80) - - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-32 CR-32 CP-32(80) - PAG-2(10) PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-33 CR-33 CP-33(80) - PAG-1(20) PGMEA(2250) EL(2800) DAA(550) Comparative Examples 3-34 CR-34 CP-34(80) - PAG-1(15) PAG-3(5) PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-35 CR-35 CP-35(80) - PAG-2(15) PAG-3(5) PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-36 CR-36 CP-36(80) - PAG-1(20) PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-37 CR-37 CP-37(80) SQ-1(8) - PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-38 CR-38 CP-38(80) SQ-1(8) PAG-1(20) PGMEA(2250) EL(2800) DAA(550) Comparative Example 3-39 CR-39 CP-38(80) AQ-1(8) PAG-2(20) PGMEA(2250) EL(2800) DAA(550) Comparative Examples 3-40 CR-40 CP-38(80) SQ-1(4) AQ-1(4) PAG-1(15) PAG-3(5) PGMEA(2250) EL(2800) DAA(550)

[0965] In Tables 4-6, the solvents, quenchers (SQ-1, AQ-1) and acid generators (PAG-1, PAG-2) are the same as described below. Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate) EL (ethyl lactate) DAA (diacetone alcohol)

[0966] Quenching agents: SQ-1, AQ-1 [Chemistry 744]

[0967] • Acid generating agents: PAG-1, PAG-2, PAG-3 [Chemistry 745]

[0968] [4] Evaluation of EUV lithography (1) [Examples 4-1 to 4-53, Comparative Examples 4-1 to 4-40] The chemical amplification resist compositions (R-1 to R-53, CR-1 to CR-40) shown in Tables 4-6 were spin-coated onto a Si substrate with a 20 nm thick silicon spin-coated hard mask (SHB-A940, silicon content 43% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd. A 50 nm thick resist film was fabricated by pre-baking at 100°C for 60 seconds using a heated plate. For the resist film, an LS pattern with a wafer size of 18 nm and a pitch of 36 nm was exposed using an ASML EUV scanning exposure machine NXE3300 (NA 0.33, σ 0.9 / 0.6, dipole illumination) while varying the exposure dose and focus (exposure pitch: 1 mJ / cm², focus pitch: 0.020 μm). After exposure, a PEB process was performed at the temperatures shown in Tables 7-9 for 60 seconds. Subsequently, the sample was immersed in a 2.38% TMAH aqueous solution for 30 seconds for development, rinsed with a washing material containing surfactant, and then rotated to dry, thus obtaining a positive pattern. The obtained LS patterns were observed using a critical dimension SEM (CG6300) manufactured by Hitachi High-Tech Corporation. Sensitivity, EL, LWR, DOF, and collapse limit were evaluated according to the methods described below. Furthermore, the development defects of the obtained LS patterns were evaluated. The results are shown in Tables 7-9.

[0969] [Sensitivity Evaluation] The optimal exposure value Eop (mJ / cm2) for obtaining an LS pattern with a linewidth of 18nm and a pitch of 36nm is determined and used as the sensitivity. The smaller the value, the higher the sensitivity.

[0970] [EL Review] The exposure amount formed within ±10% (16.2~19.8nm) of the 18nm spacing in the above LS pattern is calculated using the following formula (unit: %). The larger the value, the better the performance. EL(%) = (|E1-E2| / Eop) × 100 E1: Optimal exposure for an LS pattern with a linewidth of 16.2nm and a pitch of 36nm. E2: Optimal exposure for an LS pattern with a linewidth of 19.8nm and a pitch of 36nm. Eop: Optimal exposure for an LS pattern with a linewidth of 18nm and a pitch of 36nm.

[0971] [LWR Evaluation] The dimensions of the LS pattern obtained by Eop irradiation are measured at 10 points along the length of the line. The standard deviation (σ) of the results is then multiplied by 3 (3σ) as the LWR. The smaller this value, the more uniform the line width and the less roughness of the pattern can be obtained.

[0972] [DOF Rating] As an evaluation of focal depth, the focal range formed within ±10% (16.2~19.8nm) of the 18nm dimension in the aforementioned LS pattern is determined. The larger this value, the wider the focal depth.

[0973] [Collapse Limit Assessment of Line Patterns] The line dimensions of each exposure at the optimal focus of the aforementioned LS pattern were measured along the length of 10 points. The finest line dimension obtained without collapse was taken as the collapse limit dimension. The smaller this value, the better the collapse limit.

[0974] [Evaluation of Development Defects] An LS pattern with a linewidth of 18nm and a pitch of 36nm, formed using the optimal exposure, was inspected using a KLA-Tencor Corporation defect inspection device KLA2360 (trade name). The pixel size of the defect inspection device was set to 0.16μm, and the threshold was set to 20. Defects (number / cm²) were extracted by comparing the differences between the image and the overlapping pixel units for inspection, and the number of defects per unit area (defects / cm²) was calculated. Then, by performing defect review, development defects were extracted from all defects, and the number of development defects per unit area (defects / cm²) was calculated. Values ​​less than 0.5 were designated as A, values ​​greater than 0.5 and less than 1.0 as B, values ​​greater than 1.0 and less than 5.0 as C, and values ​​greater than 5.0 as D. Lower values ​​indicate better performance.

[0975] [Table 7] inhibitor Composition PEB temperature (°C) Optimal exposure (mJ / cm2) EL (%) LWR (nm) DOF (nm) Collapse Limit (nm) Development defects Example 4-1 R-1 100 32 19 2.2 120 11.2 A Example 4-2 R-2 100 32 17 2.2 120 11.1 A Example 4-3 R-3 100 33 18 2.2 110 10.9 A Example 4-4 R-4 100 33 16 2.5 100 11.1 A Examples 4-5 R-5 105 33 17 2.3 120 11.3 A Examples 4-6 R-6 100 34 18 2.3 110 10.9 A Examples 4-7 R-7 100 34 17 2.4 120 11.1 A Examples 4-8 R-8 95 35 16 2.4 100 11.0 A Examples 4-9 R-9 100 33 17 2.2 110 11.2 A Examples 4-10 R-10 100 34 18 2.3 110 11.1 A Example 4-11 R-11 100 33 19 2.4 110 10.9 A Example 4-12 R-12 100 33 17 2.5 120 11.1 A Example 4-13 R-13 105 34 17 2.2 110 10.9 A Example 4-14 R-14 100 33 18 2.4 100 11.1 A Examples 4-15 R-15 95 32 17 2.4 110 11.2 A Example 4-16 R-16 105 34 17 2.3 120 10.7 A Example 4-17 R-17 100 33 16 2.5 100 10.8 A Example 4-18 R-18 95 32 19 2.3 110 11.2 A Example 4-19 R-19 95 32 17 2.4 110 11.0 A Example 4-20 R-20 100 34 16 2.2 120 10.8 A Example 4-21 R-21 100 35 18 2.3 100 11.2 A Example 4-22 R-22 95 33 19 2.5 120 11.1 A Example 4-23 R-23 100 32 18 2.5 110 11.1 A Example 4-24 R-24 100 34 17 2.3 120 11.3 A Example 4-25 R-25 100 32 18 2.4 110 10.9 A Example 4-26 R-26 100 32 17 2.3 120 10.8 A Example 4-27 R-27 105 34 19 2.2 110 11.1 A Example 4-28 R-28 100 33 17 2.3 120 11.1 A Example 4-29 R-29 100 32 18 2.4 100 11.3 A Example 4-30 R-30 95 33 17 2.3 120 11.1 A

[0976] [Table 8] inhibitor Composition PEB temperature (°C) Optimal exposure (mJ / cm2) EL (%) LWR (nm) DOF (nm) Collapse Limit (nm) Development defects Example 4-31 R-31 100 32 19 2.3 110 11.0 A Example 4-32 R-32 100 34 16 2.2 120 11.3 A Example 4-33 R-33 100 32 18 2.3 100 10.7 A Example 4-34 R-34 95 32 17 2.3 100 11.1 A Examples 4-35 R-35 100 34 18 2.2 110 11.2 A Example 4-36 R-36 100 32 19 2.3 110 11.1 A Example 4-37 R-37 100 32 17 2.4 110 11.0 A Example 4-38 R-38 100 33 19 2.2 110 11.2 A Example 4-39 R-39 95 34 17 2.5 120 11.0 A Example 4-40 R-40 100 33 18 2.3 110 10.8 A Example 4-41 R-41 95 34 16 2.2 110 11.1 A Examples 4-42 R-42 100 32 18 2.4 120 11.2 A Examples 4-43 R-43 100 33 18 2.4 110 10.9 A Examples 4-44 R-44 100 33 16 2.3 100 11.3 A Examples 4-45 R-45 95 35 17 2.4 100 11.0 A Examples 4-46 R-46 95 33 19 2.2 110 10.8 A Examples 4-47 R-47 100 32 18 2.4 100 10.8 A Examples 4-48 R-48 95 32 18 2.5 120 11.1 A Examples 4-49 R-49 100 32 17 2.3 100 10.9 A Examples 4-50 R-50 100 34 19 2.2 120 11.0 A Examples 4-51 R-51 100 32 18 2.3 120 11.2 A Examples 4-52 R-52 100 32 16 2.2 110 11.0 A Examples 4-53 R-53 100 33 18 2.4 110 11.2 A

[0977] [Table 9] inhibitor Composition PEB temperature (°C) Optimal exposure (mJ / cm2) EL (%) LWR (nm) DOF (nm) Collapse Limit (nm) Development defects Comparative Example 4-1 CR-1 100 38 13 3 90 12.4 B Comparative Example 4-2 CR-2 95 39 12 3.2 90 12.1 C Comparative Example 4-3 CR-3 100 36 14 3.1 80 12.3 B Comparative Example 4-4 CR-4 105 37 14 3 90 12.5 C Comparative Examples 4-5 CR-5 100 37 14 3.2 80 12.2 B Comparative Examples 4-6 CR-6 95 41 12 2.8 90 12.5 C Comparative Examples 4-7 CR-7 100 38 12 3.1 90 13.0 B Comparative Examples 4-8 CR-8 105 37 14 3.2 90 12.8 C Comparative Examples 4-9 CR-9 95 40 14 3.2 80 13.1 B Comparative Example 4-10 CR-10 100 39 12 3 90 13.2 C Comparative Example 4-11 CR-11 95 39 13 3.2 90 12.7 B Comparative Example 4-12 CR-12 100 37 14 3.1 90 12.3 B Comparative Example 4-13 CR-13 100 41 12 3.2 90 13.0 C Comparative Example 4-14 CR-14 95 38 13 3.2 90 12.3 B Comparative Example 4-15 CR-15 105 41 12 3.1 90 12.7 C Comparative Example 4-16 CR-16 100 37 12 2.8 90 12.4 C Comparative Example 4-17 CR-17 100 39 11 3.1 80 13.1 B Comparative Example 4-18 CR-18 95 37 13 2.9 80 13.3 C Comparative Example 4-19 CR-19 100 38 12 3.1 90 12.5 B Comparative Example 4-20 CR-20 95 38 14 3 80 13.4 C Comparative Example 4-21 CR-21 100 40 13 2.9 90 12.2 B Comparative Example 4-22 CR-22 100 39 15 3 90 13.2 C Comparative Example 4-23 CR-23 100 38 13 3.2 80 12.5 C Comparative Example 4-24 CR-24 95 41 15 3.3 90 12.6 C Comparative Example 4-25 CR-25 100 38 12 3.1 90 12.2 B Comparative Example 4-26 CR-26 105 37 14 2.8 80 13.5 C Comparative Example 4-27 CR-27 100 38 13 3.1 90 12.6 B Comparative Example 4-28 CR-28 95 36 15 3.3 90 12.6 C Comparative Example 4-29 CR-29 100 40 14 3.2 90 12.2 C Comparative Example 4-30 CR-30 95 38 13 3.1 90 12.1 B Comparative Example 4-31 CR-31 100 39 12 2.8 90 12.4 C Comparative Example 4-32 CR-32 95 40 13 3.3 80 13.4 C Comparative Example 4-33 CR-33 95 39 14 3.5 90 12.7 C Comparative Example 4-34 CR-34 100 37 13 3.2 80 13.1 B Comparative Example 4-35 CR-35 100 36 15 3.4 90 12.7 C Comparative Example 4-36 CR-36 105 37 13 2.8 70 13.3 C Comparative Example 4-37 CR-37 95 38 14 3.6 70 13.3 B Comparative Example 4-38 CR-38 100 40 13 2.8 70 13.2 C Comparative Example 4-39 CR-39 95 37 13 3.5 70 13.5 C Comparative Example 4-40 CR-40 100 36 14 3.6 70 14.0 B

[0978] As shown in Tables 7-9, the chemical amplification inhibitor composition using a base polymer containing repeating units of the onium salt monomer from this invention exhibits good sensitivity and excellent EL, LWR, and DOF. Furthermore, a low collapse limit value was confirmed, demonstrating strong resistance to pattern collapse even in the formation of fine patterns. Further, suppression of development defects was also confirmed. Therefore, the chemical amplification inhibitor composition of this invention demonstrates its suitability as a material for EUV lithography.

[0979] [5] Evaluation of EUV lithography (2) [Examples 5-1 to 5-53, Comparative Examples 5-1 to 5-40] The chemically amplified resist compositions (R-1 to R-53, CR-1 to CR-10) shown in Tables 4-6 were spin-coated onto a Si substrate with a 20 nm thick silicon spin-coating hard mask (SHB-A940, silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. A 50 nm thick resist film was pre-baked at 105 °C for 60 seconds using a hot plate. The resist film was then exposed using an ASML NXE3400 EUV scanning exposure machine (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, wafer-level pitch 46 nm, +20% tolerance hole pattern mask). A 60-second PEB treatment was performed using a hot plate at the temperatures listed in Tables 10-12, followed by 30 seconds of development with a 2.38% by mass TMAH aqueous solution, resulting in a 23 nm hole pattern. Using a critical dimension SEM (CG6300) manufactured by Hitachi High-Tech Corporation, the exposure was measured when a hole size of 23 nm was formed, and this value was used as the sensitivity. In addition, the size of 50 holes at this time was measured, and three times the standard deviation (σ) of the results (3σ) was used as the CDU. The results are shown in Tables 10-12.

[0980] [Table 10] inhibitor Composition PEB temperature (°C) Optimal exposure (mJ / cm2) CDU (nm) Example 5-1 R-1 95 twenty two 2.3 Example 5-2 R-2 95 twenty two 2.3 Example 5-3 R-3 90 twenty three 2.4 Example 5-4 R-4 90 twenty two 2.5 Example 5-5 R-5 90 twenty four 2.2 Examples 5-6 R-6 95 twenty three 2.2 Examples 5-7 R-7 95 twenty three 2.3 Examples 5-8 R-8 90 twenty four 2.3 Examples 5-9 R-9 95 twenty three 2.4 Examples 5-10 R-10 95 twenty three 2.4 Examples 5-11 R-11 95 twenty two 2.2 Examples 5-12 R-12 90 twenty four 2.4 Examples 5-13 R-13 90 twenty three 2.2 Examples 5-14 R-14 90 25 2.3 Examples 5-15 R-15 90 twenty two 2.3 Examples 5-16 R-16 85 twenty three 2.4 Examples 5-17 R-17 95 twenty four 2.5 Example 5-18 R-18 95 twenty four 2.3 Example 5-19 R-19 90 twenty four 2.3 Example 5-20 R-20 95 twenty three 2.2 Example 5-21 R-21 95 twenty two 2.3 Example 5-22 R-22 95 twenty three 2.3 Example 5-23 R-23 95 25 2.4 Example 5-24 R-24 95 twenty four 2.2 Example 5-25 R-25 95 twenty three 2.3 Example 5-26 R-26 95 twenty three 2.4 Example 5-27 R-27 95 twenty three 2.2 Example 5-28 R-28 95 twenty three 2.3 Example 5-29 R-29 90 twenty four 2.4 Examples 5-30 R-30 95 twenty four 2.4

[0981] [Table 11] inhibitor Composition PEB temperature (°C) Optimal exposure (mJ / cm2) CDU (nm) Example 5-31 R-31 95 twenty three 2.5 Example 5-32 R-32 95 twenty two 2.2 Example 5-33 R-33 95 25 2.3 Examples 5-34 R-34 90 twenty three 2.4 Examples 5-35 R-35 95 twenty four 2.4 Examples 5-36 R-36 95 twenty four 2.3 Example 5-37 R-37 90 twenty two 2.2 Example 5-38 R-38 90 twenty two 2.2 Example 5-39 R-39 95 twenty four 2.3 Examples 5-40 R-40 95 twenty two 2.4 Example 5-41 R-41 95 twenty four 2.2 Example 5-42 R-42 90 twenty three 2.3 Examples 5-43 R-43 95 25 2.3 Examples 5-44 R-44 95 twenty two 2.2 Examples 5-45 R-45 90 twenty three 2.3 Examples 5-46 R-46 95 twenty four 2.4 Examples 5-47 R-47 90 twenty three 2.3 Examples 5-48 R-48 90 twenty three 2.4 Example 5-49 R-49 95 twenty three 2.5 Examples 5-50 R-50 90 twenty four 2.2 Examples 5-51 R-51 95 twenty two 2.3 Examples 5-52 R-52 95 25 2.4 Examples 5-53 R-53 95 twenty three 2.3

[0982] [Table 12] inhibitor Composition PEB temperature (°C) Optimal exposure (mJ / cm2) CDU (nm) Comparative Example 5-1 CR-1 95 30 2.8 Comparative Example 5-2 CR-2 90 28 2.9 Comparative Example 5-3 CR-3 90 27 2.9 Comparative Example 5-4 CR-4 95 29 2.8 Comparative Example 5-5 CR-5 90 29 2.9 Comparative Examples 5-6 CR-6 95 28 2.7 Comparative Examples 5-7 CR-7 95 28 2.8 Comparative Examples 5-8 CR-8 95 28 2.9 Comparative Examples 5-9 CR-9 90 28 2.8 Comparative Examples 5-10 CR-10 95 28 2.7 Comparative Example 5-11 CR-11 95 29 2.9 Comparative Example 5-12 CR-12 90 29 2.8 Comparative Example 5-13 CR-13 90 28 2.8 Comparative Example 5-14 CR-14 90 28 2.9 Comparative Example 5-15 CR-15 95 28 3.0 Comparative Example 5-16 CR-16 85 30 2.8 Comparative Example 5-17 CR-17 95 28 2.8 Comparative Example 5-18 CR-18 95 27 2.7 Comparative Example 5-19 CR-19 90 30 2.9 Comparative Example 5-20 CR-20 95 28 2.9 Comparative Example 5-21 CR-21 95 28 2.8 Comparative Example 5-22 CR-22 95 28 2.7 Comparative Example 5-23 CR-23 95 27 2.9 Comparative Example 5-24 CR-24 95 28 2.9 Comparative Example 5-25 CR-25 95 27 2.8 Comparative Example 5-26 CR-26 95 28 2.7 Comparative Example 5-27 CR-27 95 27 2.8 Comparative Example 5-28 CR-28 95 28 2.8 Comparative Example 5-29 CR-29 90 30 2.8 Comparative Example 5-30 CR-30 90 27 2.7 Comparative Example 5-31 CR-31 95 29 2.8 Comparative Example 5-32 CR-32 90 29 2.7 Comparative Example 5-33 CR-33 95 28 2.8 Comparative Example 5-34 CR-34 95 29 2.7 Comparative Example 5-35 CR-35 95 29 2.7 Comparative Example 5-36 CR-36 95 27 2.8 Comparative Example 5-37 CR-37 90 30 3.0 Comparative Example 5-38 CR-38 90 31 3.3 Comparative Example 5-39 CR-39 90 32 3.1 Comparative Example 5-40 CR-40 90 32 3.3

[0983] The results shown in Tables 10-12 confirm that the chemical amplification inhibitor composition system of the present invention has good sensitivity and excellent performance in CDU.

[0984] [6] Evaluation of dry etching resistance [Examples 6-1 to 6-50, Comparative Examples 6-1 to 6-38] Dissolve 2g of each polymer (polymers P-1 to P-50 and comparative polymers CP-1 to CP-10) shown in Tables 1 and 2 in 10g of cyclohexanone. The polymer solution was filtered through a 0.2μm filter and then spin-coated onto a Si substrate to form a film with a thickness of 300nm. The film was then evaluated under the following conditions. Etching test using CHF3 / CF4 based gases: 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. The etching conditions are as follows. Chamber pressure 40 Pa RF power 1000W 9mm gap CHF3 gas flow rate 30 mL / min CF4 gas flow rate 30 mL / min Ar gas flow rate 100 mL / min 60 seconds The evaluation system indicates that films with smaller thickness differences, i.e., smaller reductions, have higher etching resistance. The results of dry etching resistance are shown in Tables 13-15.

[0985] [Table 13] polymer CHF3 / CF4-based gas etching rate (nm / min) Example 6-1 P-1 93 Example 6-2 P-2 95 Example 6-3 P-3 94 Example 6-4 P-4 95 Example 6-5 P-5 93 Example 6-6 P-6 93 Examples 6-7 P-7 94 Examples 6-8 P-8 96 Examples 6-9 P-9 96 Examples 6-10 P-10 97 Examples 6-11 P-11 95 Examples 6-12 P-12 94 Examples 6-13 P-13 95 Examples 6-14 P-14 95 Examples 6-15 P-15 96 Examples 6-16 P-16 97 Examples 6-17 P-17 94 Examples 6-18 P-18 93 Examples 6-19 P-19 94 Examples 6-20 P-20 95 Example 6-21 P-21 94 Example 6-22 P-22 96 Example 6-23 P-23 95 Example 6-24 P-24 96 Example 6-25 P-25 97 Example 6-26 P-26 94 Example 6-27 P-27 95 Example 6-28 P-28 96 Example 6-29 P-29 94 Examples 6-30 P-30 95

[0986] [Table 14] polymer CHF3 / CF4-based gas etching rate (nm / min) Example 6-31 P-31 95 Example 6-32 P-32 95 Example 6-33 P-33 96 Examples 6-34 P-34 93 Examples 6-35 P-35 94 Examples 6-36 P-36 95 Examples 6-37 P-37 96 Examples 6-38 P-38 96 Examples 6-39 P-39 97 Examples 6-40 P-40 94 Example 6-41 P-41 96 Examples 6-42 P-42 97 Examples 6-43 P-43 94 Examples 6-44 P-44 95 Examples 6-45 P-45 96 Examples 6-46 P-46 95 Examples 6-47 P-47 94 Examples 6-48 P-48 96 Examples 6-49 P-49 95 Examples 6-50 P-50 95

[0987] [Table 15] polymer CHF3 / CF4-based gas etching rate (nm / min) Comparative Example 6-1 CP-1 105 Comparative Example 6-2 CP-2 101 Comparative Example 6-3 CP-3 102 Comparative Example 6-4 CP-4 102 Comparative Example 6-5 CP-5 102 Comparative Example 6-6 CP-6 103 Comparative Examples 6-7 CP-7 104 Comparative Examples 6-8 CP-8 103 Comparative Examples 6-9 CP-9 104 Comparative Examples 6-10 CP-10 101 Comparative Example 6-11 CP-11 105 Comparative Examples 6-12 CP-12 103 Comparative Example 6-13 CP-13 104 Comparative Example 6-14 CP-14 109 Comparative Example 6-15 CP-15 103 Comparative Example 6-16 CP-16 107 Comparative Example 6-17 CP-17 100 Comparative Example 6-18 CP-18 106 Comparative Example 6-19 CP-19 103 Comparative Example 6-20 CP-20 102 Comparative Example 6-21 CP-21 105 Comparative Example 6-22 CP-22 102 Comparative Example 6-23 CP-23 103 Comparative Example 6-24 CP-24 105 Comparative Example 6-25 CP-25 101 Comparative Example 6-26 CP-26 103 Comparative Example 6-27 CP-27 106 Comparative Example 6-28 CP-28 102 Comparative Example 6-29 CP-29 103 Comparative Example 6-30 CP-30 105 Comparative Example 6-31 CP-31 107 Comparative Example 6-32 CP-32 109 Comparative Example 6-33 CP-33 104 Comparative Example 6-34 CP-34 106 Comparative Example 6-35 CP-35 105 Comparative Example 6-36 CP-36 103 Comparative Example 6-37 CP-37 107 Comparative Example 6-38 CP-38 114

[0988] Based on the results shown in Tables 13-15, it was confirmed that the polymer system of the present invention has excellent dry etching resistance to CHF3 / CF4 gas.

Claims

1. A strontium salt type monomer, represented by the following formula (a1): Wherein, n2 is 1, 2, 3, or 4; n3 is 1 or 2; n4 is 0, 1, or 2; however, 0 ≦ n2 + n3 + n4 ≦ 5; n6 is 1, 2, 3, or 4; n7 is 0, 1, or 2; however, 0 ≦ n6 + n7 ≦ 5; n8 is 1 or 2; RF 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, a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, or a pentafluorosulfonium group; when n6 is 2, 3, or 4, each RF may be the same or different from the others; R1 and R2 are each independently a halogen atom other than fluorine, nitro, cyano, hydroxyl, carboxyl, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms containing heteroatoms; when n4 is 2, each R1 can be the same or different, and two R1s can also bond to each other to form a ring with the carbon atoms of these bonds; when n7 is 2, each R2 can be the same or different, and two R2s can also bond to each other to form a ring with the carbon atoms of these bonds; L1 is an ether bond, ester bond, or carbonate bond; RAL is an unstable acid group; in addition, two of the three aromatic rings bonded to S+ can also bond to each other to form a ring with the sulfur atoms of these bonds; Z- is the anion represented by the following formula (Z); 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 or 1; however, m1 is 0. When m1 is 1, the system is 0≦m2+m3+m11≦4; when m4 is 0, the system is 0≦m2+m3+m11≦6; when m4 is 0, the system is 0≦m5+m6≦4; when m4 is 1, the system is 0≦m5+m6≦6; when m7 is 0, the system is 0≦m8+m9≦5; when m7 is 1, the system is 0≦m8+m9≦7; furthermore, 1≦m2+m5+m8≦4. RA consists of hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups; R3, R4, and R5 are each independently a halogen atom other than iodine, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy carbonyl group with 1 to 20 carbon atoms containing heteroatoms; when m3 is 2 or 3, each R3 can be the same or different, and two R3s can also bond to each other to form a ring with the bonded carbon atoms; when m6 is 2 or 3, each R4 can be the same or different, and two R4s can also bond to each other to form a ring with the bonded carbon atoms; when m9 is 2 or 3, each R5 can be the same or different, and two R5s can also bond to each other to form a ring with the bonded carbon atoms.LA1, LA2, LB1, and LB2 are each independently composed of single bonds, ether bonds, carbonyl groups, ester bonds, sulfonate bonds, amide bonds, sulfonamide bonds, carbonate bonds, or carbamate bonds; XL1 and XL2 are each independently composed of single bonds, or may contain heteroatoms with 1 to 40 carbon atoms in an alkyl group.

2. As in request item 1, the strontium salt type monomer, wherein, The unstable group system of this acid is represented by the following formula (AL-1) or (AL-2): where p1 and p2 are each independently 0 or 1; q1 and q2 are each independently 0, 1, 2, 3 or 4; RL1 and RL2 are each independently a hydrocarbon group having 1 to 12 carbon atoms; RL3 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; the -CH2- portion of the hydrocarbon group represented by RL1, RL2, and RL3 can also be substituted by -O- or -S-. In the case where the hydrocarbon group contains an aromatic ring, part or all of the hydrogen atoms of the aromatic ring can also be substituted by a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms containing a halogen atom, or an alkoxy group having 1 to 4 carbon atoms containing a halogen atom; in addition, RL1 and RL2 can also bond together with these bonded carbon atoms to form a ring, and the -CH2- portion of the ring can also be substituted by -O- or -S-; however, in the case where RL3 is a hydrogen atom, RL1 and RL2 are bonded together with these bonded carbon atoms to form an alicyclic ring containing multiple bonds; in addition, a portion of the hydrogen atoms of the alicyclic ring can also be substituted by a halogen atom. RL4 and RL5 are each independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms; RL6 is a hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- portion of this hydrocarbon group can also be substituted by -O- or -S-; In addition, RL5 and RL6 can also bond with each other to form a heterocyclic group with 3 to 20 carbon atoms together with the carbon atoms of these bonds and LB, and the -CH2- portion of this heterocyclic group can also be substituted by -O- or -S-; LB is -O- or -S-; RLa~RLd are each independently a hydrogen atom, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms; * indicates an atomic bond with L1.

3. A strontium salt type quenching agent, comprising strontium salt type monomers as claimed in claim 1 or 2.

4. A polymer comprising repeating units from a strontium salt-type quencher as claimed in claim 3.

5. The polymer of claim 4 further contains at least one of the repeating units selected from the following formula (b1), the following formula (b2), and the following formula (b3): ​​wherein RA is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; X1 is a single bond, a phenyl group, a naphthyl group, *-C(=O)-O-X11-, or *-C(=O)-N(H)-X11-, which may also be substituted by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group containing fluorine atoms with 1 to 10 carbon atoms, a saturated hydrocarbon group containing fluorine atoms with 1 to 10 carbon atoms, an oxygen group, or a halogen atom; X11 is a saturated hydrocarbon group with 1 to 10 carbon atoms, a phenyl group, or a naphthyl group, which may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring; X2 represents a single bond, *-C(=O)-O- or *-C(=O)-N(H)-; * indicates an atomic bond with a carbon atom in the main chain; R11 represents a halogen atom, cyano, hydroxyl, nitro, pentafluorothio, or may contain a hydrocarbon group with 1-20 carbon atoms, a hydrocarbon oxygen group with 1-20 carbon atoms, a hydrocarbon carbonyl group with 2-20 carbon atoms, a hydrocarbon carbonyl oxygen group with 2-20 carbon atoms, or a hydrocarbon oxygen carbonyl group with 2-20 carbon atoms; when a1 is 2, 3, or 4, each R11 can be the same or different; AL1 and AL2 are each independently acid-labile groups; a1 is 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; RA is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; X3 is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-; * indicates an atomic bond with a carbon atom of the main chain; X4 is a single bond, an aliphatic hydrocarbon group with 1 to 4 carbon atoms, a carbonyl group, a sulfonyl group, or a group obtained by combination of these; X5 and X6 are each independently an oxygen atom or a sulfur atom; however, X4 and X6 are bonded to adjacent carbon atoms of the aromatic ring; R12 and R13 are each independently a hydrogen atom, or may also contain a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; in addition, R12 and R13 may also bond to each other and form a ring together with such bonded carbon atoms; R14 can be a halogen atom, hydroxyl group, cyano group, nitro group, pentafluorothio group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon thio group with 1 to 20 carbon atoms, or -N(R14A)(R14B); R14A and R14B are each independently a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms; when b2 is 2 or more, each R14 can be the same or different from each other, and multiple R14s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings of these bonds.

6. The polymer of claim 4 further contains repeating units represented by the following formula (c): Wherein, RA is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; Y1 is a single bond, *-C(=O)-O- or *-C(=O)-N(H)-; * represents an atomic bond with a carbon atom of the main chain; R21 is a halogen atom, a carboxyl group, a nitro group, a cyano group, a pentafluorothio group, or may contain a hydrocarbon group with 1 to 20 carbon atoms of heteroatoms, or may contain a hydrocarbon oxy group with 1 to 20 carbon atoms of heteroatoms, or may contain a hydrocarbon carbonyl group with 2 to 20 carbon atoms of heteroatoms, or may contain a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms of heteroatoms, or may contain a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms of heteroatoms; c1 is 1, 2, 3 or 4; c2 is 0, 1, 2 or 3; however, 1 ≤ c1 + c2 ≤ 5.

7. The polymer of claim 4 further contains repeating units from a fluorosulfonic acid anion having a polymerizable group and at least one iodine atom, and a strontium cation.

8. The polymer of claim 4 further contains repeating units represented by the following formula (e); wherein, RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z1 is a single bond, a phenyl group, a naphthyl group, *-C(=O)-O-Z11- or *-C(=O)-N(H)-Z11-, the phenyl group or naphthyl group may also be substituted by a hydroxyl group, a nitro group, a cyano group, a saturated hydrocarbon group containing fluorine atoms with 1 to 10 carbon atoms, a saturated hydrocarbon group containing fluorine atoms with 1 to 10 carbon atoms, an oxygen group, or a halogen atom; * represents an atomic bond with a carbon atom of the main chain; Z11 is a saturated hydrocarbon group with 1 to 10 carbon atoms, a phenyl group, or a naphthyl group, the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring; R51 is a group with 1 to 20 carbon atoms, or a structure containing at least one of the following: 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)-).

9. A chemical amplification inhibitor composition comprising (A) a base polymer comprising a polymer as claimed in claim 4.

10. The chemical amplification inhibitor composition of claim 9 further contains (B) an organic solvent.

11. The chemical amplification inhibitor composition of claim 9 further contains (C) a quencher.

12. The chemical amplification inhibitor composition of claim 9 further contains (D) an acid generating agent.

13. The chemical amplification inhibitor composition of claim 9 further contains (E) surfactant.

14. A pattern forming method comprising the steps of: forming a resist film on a substrate using a chemical amplifying resist composition as claimed in claim 9, exposing the resist film to high-energy rays, and developing the exposed resist film using a developing solution.

15. The pattern forming method as described in claim 14, wherein, The high-energy rays are ArF excimer laser light with a wavelength of 193nm or KrF excimer laser light with a wavelength of 248nm, electron beams or extreme ultraviolet light with a wavelength of 3~15nm.

Images