Resist pattern forming method

Abstract

The present invention relates to a resist pattern forming method. The object of the present invention is to provide a non-chemically amplified resist composition excellent in limit resolution in optical lithography using high-energy rays, and a pattern forming method using the resist composition. The means for solving the object is a resist pattern forming method comprising the steps of: (i) forming a resist film on a substrate or a lower layer film of a substrate on which a lower layer film is laminated, using a resist composition containing a high-valent iodine compound, a carboxyl group-containing compound, and a solvent, (ii) exposing the aforementioned resist film to high-energy rays, and (iii) developing the aforementioned exposed resist film using a developer containing an organic acid, thereby forming a negative pattern.

Description

Technical Field

[0001] This invention relates to a method for forming resist patterns. Background Technology

[0002] With the expansion of the IoT market, there is a growing demand for high integration, high speed, and low power consumption in LSI (Light Detector System), and the miniaturization of patterning is also progressing rapidly. In particular, logic devices are leading the way in miniaturization. Regarding the most advanced miniaturization technologies, mass production of 10nm node devices using ArF immersion lithography with dual, triple, and quadruple patterning is already underway. Furthermore, research is progressing on next-generation 7nm node devices using extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm.

[0003] As miniaturization progresses, image blurring caused by acid diffusion has become a problem (Non-Patent Literature 1). To ensure the resolution of fine patterns with a processing size of less than 45 nm, it has been proposed that not only is the improvement of dissolution contrast, as previously advocated, important, but also the control of acid diffusion is crucial (Non-Patent Literature 2). However, since chemically amplified resist compositions improve sensitivity and contrast through acid diffusion, if acid diffusion is suppressed to the limit by lowering the post-exposure baking (PEB) temperature or shortening the PEB time, sensitivity and contrast will be significantly reduced.

[0004] Adding acid-generating agents that produce bulky acids is effective in suppressing acid diffusion. Therefore, it has been proposed to use onium salts of polymerizable olefins as acid-generating agents in polymer copolymerization. However, considering acid diffusion, in the patterning of resist films with dimensions smaller than 16 nm, it is believed that chemically amplified resist compositions are no longer suitable for patterning, and the development of non-chemically amplified resist compositions is desired.

[0005] Materials used in non-chemically amplified resist compositions include polymethyl methacrylate (PMMA). PMMA is a positive resist material whose solubility in organic solvent developers is improved by breaking down the main chain and reducing the molecular weight through EUV irradiation.

[0006] Hydrosilsesquioxane (HSQ) undergoes crosslinking via the condensation reaction of silanols produced by EUV irradiation, thereby becoming a negative resist material insoluble in alkaline developers. Additionally, chlorinated calixarnes also function as negative resist materials. These negative resist materials, due to their small molecular size before crosslinking and the absence of blurring caused by acid diffusion, can be used as pattern transfer materials with low edge roughness and very high resolution, showcasing the resolving limits of exposure devices. However, the sensitivity of these materials is insufficient and further improvements are needed.

[0007] One of the main reasons hindering material development for EUV lithography applications is the low photon count in EUV exposure. EUV energy is significantly higher than ArF excimer lasers, and the photon count in EUV exposure is only one-fourteenth that of ArF exposure. Furthermore, the size of patterns formed by EUV exposure is less than half that of ArF exposure. Therefore, EUV exposure is susceptible to variations in photon count. These variations in photon count in extremely short wavelength emission regions constitute shot noise, a physical phenomenon that cannot be eliminated. Thus, so-called stochastics are a concern. While the effects of shot noise cannot be eliminated, we will discuss how to reduce them. Due to shot noise, not only do dimensional uniformity (CDU) and linewidth roughness (LWR) increase, but there is also a one in a million chance of observing hole blockage. Hole blockage leads to poor conductivity and transistor malfunction, thus negatively impacting overall device performance. When considering practical sensitivity, resist compositions with PMMA and HSQ as the main components are greatly affected by randomness and cannot achieve the desired resolution.

[0008] Regarding methods to reduce shot noise in resists, the introduction of elements with high absorption for EUV light has attracted attention. Patent Document 1 proposes a chemically amplified resist composition containing iodine atoms with high absorption for EUV light. However, as mentioned earlier, chemically amplified resist compositions cannot achieve excellent resolution in EUV lithography, where processing dimensions are becoming increasingly smaller. Especially in line and space patterns, as the pattern size decreases, pattern collapse and line breaks increase significantly, so reducing these issues is closely related to improving the limiting resolution.

[0009] Patent Document 2 proposes a negative resist composition using tin compounds. This composition uses tin, which has high absorption under EUV light, as the main component, thus improving randomness and achieving high sensitivity and resolution. However, such metal resists suffer from several issues, including insufficient solubility in resist solvents, storage stability, and defects caused by etching residues. Furthermore, since the exposed portion of the metal resist is primarily composed of metal oxides, it is a negative resist insoluble in the developer. Therefore, when used for patterning contact holes, an additional inversion process is required, raising concerns about cost.

[0010] Existing technical documents

[0011] Patent documents

[0012] [Patent Document 1] Japanese Patent Application Publication No. 2018-5224

[0013] [Patent Document 2] Japanese Patent Publication No. 2021-503482

[0014] Non-patent literature

[0015] [Non-Patent Literature 1] SPIE Vol. 5039 p1 (2003)

[0016] [Non-Patent Literature 2] SPIE Vol. 6520 p65203L-1 (2007) Summary of the Invention

[0017] [The problem that the invention aims to solve]

[0018] The present invention was made in view of the foregoing circumstances, and aims to provide a non-chemically amplified resist composition with excellent limiting resolution in optical lithography using high-energy rays, especially in electron beam (EB) lithography and EUV lithography, and a pattern formation method using the resist composition.

[0019] [Methods for solving the problem]

[0020] After repeated and in-depth explorations to achieve the aforementioned objectives, the inventors have obtained the following insights, and thus completed the present invention: a resist composition with a predetermined high-valent iodine compound and a carboxyl-containing compound (polymer or monomer compound) as the main components provides a resist film exhibiting excellent resolution and is extremely effective for precision micro-machining when using organic acids as the developer.

[0021] That is, the present invention provides the following method for forming resist patterns.

[0022] 1. A method for forming a resist pattern, comprising the following steps:

[0023] (i) A resist film is formed on a substrate or on the lower layer of a substrate having a lower layer film, using a resist composition containing a high-valent iodine compound, a carboxyl-containing compound, and a solvent.

[0024] (ii) Expose the aforementioned resist film to high-energy radiation, and

[0025] (iii) The previously exposed resist film is developed using a developer containing organic acid to form a negative pattern.

[0026] 2. The resist pattern forming method of 1, wherein the aforementioned high-valent iodine compound comprises at least one compound selected from any of the following formulas (1) to (16).

[0027] [Chemistry 1]

[0028]

[0029] [Chemistry 2]

[0030]

[0031] In the formula, m1 is 0, 1, or 2. When m1 is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1 ≤ n1 + n2 ≤ 6. When m1 is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1 ≤ n1 + n2 ≤ 8. When m1 is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1 ≤ n1 + n2 ≤ 10.

[0032] n3 is 1 or 2, n4 is 0, 1, 2, 3 or 4, and 1 ≤ n3 + n4 ≤ 5. n5 is 1 or 2, n6 is 0, 1, 2, 3 or 4, and 1 ≤ n5 + n6 ≤ 5.

[0033] n7 is 0, 1, 2, 3 or 4, and n8 is 1, 2, 3 or 4.

[0034] m2 is 0, 1, or 2. When m2 is 0, n9 is 0, 1, 2, 3, or 4; when m2 is 1, n9 is 0, 1, 2, 3, 4, 5, or 6; when m2 is 2, n9 is 0, 1, 2, 3, 4, 5, 6, 7, or 8.

[0035] m3 is 0, 1, or 2. When m3 is 0, n10 is 0, 1, 2, 3, or 4; when m3 is 1, n10 is 0, 1, 2, 3, 4, 5, or 6; when m3 is 2, n10 is 0, 1, 2, 3, 4, 5, 6, 7, or 8.

[0036] m4 is 0 or 1. When m4 is 0, n11 is 0, 1, 2, 3 or 4. When m4 is 1, n11 is 0, 1, 2, 3, 4, 5 or 6.

[0037] m5 is 0 or 1. When m5 is 0, n12 is 0, 1, 2, 3 or 4. When m5 is 1, n12 is 0, 1, 2, 3, 4, 5 or 6.

[0038] n13 and n14 are independently 0, 1, 2, 3, 4, 5 or 6.

[0039] n15 and n16 are independently 0, 1, 2 or 3.

[0040] m6 is 0, 1, or 2. When m6 is 0, n17 is 0, 1, 2, 3, or 4; when m6 is 1, n17 is 0, 1, 2, 3, 4, 5, or 6; when m6 is 2, n17 is 0, 1, 2, 3, 4, 5, 6, 7, or 8.

[0041] m7 is 0, 1, or 2. When m7 is 0, n18 is 0, 1, 2, or 3; when m7 is 1, n18 is 0, 1, 2, 3, 4, or 5; when m7 is 2, n18 is 0, 1, 2, 3, 4, 5, 6, or 7.

[0042] m8 is 0, 1, or 2. When m8 is 0, n19 is 0, 1, 2, or 3, and n20 is 0 or 1. When m8 is 1, n19 is 0, 1, 2, 3, 4, or 5, and n20 is 0 or 1. When m8 is 2, n19 is 0, 1, 2, 3, 4, 5, 6, or 7, and n20 is 0 or 1.

[0043] n21 is 0, 1, 2 or 3, n22 is 0, 1 or 2, n23 is 0, 1, 2, 3 or 4, n24 is 0, 1 or 2, n25 is 0 or 1, and n26 is 0, 1, 2 or 3.

[0044] R 1 ~R 31 Each group consists independently of a halogen atom or may contain heteroatoms and is a hydrocarbon group with 1 to 10 carbon atoms. Also, R 21 and R 22 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0045] R 41 ~R 44 R 47 R 49 ~R 56 R 59 R 60 and R 61 ~R 68 Each R is an independent hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. When n2 is 2 or more, each R 41 They can be the same or different, and there are multiple Rs. 41 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R 42 They can be the same or different, and there are multiple Rs. 42 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R 43 They can be the same or different, and there are multiple Rs. 43 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R 44 They can be the same or different, and there are multiple Rs. 44 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n9 is 2 or more, each R 47 They can be the same or different, and there are multiple Rs. 47They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n10 is 2 or more, each R 49 They can be the same or different, and there are multiple Rs. 49 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n11 is 2 or more, each R 50 They can be the same or different, and there are multiple Rs. 50 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n12 is 2 or more, each R 51 They can be the same or different, and there are multiple Rs. 51 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n13 is 2 or more, each R 52 They can be the same or different, and there are multiple Rs. 52 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n14 is 2 or more, each R 53 They can be the same or different, and there are multiple Rs. 53 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n15 is 2 or more, each R 54 They can be the same or different, and there are multiple Rs. 54 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n16 is 2 or more, each R 55 They can be the same or different, and there are multiple Rs. 55 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n17 is 2 or more, each R 56 They can be the same or different, and there are multiple Rs. 56 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n18 is 2 or more, each R 59 They can be the same or different, and there are multiple Rs. 59 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n19 is 2 or more, each R 60 They can be the same or different, and there are multiple Rs. 60 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n21 is 2 or more, each R 61 They can be the same or different, and there are multiple Rs. 61 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n22 is 2 or more, each R 63 They can be the same or different, and there are multiple Rs. 63 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n23 is 2 or more, each R 64 They can be the same or different, and there are multiple Rs.64 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n24 is 2 or more, each R 65 They can be the same or different, and there are multiple Rs. 65 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n26 is 2 or more, each R 68 They can be the same or different, and there are multiple Rs. 68 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0046] R 45 When n8 is 1, 3, or 4, it is an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, it is an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, thioketone bond, an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valent hydrocarbon group or (n8) valent heterocyclic group can be substituted by groups containing heteroatoms, and part of the -CH2- of the aforementioned (n8) valent hydrocarbon group can also be substituted by groups containing heteroatoms, and R... 44 and R 45 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0047] R 48 It is a carbonyl group or may contain heteroatoms and is a hydrocarbon group with 1 to 10 carbon atoms.

[0048] R 56 It is a hydrocarbon group with 1 to 10 carbon atoms that is either a halogen atom or may contain heteroatoms.

[0049] R 57 It is a hydrocarbon group with 1 to 10 carbon atoms that is either a halogen atom or may contain heteroatoms.

[0050] 1. 2. 3. 4. 5. 6. 7 and 8 represents the atomic bond of the carbon atom or heteroatom in the aromatic ring or heterocycle in the formula. However, 1 and 2. 3 and 4. 5 and 6 and 7 and 8. Bonded to adjacent atoms on an aromatic ring or adjacent atoms on a heterocyclic ring.

[0051] L 1 It can be unbonded, single bond, -O-, -S-, -NH- or -CH2-.

[0052] X is -S- or -N(R) 58 )-. R 58 It consists of a hydrocarbon group with 1 to 20 carbon atoms, which may be hydrogen atoms, halogen atoms, or heteroatoms.

[0053] X 1 and X 2 Each independently -OX 11 -or -X 12 -C(=O)-。 X 3 for -OX 11 -、 -SX 11 -or -X 12 -C(=O)-。 X 11 It is a carbonyl group or may contain heteroatoms and is a hydrocarbon group with 1 to 10 carbon atoms. X 12 -S- or -N(R) 69 )-. R 69 It consists of a hydrocarbon group with 1 to 20 carbon atoms, which may be hydrogen atoms, halogen atoms, or heteroatoms.

[0054] 3. The method for forming a resist pattern as described in 1. or 2, wherein the aforementioned carboxyl-containing compound is a carboxyl-containing polymer containing a repeating unit represented by the following formula (a-1) or a carboxylic acid compound represented by the following formula (a-2).

[0055] [Chemistry 3]

[0056]

[0057] In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group.

[0058] X A For single bonds, phenylene, naphthylene or -C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. It represents the atomic bonds between carbon atoms in the main chain and the main chain.

[0059] p can be 1, 2, 3 or 4.

[0060] R a1 When p is 1, 3, or 4, it is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms. When p is 2, it is an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, p-valent hydrocarbon group with 1 to 40 carbon atoms, or a p-valent heterocyclic group with 2 to 40 carbon atoms. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group may be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned p-valent hydrocarbon group may also be substituted by a group containing a heteroatom.

[0061] R a2 It is a single bond or a hydrocarbon group with 1 to 20 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group may be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group may also be replaced by a group containing a heteroatom. When p is 2, 3 or 4, each R a2 They can be the same or different.

[0062] 4. A method for forming a resist pattern as described in any one of 1 to 3, wherein the aforementioned organic acid comprises at least one compound selected from any one of the following formulas (b-1) to (b-7).

[0063] [Chemistry 4]

[0064]

[0065] In the formula, k is 1, 2, 3 or 4.

[0066] Rf 1 and Rf 2 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms, but all Rf 1 and Rf 2 It cannot be both hydrogen atoms at the same time.

[0067] R b1 It consists of a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group with 1 to 50 carbon atoms that may also contain heteroatoms.

[0068] R b2 It is a hydrocarbon group with 1 to 50 carbon atoms, consisting of hydrogen atoms, halogen atoms, hydroxyl groups, or heteroatoms. However, this excludes cases where the hydrogen atoms at the α and β positions of the sulfonic acid group are replaced by fluorine atoms or fluoroalkyl groups.

[0069] R b3 It consists of a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group with 1 to 50 carbon atoms that may also contain heteroatoms.

[0070] R b4It is a hydrocarbon group with 1 to 50 carbon atoms, consisting of hydrogen atoms, halogen atoms, hydroxyl groups, or heteroatoms. However, this excludes cases where the hydrogen atoms at the α and β positions of the carboxyl group are replaced by fluorine atoms or fluoroalkyl groups.

[0071] R b5 and R b6 Each can be an independent hydrocarbon group with 1 to 50 carbon atoms, which may also contain heteroatoms.

[0072] R b7 ~R b9 Each can be an independent hydrocarbon group with 1 to 50 carbon atoms, which may also contain heteroatoms.

[0073] R b10 It is a fluorine atom or a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and the fluorinated hydrocarbon group may also contain a hydroxyl group, an ether bond, or an ester bond. R b11 It consists of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and this hydrocarbon group may also contain a hydroxyl group, an ether bond, or an ester bond. Also, R b10 With R b11 They can also bond to each other and form rings together with the atoms they are bonded to.

[0074] 5. A method for forming a resist pattern as described in any one of 1 to 4, wherein the aforementioned high-energy rays are i-rays, KrF excimer lasers, ArF excimer lasers, EB or EUV.

[0075] [The effects of the invention]

[0076] The aforementioned resist composition is particularly useful in optical lithography using i-rays, KrF excimer lasers, ArF excimer lasers, EB or EUV, where it combines high sensitivity and high resolution to form fine patterns. Detailed Implementation

[0077] [Resist Composition]

[0078] The resist composition used in the resist pattern forming method of the present invention contains a predetermined high-valent iodine compound, a carboxyl-containing compound, and a solvent.

[0079] [High-valent iodine compounds]

[0080] The aforementioned high-valent iodine compound shall preferably be at least one of the high-valent iodine compounds represented by any of the following formulas (1) to (16).

[0081] [Chemistry 5]

[0082]

[0083] [Chemistry 6]

[0084]

[0085] In equation (1), m1 is 0, 1, or 2. When m1 is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1 ≤ n1 + n2 ≤ 6. When m1 is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1 ≤ n1 + n2 ≤ 8. When m1 is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1 ≤ n1 + n2 ≤ 10.

[0086] In equation (2), n3 is 1 or 2, n4 is 0, 1, 2, 3 or 4, and 1≤n3+n4≤5, n5 is 1 or 2, n6 is 0, 1, 2, 3 or 4, and 1≤n5+n6≤5.

[0087] In equation (3), n7 is 0, 1, 2, 3 or 4, and n8 is 1, 2, 3 or 4.

[0088] In formula (4), m2 is 0, 1 or 2. When m2 is 0, n9 is 0, 1, 2, 3 or 4; when m2 is 1, n9 is 0, 1, 2, 3, 4, 5 or 6; when m2 is 2, n9 is 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0089] In formula (5), m3 is 0, 1 or 2. When m3 is 0, n10 is 0, 1, 2, 3 or 4; when m3 is 1, n10 is 0, 1, 2, 3, 4, 5 or 6; when m3 is 2, n10 is 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0090] In equation (6), m4 is 0 or 1. When m4 is 0, n11 is 0, 1, 2, 3 or 4. When m4 is 1, n11 is 0, 1, 2, 3, 4, 5 or 6.

[0091] In equation (6), m5 is 0 or 1. When m5 is 0, n12 is 0, 1, 2, 3 or 4. When m5 is 1, n12 is 0, 1, 2, 3, 4, 5 or 6.

[0092] In equation (7), n13 and n14 are 0, 1, 2, 3, 4, 5 or 6.

[0093] In equation (8), n15 and n16 are 0, 1, 2 or 3.

[0094] In formula (9), m6 is 0, 1 or 2. When m6 is 0, n17 is 0, 1, 2, 3 or 4; when m6 is 1, n17 is 0, 1, 2, 3, 4, 5 or 6; when m6 is 2, n17 is 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0095] In formula (10), m7 is 0, 1 or 2. When m7 is 0, n18 is 0, 1, 2 or 3; when m7 is 1, n18 is 0, 1, 2, 3, 4 or 5; when m7 is 2, n18 is 0, 1, 2, 3, 4, 5, 6 or 7.

[0096] In formula (10), m8 is 0, 1 or 2. When m8 is 0, n19 is 0, 1, 2 or 3, and n20 is 0 or 1. When m8 is 1, n19 is 0, 1, 2, 3, 4 or 5, and n20 is 0 or 1. When m8 is 2, n19 is 0, 1, 2, 3, 4, 5, 6 or 7, and n20 is 0 or 1.

[0097] In equation (11), n21 is 0, 1, 2, or 3. In equation (12), n22 is 0, 1, or 2. In equation (13), n23 is 0, 1, 2, 3, or 4. In equation (14), n24 is 0, 1, or 2. In equation (15), n25 is 0 or 1. In equation (16), n26 is 0, 1, 2, or 3.

[0098] In equations (1) to (16), R 1 ~R 31 Each group consists independently of a halogen atom or may contain heteroatoms and is a hydrocarbon group with 1 to 10 carbon atoms. Also, R 21 and R 22 They can also bond to each other and form rings together with the carbon atoms they are bonded to.

[0099] R 1 ~R 31 Examples of halogen atoms that can be represented include: fluorine, chlorine, bromine, and iodine atoms. R 1 ~R 31 The hydrocarbon groups representing 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 10 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6[Cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms, such as decyl and adamantyl; alkenyl groups such as vinyl and allyl; aryl groups with 6 to 10 carbon atoms, such as phenyl and naphthyl; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.] 1 ~R 31 It should preferably be a hydrocarbon group with 1 to 4 carbon atoms.

[0100] In equations (1) to (16), R 41 ~R 44 R 47 R 49 ~R 56 R 59 R 60 and R 61 ~R 68 Each R is an independent hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. When n2 is 2 or more, each R 41 They can be the same or different, and there are multiple Rs. 41 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R 42 They can be the same or different, and there are multiple Rs. 42 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R 43 They can be the same or different, and there are multiple Rs. 43 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R 44 They can be the same or different, and there are multiple Rs. 44 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n9 is 2 or more, each R 47 They can be the same or different, and there are multiple Rs. 47 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n10 is 2 or more, each R 49 They can be the same or different, and there are multiple Rs. 49 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n11 is 2 or more, each R 50 They can be the same or different, and there are multiple Rs. 50They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n12 is 2 or more, each R 51 They can be the same or different, and there are multiple Rs. 51 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n13 is 2 or more, each R 52 They can be the same or different, and there are multiple Rs. 52 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n14 is 2 or more, each R 53 They can be the same or different, and there are multiple Rs. 53 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n15 is 2 or more, each R 54 They can be the same or different, and there are multiple Rs. 54 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n16 is 2 or more, each R 55 They can be the same or different, and there are multiple Rs. 55 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n17 is 2 or more, each R 56 They can be the same or different, and there are multiple Rs. 56 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n18 is 2 or more, each R 59 They can be the same or different, and there are multiple Rs. 59 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n19 is 2 or more, each R 60 They can be the same or different, and there are multiple Rs. 60 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n21 is 2 or more, each R 61 They can be the same or different, and there are multiple Rs. 61 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n22 is 2 or more, each R 63 They can be the same or different, and there are multiple Rs. 63 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n23 is 2 or more, each R 64 They can be the same or different, and there are multiple Rs. 64 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n24 is 2 or more, each R 65 They can be the same or different, and there are multiple Rs. 65 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n26 is 2 or more, each R 68 They can be the same or different, and there are multiple Rs.68 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0101] R 41 ~R 44 R 47 R 49 ~R 56 R 59 R 60 and R 61 ~R 68 Examples of halogen atoms that can be represented include: fluorine, chlorine, bromine, and iodine atoms. R 41 ~R 44 R 47 R 49 ~R 56 R 59 R 60 and R 61 ~R 68 The hydrocarbon groups representing 1 to 40 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, these groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, amide, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.]

[0102] In equation (3), R 45When n8 is 1, 3, or 4, it is an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, it is an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, thioketone bond, an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valent hydrocarbon group or (n8) valent heterocyclic group can be substituted by groups containing heteroatoms, and part of the -CH2- of the aforementioned (n8) valent hydrocarbon group can also be substituted by groups containing heteroatoms, and R... 44 and R 45 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0103] R 45 The (n8) valence hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned (n8) valence hydrocarbon group is a group obtained by removing (n8) hydrogen atoms from a hydrocarbon. Examples of such hydrocarbons include: alkanes with 1-40 carbon atoms, alkenes with 2-40 carbon atoms, alkynes with 2-40 carbon atoms, cyclic saturated hydrocarbons with 3-40 carbon atoms, cyclic unsaturated hydrocarbons with 3-40 carbon atoms, and aromatic hydrocarbons with 6-40 carbon atoms.

[0104] Specific examples of alkanes with 1 to 40 carbon atoms mentioned above include: methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[0105] Specific examples of the aforementioned alkenes with 2 to 40 carbon atoms include: ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and their structural isomers.

[0106] Specific examples of the aforementioned alkynes with 2 to 40 carbon atoms include: acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, and their structural isomers.

[0107] Specific examples of the aforementioned cyclic saturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norcamphene, etc.

[0108] Specific examples of the aforementioned cyclic unsaturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norcamphene.

[0109] Specific examples of aromatic hydrocarbons with 6 to 40 carbon atoms mentioned above include: benzene, naphthalene, biphenyl, etc.

[0110] R 45 The (n8) valence heterocyclic group is a group obtained by removing (n8) hydrogen atoms from a heterocyclic compound. Examples of such heterocyclic compounds include furan, pyridine, pyrazole, and tetrahydrothiazole.

[0111] R 45 In the (n8) valence hydrocarbon group or (n8) valence heterocyclic group, some or all of its hydrogen atoms may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, resulting in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, iodine, etc. Furthermore, in the aforementioned (n8) valence hydrocarbon group, a portion of its -CH2- group may be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms, resulting in the presence of carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, carbamate bonds, amide bonds, lactone rings, sulopentalide rings, carboxylic anhydrides (-C(=O)-OC(=O)-), etc.

[0112] In equation (4), R 48 It is a carbonyl group or a hydrocarbon group with 1 to 10 carbon atoms, which may also contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. R 48 Specific examples of the alkylene group can be listed and illustrated in the description of formula (a-2) below, where it is represented as R. a2 The same example applies to the alkylene groups that have 1 to 10 carbon atoms.

[0113] In equation (9), R 56 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. R 56 Specific examples of halogen atoms and hydrocarbon groups can be listed and illustrated as R 1 ~R 31 The same examples represent halogen atoms and hydrocarbon groups.

[0114] In equation (9), R 57 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. R 57 Specific examples of halogen atoms and hydrocarbon groups can be listed and illustrated as R 1 ~R 31 The same examples represent halogen atoms and hydrocarbon groups.

[0115] In equations (5) and (14)~(16), 1. 2. 3. 4. 5. 6. 7 and 8 represents the atomic bond of the carbon atom or heteroatom in the aromatic ring or heterocycle in the formula. However, 1 and 2. 3 and 4. 5 and 6 and 7 and 8. Bonded to adjacent atoms on an aromatic ring or adjacent atoms on a heterocyclic ring.

[0116] In equation (6), L 1 It can be unbonded, single bond, -O-, -S-, -NH- or -CH2-.

[0117] In equation (9), X is -S- or -N(R) 58 )-. R 58 It is a hydrocarbon group with 1 to 20 carbon atoms, consisting of hydrogen atoms, halogen atoms, or heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. R 58 Specific examples of halogen atoms and hydrocarbon groups can be listed and illustrated as R 1 ~R 31 The same examples represent halogen atoms and hydrocarbon groups.

[0118] X 1 and X 2 Each independently -OX 11 -or -X 12 -C(=O)-。 X 3 for -OX 11 -、 -SX 11 -or -X 12 -C(=O)-。 X 11 It is a carbonyl group or a hydrocarbon group with 1 to 10 carbon atoms, which may also contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. X 11 Specific examples of the alkylene group can be listed and illustrated in the description of formula (a-2) below, where it is represented as R. a2 The same example applies to those with 1 to 10 carbon atoms in the alkylene group. X 12 -S- or -N(R) 69 )-. R 69 It is a hydrocarbon group with 1 to 20 carbon atoms, consisting of hydrogen atoms, halogen atoms, or heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. R 69 Specific examples of halogen atoms and hydrocarbon groups can be listed and illustrated as R 1 ~R31 The same examples represent halogen atoms and hydrocarbon groups.

[0119] Specific examples of high-valent iodine compounds represented by formula (1) are listed below, but are not limited thereto.

[0120] [Chemistry 7]

[0121]

[0122] [Chemistry 8]

[0123]

[0124] [Chemistry 9]

[0125]

[0126] [Chemistry 10]

[0127]

[0128] [Chemistry 11]

[0129]

[0130] [Chemistry 12]

[0131]

[0132] [Chemistry 13]

[0133]

[0134] [Chemistry 14]

[0135]

[0136] [Chemistry 15]

[0137]

[0138] [Chemistry 16]

[0139]

[0140] [Chemistry 17]

[0141]

[0142] [Chemistry 18]

[0143]

[0144] Specific examples of high-valent iodine compounds represented by equation (2) are listed below, but are not limited thereto.

[0145] [Chemistry 19]

[0146]

[0147] [Chemistry 20]

[0148]

[0149] [Chemistry 21]

[0150]

[0151] [Chemistry 22]

[0152]

[0153] Specific examples of high-valent iodine compounds represented by equation (3) are listed below, but are not limited thereto.

[0154] [Chemistry 23]

[0155]

[0156] [Chemistry 24]

[0157]

[0158] [Chemistry 25]

[0159]

[0160] [Chemistry 26]

[0161]

[0162] [Chemistry 27]

[0163]

[0164] [Chemistry 28]

[0165]

[0166] Specific examples of high-valent iodine compounds represented by formula (4) are shown below, but are not limited thereto. Additionally, in the following formula, Me is a methyl group.

[0167] [Chemistry 29]

[0168]

[0169] [Chemistry 30]

[0170]

[0171] [Chemistry 31]

[0172]

[0173] [Chemistry 32]

[0174]

[0175] [Chemistry 33]

[0176]

[0177] [Chemistry 34]

[0178]

[0179] [Chemistry 35]

[0180]

[0181] [Chemistry 36]

[0182]

[0183] [Chemistry 37]

[0184]

[0185] [Chemistry 38]

[0186]

[0187] [Chemistry 39]

[0188]

[0189] [Chemistry 40]

[0190]

[0191] [Chemistry 41]

[0192]

[0193] [Chemistry 42]

[0194]

[0195] [Chemistry 43]

[0196]

[0197] [Chemistry 44]

[0198]

[0199] [Chemistry 45]

[0200]

[0201] [Chemistry 46]

[0202]

[0203] [Chemistry 47]

[0204]

[0205] [Chemistry 48]

[0206]

[0207] [Chemistry 49]

[0208]

[0209] [Transformation 50]

[0210]

[0211] [Chemistry 51]

[0212]

[0213] [Chemistry 52]

[0214]

[0215] [Chemistry 53]

[0216]

[0217] [Chemistry 54]

[0218]

[0219] [Chemistry 55]

[0220]

[0221] [Chemistry 56]

[0222]

[0223] [Chemistry 57]

[0224]

[0225] [Chem.58]

[0226]

[0227] [Chemistry 59]

[0228]

[0229] [Transformation 60]

[0230]

[0231] [Chemistry 61]

[0232]

[0233] [Chemistry 62]

[0234]

[0235] [Chemistry 63]

[0236]

[0237] [Chemistry 64]

[0238]

[0239] [Chemistry 65]

[0240]

[0241] [Chemistry 66]

[0242]

[0243] [Chemistry 67]

[0244]

[0245] [Chemistry 68]

[0246]

[0247] [Chemistry 69]

[0248]

[0249] [Chemistry 70]

[0250]

[0251] [Chemistry 71]

[0252]

[0253] [Chemistry 72]

[0254]

[0255] [Chemistry 73]

[0256]

[0257] [Chemistry 74]

[0258]

[0259] [Chemistry 75]

[0260]

[0261] [Chemistry 76]

[0262]

[0263] [Chemistry 77]

[0264]

[0265] [Chemistry 78]

[0266]

[0267] [Chemistry 79]

[0268]

[0269] [Chemistry 80]

[0270]

[0271] [Chemistry 81]

[0272]

[0273] [Chemistry 82]

[0274]

[0275] [Chemistry 83]

[0276]

[0277] [Chemistry 84]

[0278]

[0279] Specific examples of high-valent iodine compounds represented by equation (5) are listed below, but are not limited thereto.

[0280] [Chemistry 85]

[0281]

[0282] [Chemistry 86]

[0283]

[0284] [Chemistry 87]

[0285]

[0286] [Chemistry 88]

[0287]

[0288] [Chemistry 89]

[0289]

[0290] [Chemistry 90]

[0291]

[0292] [Chemistry 91]

[0293]

[0294] [Chemistry 92]

[0295]

[0296] [Chemistry 93]

[0297]

[0298] [Chemistry 94]

[0299]

[0300] [Chem. 95]

[0301]

[0302] [Chemistry 96]

[0303]

[0304] [Chemistry 97]

[0305]

[0306] [Chem. 98]

[0307]

[0308] [Chemistry 99]

[0309]

[0310] [Chemistry 100]

[0311]

[0312] Specific examples of high-valent iodine compounds represented by equation (6) are shown below, but are not limited thereto. Additionally, in the following equation, L...1 Same as above.

[0313] [Chemistry 101]

[0314]

[0315] [Chemistry 102]

[0316]

[0317] [Chemistry 103]

[0318]

[0319] [Chemistry 104]

[0320]

[0321] [Chemistry 105]

[0322]

[0323] [Chemistry 106]

[0324]

[0325] [Chemistry 107]

[0326]

[0327] [Chemistry 108]

[0328]

[0329] [Chemistry 109]

[0330]

[0331] [Chemical 110]

[0332]

[0333] [Chemistry 111]

[0334]

[0335] [Chemistry 112]

[0336]

[0337] [Chemistry 113]

[0338]

[0339] [Chemistry 114]

[0340]

[0341] [Chemistry 115]

[0342]

[0343] [Chemistry 116]

[0344]

[0345] [Chemistry 117]

[0346]

[0347] [Chemistry 118]

[0348]

[0349] [Chemistry 119]

[0350]

[0351] [Chemistry 120]

[0352]

[0353] [Chemistry 121]

[0354]

[0355] [Chemistry 122]

[0356]

[0357] [Chemistry 123]

[0358]

[0359] [Chemistry 124]

[0360]

[0361] Specific examples of high-valent iodine compounds represented by formula (7) are listed below, but are not limited thereto.

[0362] [Chemistry 125]

[0363]

[0364] [Chemistry 126]

[0365]

[0366] [Chemistry 127]

[0367]

[0368] [Chemistry 128]

[0369]

[0370] [Chemistry 129]

[0371]

[0372] [Chemistry 130]

[0373]

[0374] [Chemistry 131]

[0375]

[0376] [Chemistry 132]

[0377]

[0378] Specific examples of high-valent iodine compounds represented by equation (8) are listed below, but are not limited thereto.

[0379] [Chemistry 133]

[0380]

[0381] [Chemistry 134]

[0382]

[0383] [Chemistry 135]

[0384]

[0385] [Chemistry 136]

[0386]

[0387] Specific examples of high-valent iodine compounds represented by equation (9) are listed below, but are not limited thereto.

[0388] [Chemistry 137]

[0389]

[0390] [Chemistry 138]

[0391]

[0392] [Chemistry 139]

[0393]

[0394] [Chemistry 140]

[0395]

[0396] [Chemistry 141]

[0397]

[0398] [Chemistry 142]

[0399]

[0400] [Chemistry 143]

[0401]

[0402] [Chemistry 144]

[0403]

[0404] [Chemistry 145]

[0405]

[0406] [Chemistry 146]

[0407]

[0408] [Chemistry 147]

[0409]

[0410] [Chemistry 148]

[0411]

[0412] [Chemistry 149]

[0413]

[0414] [Chemistry 150]

[0415]

[0416] [Chemistry 151]

[0417]

[0418] [Chemistry 152]

[0419]

[0420] Specific examples of high-valent iodine compounds represented by formula (10) are listed below, but are not limited thereto.

[0421] [Chemistry 153]

[0422]

[0423] [Chemistry 154]

[0424]

[0425] [Chemistry 155]

[0426]

[0427] [Chemistry 156]

[0428]

[0429] [Chemistry 157]

[0430]

[0431] [Chemistry 158]

[0432]

[0433] [Chemistry 159]

[0434]

[0435] [Chemistry 160]

[0436]

[0437] [Chemistry 161]

[0438]

[0439] [Chemistry 162]

[0440]

[0441] [Chemistry 163]

[0442]

[0443] [Chemistry 164]

[0444]

[0445] [Chemistry 165]

[0446]

[0447] [Chemistry 166]

[0448]

[0449] [Chemistry 167]

[0450]

[0451] [Chemistry 168]

[0452]

[0453] [Chemistry 169]

[0454]

[0455] [Chemistry 170]

[0456]

[0457] [Chemistry 171]

[0458]

[0459] [Chemistry 172]

[0460]

[0461] [Chemistry 173]

[0462]

[0463] [Chemistry 174]

[0464]

[0465] [Chemistry 175]

[0466]

[0467] [Chemistry 176]

[0468]

[0469] [Chemistry 177]

[0470]

[0471] [Chemistry 178]

[0472]

[0473] [Chemistry 179]

[0474]

[0475] [Chemistry 180]

[0476]

[0477] [Chemistry 181]

[0478]

[0479] [Chemistry 182]

[0480]

[0481] [Chemistry 183]

[0482]

[0483] [Chemistry 184]

[0484]

[0485] [Chemistry 185]

[0486]

[0487] [Chemistry 186]

[0488]

[0489] [Chemistry 187]

[0490]

[0491] [Chemistry 188]

[0492]

[0493] [Chemistry 189]

[0494]

[0495] [Chemistry 190]

[0496]

[0497] [Chemistry 191]

[0498]

[0499] [Chemistry 192]

[0500]

[0501] [Chemistry 193]

[0502]

[0503] [Chemistry 194]

[0504]

[0505] [Chemistry 195]

[0506]

[0507] [Chemistry 196]

[0508]

[0509] [Chemistry 197]

[0510]

[0511] [Chemistry 198]

[0512]

[0513] [Chemistry 199]

[0514]

[0515] [Chem.200]

[0516]

[0517] [Chemical Engineering 201]

[0518]

[0519] [Chemical Engineering 202]

[0520]

[0521] [Chemical Engineering 203]

[0522]

[0523] [Chemical 204]

[0524]

[0525] [Chemical Engineering 205]

[0526]

[0527] [Chemical Engineering 206]

[0528]

[0529] Specific examples of high-valent iodine compounds represented by formula (11) are listed below, but are not limited thereto.

[0530] [Chemical 207]

[0531]

[0532] [Chemical Engineering 208]

[0533]

[0534] [Chemical Engineering 209]

[0535]

[0536] [Chemical 210]

[0537]

[0538] [Chemistry 211]

[0539]

[0540] [Chemistry 212]

[0541]

[0542] [Chemistry 213]

[0543]

[0544] [Chemistry 214]

[0545]

[0546] Specific examples of high-valent iodine compounds represented by formula (12) are listed below, but are not limited thereto.

[0547] [Chemical 215]

[0548]

[0549] [Chemistry 216]

[0550]

[0551] [Chemistry 217]

[0552]

[0553] [Chemistry 218]

[0554]

[0555] [Chemistry 219]

[0556]

[0557] [Chem.220]

[0558]

[0559] [Chemistry 221]

[0560]

[0561] [Chemistry 222]

[0562]

[0563] [Chemistry 223]

[0564]

[0565] [Chemistry 224]

[0566]

[0567] [Chemistry 225]

[0568]

[0569] [Chemistry 226]

[0570]

[0571] Specific examples of high-valent iodine compounds represented by formula (13) are listed below, but are not limited thereto.

[0572] [Chemistry 227]

[0573]

[0574] [Chemistry 228]

[0575]

[0576] [Chemistry 229]

[0577]

[0578] [Chemistry 230]

[0579]

[0580] [Chemistry 231]

[0581]

[0582] [Chemistry 232]

[0583]

[0584] [Chemistry 233]

[0585]

[0586] [Chemistry 234]

[0587]

[0588] Specific examples of high-valent iodine compounds represented by formula (14) are shown below, but are not limited thereto. Additionally, in the following formula, Me is a methyl group. 3 and 4. Same as above.

[0589] [Chemistry 235]

[0590]

[0591] [Chemistry 236]

[0592]

[0593] [Chemistry 237]

[0594]

[0595] [Chemistry 238]

[0596]

[0597] [Chemistry 239]

[0598]

[0599] [Chemistry 240]

[0600]

[0601] [Chemistry 241]

[0602]

[0603] [Chemistry 242]

[0604]

[0605] [Chemistry 243]

[0606]

[0607] [Chemistry 244]

[0608]

[0609] [Chemistry 245]

[0610]

[0611] [Chemistry 246]

[0612]

[0613] [Chemistry 247]

[0614]

[0615] [Chemistry 248]

[0616]

[0617] [Chemistry 249]

[0618]

[0619] [Chemistry 250]

[0620]

[0621] [Chemistry 251]

[0622]

[0623] [Chemistry 252]

[0624]

[0625] [Chemistry 253]

[0626]

[0627] [Chemistry 254]

[0628]

[0629] [Chemistry 255]

[0630]

[0631] [Chemistry 256]

[0632]

[0633] [Chemistry 257]

[0634]

[0635] [Chemistry 258]

[0636]

[0637] [Chemistry 259]

[0638]

[0639] [Chemistry 260]

[0640]

[0641] [Chemistry 261]

[0642]

[0643] [Chemistry 262]

[0644]

[0645] [Chemistry 263]

[0646]

[0647] [Chemistry 264]

[0648]

[0649] [Chemistry 265]

[0650]

[0651] [Chemistry 266]

[0652]

[0653] [Chemistry 267]

[0654]

[0655] [Chemistry 268]

[0656]

[0657] [Chemistry 269]

[0658]

[0659] [Chemistry 270]

[0660]

[0661] [Chemistry 271]

[0662]

[0663] [Chemistry 272]

[0664]

[0665] [Chemistry 273]

[0666]

[0667] [Chemistry 274]

[0668]

[0669] [Chemistry 275]

[0670]

[0671] [Chemistry 276]

[0672]

[0673] [Chemistry 277]

[0674]

[0675] [Chemistry 278]

[0676]

[0677] [Chemistry 279]

[0678]

[0679] [Chemistry 280]

[0680]

[0681] [Chemistry 281]

[0682]

[0683] [Chemistry 282]

[0684]

[0685] [Chemistry 283]

[0686]

[0687] [Chemistry 284]

[0688]

[0689] [Chemistry 285]

[0690]

[0691] [Chemistry 286]

[0692]

[0693] [Chemistry 287]

[0694]

[0695] [Chemistry 288]

[0696]

[0697] [Chemistry 289]

[0698]

[0699] [Chemistry 290]

[0700]

[0701] [Chemistry 291]

[0702]

[0703] [Chemistry 292]

[0704]

[0705] [Chemistry 293]

[0706]

[0707] [Chemistry 294]

[0708]

[0709] Specific examples of high-valent iodine compounds represented by equation (15) are shown below, but are not limited thereto. Additionally, in the following equation, 5 and 6 is the same as above.

[0710] [Chemistry 295]

[0711]

[0712] [Chemistry 296]

[0713]

[0714] [Chemistry 297]

[0715]

[0716] [Chemistry 298]

[0717]

[0718] [Chemistry 299]

[0719]

[0720] [Chemical 300]

[0721]

[0722] [Chemical Engineering 301]

[0723]

[0724] [Chemical 302]

[0725]

[0726] [Chemical 303]

[0727]

[0728] [Chemical 304]

[0729]

[0730] [Chemical 305]

[0731]

[0732] [Chemical 306]

[0733]

[0734] [Chemical 307]

[0735]

[0736] [Chemical 308]

[0737]

[0738] [Chemical 309]

[0739]

[0740] [Chemical 310]

[0741]

[0742] [Chemistry 311]

[0743]

[0744] [Chemistry 312]

[0745]

[0746] [Chemistry 313]

[0747]

[0748] [Chemical 314]

[0749]

[0750] [Chemical 315]

[0751]

[0752] [Chemistry 316]

[0753]

[0754] [Chemistry 317]

[0755]

[0756] [Chemistry 318]

[0757]

[0758] [Chemistry 319]

[0759]

[0760] [Chemistry 320]

[0761]

[0762] [Chemistry 321]

[0763]

[0764] [Chemistry 322]

[0765]

[0766] [Chemistry 323]

[0767]

[0768] [Chemistry 324]

[0769]

[0770] [Chemistry 325]

[0771]

[0772] [Chemistry 326]

[0773]

[0774] [Chemistry 327]

[0775]

[0776] [Chemistry 328]

[0777]

[0778] [Chemistry 329]

[0779]

[0780] [Chemistry 330]

[0781]

[0782] [Chemistry 331]

[0783]

[0784] [Chemistry 332]

[0785]

[0786] [Chemistry 333]

[0787]

[0788] [Chemistry 334]

[0789]

[0790] [Chemistry 335]

[0791]

[0792] [Chemistry 336]

[0793]

[0794] [Chemistry 337]

[0795]

[0796] [Chemistry 338]

[0797]

[0798] [Chemistry 339]

[0799]

[0800] [Transformation 340]

[0801]

[0802] [Chemistry 341]

[0803]

[0804] [Chemistry 342]

[0805]

[0806] [Chemistry 343]

[0807]

[0808] [Chemistry 344]

[0809]

[0810] [Chemistry 345]

[0811]

[0812] [Chemistry 346]

[0813]

[0814] [Chemistry 347]

[0815]

[0816] [Chemistry 348]

[0817]

[0818] [Chemistry 349]

[0819]

[0820] [Chemical 350]

[0821]

[0822] [Chemistry 351]

[0823]

[0824] [Chemistry 352]

[0825]

[0826] [Chemistry 353]

[0827]

[0828] [Chemistry 354]

[0829]

[0830] [Chemistry 355]

[0831]

[0832] [Chemistry 356]

[0833]

[0834] [Chemistry 357]

[0835]

[0836] [Chemistry 358]

[0837]

[0838] [Chemical Formula 359]

[0839]

[0840] [Chemical Formula 360]

[0841]

[0842] [Chemical Formula 361]

[0843]

[0844] [Chemical Formula 362]

[0845]

[0846] [Chemical Formula 363]

[0847]

[0848] [Chemical Formula 364]

[0849]

[0850] [Chemical Formula 365]

[0851]

[0852] [Chemical Formula 366]

[0853]

[0854] [Chemical Formula 367]

[0855]

[0856] [Chemical Formula 368]

[0857]

[0858] [Chemical Formula 369]

[0859]

[0860] [Chemical Formula 370]

[0861]

[0862] [Chemical Formula 371]

[0863]

[0864] [Chemical Formula 372]

[0865]

[0866] [Chemistry 373]

[0867]

[0868] [Chemistry 374]

[0869]

[0870] [Chemistry 375]

[0871]

[0872] [Chemistry 376]

[0873]

[0874] [Chemistry 377]

[0875]

[0876] [Chemistry 378]

[0877]

[0878] [Chemistry 379]

[0879]

[0880] [Chemistry 380]

[0881]

[0882] [Chemistry 381]

[0883]

[0884] [Chemistry 382]

[0885]

[0886] [Chemistry 383]

[0887]

[0888] [Chem. 384]

[0889]

[0890] [Chem. 385]

[0891]

[0892] [Chemistry 386]

[0893]

[0894] [Chemistry 387]

[0895]

[0896] [Chem.388]

[0897]

[0898] [Chemistry 389]

[0899]

[0900] [Chemistry 390]

[0901]

[0902] [Chemistry 391]

[0903]

[0904] [Chemistry 392]

[0905]

[0906] [Chemistry 393]

[0907]

[0908] [Chem. 394]

[0909]

[0910] [Chemistry 395]

[0911]

[0912] [Chemistry 396]

[0913]

[0914] [Chemistry 397]

[0915]

[0916] [Chemistry 398]

[0917]

[0918] [Chemistry 399]

[0919]

[0920] [Chemical 400]

[0921]

[0922] [Chemical Engineering 401]

[0923]

[0924] [Chemical 402]

[0925]

[0926] [Chemical 403]

[0927]

[0928] [Chemical 404]

[0929]

[0930] [Chemical 405]

[0931]

[0932] [Chemical 406]

[0933]

[0934] [Chemical 407]

[0935]

[0936] [Chemical 408]

[0937]

[0938] [Chemical 409]

[0939]

[0940] [Chemical 410]

[0941]

[0942] [Chemistry 411]

[0943]

[0944] Specific examples of high-valent iodine compounds represented by equation (16) are listed below, but are not limited thereto. Additionally, in the following equation, 7 and 8 is the same as above.

[0945] [Chemistry 412]

[0946]

[0947] [Chemistry 413]

[0948]

[0949] [Chemistry 414]

[0950]

[0951] [Chemical 415]

[0952]

[0953] [Chemistry 416]

[0954]

[0955] [Chemistry 417]

[0956]

[0957] [Chemistry 418]

[0958]

[0959] [Chemistry 419]

[0960]

[0961] [Chemistry 420]

[0962]

[0963] [Chemistry 421]

[0964]

[0965] [Chemistry 422]

[0966]

[0967] [Chemistry 423]

[0968]

[0969] [Chemistry 424]

[0970]

[0971] [Chemical 425]

[0972]

[0973] [Chemistry 426]

[0974]

[0975] [Chemistry 427]

[0976]

[0977] [Chemistry 428]

[0978]

[0979] [Chemistry 429]

[0980]

[0981] [Chemistry 430]

[0982]

[0983] [Chemistry 431]

[0984]

[0985] [Chemistry 432]

[0986]

[0987] [Chemistry 433]

[0988]

[0989] [Chemistry 434]

[0990]

[0991] [Chemistry 435]

[0992]

[0993] [Chemistry 436]

[0994]

[0995] [Chemistry 437]

[0996]

[0997] [Chemistry 438]

[0998]

[0999] [Chemistry 439]

[1000]

[1001] [Chemistry 440]

[1002]

[1003] [Chemistry 441]

[1004]

[1005] [Chemistry 442]

[1006]

[1007] [Chemistry 443]

[1008]

[1009] [Chemistry 444]

[1010]

[1011] [Chemistry 445]

[1012]

[1013] [Chemistry 446]

[1014]

[1015] [Chemistry 447]

[1016]

[1017] [Chemistry 448]

[1018]

[1019] [Chemistry 449]

[1020]

[1021] [Chemistry 450]

[1022]

[1023] [Chemistry 451]

[1024]

[1025] [Chemistry 452]

[1026]

[1027] [Chemistry 453]

[1028]

[1029] [Chemistry 454]

[1030]

[1031] [Chemistry 455]

[1032]

[1033] [Chemistry 456]

[1034]

[1035] [Chemistry 457]

[1036]

[1037] [Chemistry 458]

[1038]

[1039] [Chemistry 459]

[1040]

[1041] [Chemistry 460]

[1042]

[1043] [Chemistry 461]

[1044]

[1045] [Chemistry 462]

[1046]

[1047] [Chemistry 463]

[1048]

[1049] [Chemistry 464]

[1050]

[1051] [Chemistry 465]

[1052]

[1053] [Chemistry 466]

[1054]

[1055] [Chemistry 467]

[1056]

[1057] [Chemistry 468]

[1058]

[1059] [Chemistry 469]

[1060]

[1061] [Chemistry 470]

[1062]

[1063] [Chemistry 471]

[1064]

[1065] [Chemistry 472]

[1066]

[1067] [Chemistry 473]

[1068]

[1069] [Chemistry 474]

[1070]

[1071] [Chemistry 475]

[1072]

[1073] [Chemistry 476]

[1074]

[1075] [Chemistry 477]

[1076]

[1077] [Chemistry 478]

[1078]

[1079] [Chemistry 479]

[1080]

[1081] [Chemistry 480]

[1082]

[1083] [Chemistry 481]

[1084]

[1085] [Chemistry 482]

[1086]

[1087] [Chemistry 483]

[1088]

[1089] [Chemistry 484]

[1090]

[1091] [Chemistry 485]

[1092]

[1093] [Chemistry 486]

[1094]

[1095] [Chemistry 487]

[1096]

[1097] [Chemistry 488]

[1098]

[1099] [Chemistry 489]

[1100]

[1101] [Compounds containing carboxyl groups]

[1102] The aforementioned carboxyl-containing compounds are preferably polymers containing repeating units represented by the following formula (a-1) or carboxylic acid compounds represented by the following formula (a-2).

[1103] [Chemistry 490]

[1104]

[1105] In equation (a-1), R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A It is a single bond, phenylene, naphthylene or -C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. It represents the atomic bonds between carbon atoms in the main chain and the main chain.

[1106] In equation (a-2), p is 1, 2, 3 or 4.

[1107] In equation (a-2), R a1When p is 1, 3, or 4, it is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms. When p is 2, it is an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, p-valent hydrocarbon group with 1 to 40 carbon atoms, or a p-valent heterocyclic group with 2 to 40 carbon atoms. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group may be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned p-valent hydrocarbon group may also be substituted by a group containing a heteroatom.

[1108] In equation (a-2), R a2 It is a single bond or a hydrocarbon group with 1 to 20 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group may be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group may also be replaced by a group containing a heteroatom. When p is 2, 3 or 4, each R a2 They can be the same or different.

[1109] R a1 The p-valent hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned p-valent hydrocarbon group is a group obtained by removing p hydrogen atoms from a hydrocarbon. Examples of such hydrocarbons include: alkanes with 1-40 carbon atoms, alkenes with 2-40 carbon atoms, alkynes with 2-40 carbon atoms, cyclic saturated hydrocarbons with 3-40 carbon atoms, cyclic unsaturated hydrocarbons with 3-40 carbon atoms, and aromatic hydrocarbons with 6-40 carbon atoms.

[1110] The aforementioned alkanes with 1 to 40 carbon atoms include: methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[1111] The aforementioned alkenes with 2 to 40 carbon atoms include: ethylene, propylene, butene, pentene, hexene, hepten, octene, nonene, decene, and their structural isomers.

[1112] The aforementioned alkynes with 2 to 40 carbon atoms can be listed as follows: acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, and their structural isomers.

[1113] Examples of cyclic saturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norcamphene, etc.

[1114] Examples of cyclic unsaturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropylene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norcamphene.

[1115] Aromatic hydrocarbons with 6 to 40 carbon atoms mentioned above include: benzene, naphthalene, biphenyl, etc.

[1116] R a1The p-valent heterocyclic group represents a group obtained by removing p hydrogen atoms from a heterocyclic compound. Examples of such heterocyclic compounds include furan, pyridine, pyrazole, and tetrahydrothiazole.

[1117] In the aforementioned p-valent hydrocarbon groups or p-valent heterocyclic groups, some or all of the hydrogen atoms can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, resulting in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, and iodine atoms. Furthermore, in the aforementioned p-valent hydrocarbon groups, a portion of the -CH2- group can be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms, resulting in the presence of carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, carbamate bonds, lactone rings, sulfonyl lactone rings, and carboxylic anhydrides (-C(=O)-OC(=O)-), etc.

[1118] R a2 The derivatized hydrocarbon group 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-1,2-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, Alkyl groups with 1 to 20 carbon atoms, such as 11-diyl and dodecane-1,12-diyl; cyclic saturated alkylene groups with 3 to 20 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norcamphenediyl, and adamantanediyl; unsaturated aliphatic alkylene groups with 2 to 20 carbon atoms, such as vinylene and propene-1,3-diyl; aryl groups with 6 to 20 carbon atoms, such as phenylene and naphthylene; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned alkylene group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and a portion of the -CH2- constituting the aforementioned alkylene group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, carbamate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides, etc.

[1119] Among the carboxylic acid compounds represented by formula (a-2), those with p=2, 3, or 4 are preferable. In this case, when mixed with high-valent iodine compounds, it is easy to form a high-molecular-weight, robust resist film, which is ideal considering etching resistance and developer resistance.

[1120] Specific examples of the repeating unit containing a carboxyl group represented by formula (a-1) are shown below, but are not limited to these. Additionally, in the following formula, R... A Same as above.

[1121] [Chemistry 491]

[1122]

[1123] [Chemistry 492]

[1124]

[1125] The carboxylic acid compounds represented by formula (a-2) can be listed below, but are not limited to.

[1126] [Chemistry 493]

[1127]

[1128] [Chemistry 494]

[1129]

[1130] [Chemistry 495]

[1131]

[1132] [Chemistry 496]

[1133]

[1134] [Chemistry 497]

[1135]

[1136] [Chemistry 498]

[1137]

[1138] The aforementioned carboxyl-containing polymers may also contain repeating units other than those represented by formula (a-1) (hereinafter also referred to as other repeating units). There are no particular limitations on the aforementioned other repeating units, but they should preferably be those that improve the solubility of polymers that are poorly soluble in solvents when containing only repeating units with carboxyl groups. The aforementioned other repeating units should preferably be repeating units with a ring structure that is expected to have high etch resistance due to a rigid backbone, or repeating units containing a styrene backbone.

[1139] Specific examples of the aforementioned repeating units may be listed below, but are not limited to these. Additionally, in the following formula, R... A As mentioned above, X B They are either -CH2- or -O-, respectively.

[1140] [Chemistry 499]

[1141]

[1142] [Chemical 500]

[1143]

[1144] [Chemical 501]

[1145]

[1146] [Chemical 502]

[1147]

[1148] [Chemical 503]

[1149]

[1150] [Chemical 504]

[1151]

[1152] [Chemical 505]

[1153]

[1154] [Chemical 506]

[1155]

[1156] [Chem. 507]

[1157]

[1158] [Chem.508]

[1159]

[1160] [Chemical 509]

[1161]

[1162] [Chem.510]

[1163]

[1164] [Chem.511]

[1165]

[1166] [Chem.512]

[1167]

[1168] [Chem.513]

[1169]

[1170] [Chem.514]

[1171]

[1172] [Chem.515]

[1173]

[1174] [Chem.516]

[1175]

[1176] [Chem.517]

[1177]

[1178] [Chem.518]

[1179]

[1180] [Chem.519]

[1181]

[1182] [Chem.520]

[1183]

[1184] [Chem.521]

[1185]

[1186] [Chem.522]

[1187]

[1188] [Chem.523]

[1189]

[1190] [Chem.524]

[1191]

[1192] [Chem.525]

[1193]

[1194] [Chem.526]

[1195]

[1196] [Chem.527]

[1197]

[1198] [Chem.528]

[1199]

[1200] In the aforementioned carboxyl-containing polymers, the molar ratio of carboxyl-containing repeating units to other repeating units should preferably be 10:90~90:10, more preferably 15:85~85:15, and even more preferably 20:80~80:20.

[1201] The weight-average molecular weight (Mw) of the aforementioned carboxyl-containing polymers is preferably 1,000 to 500,000, more preferably 3,000 to 100,000, and even more preferably 3,000 to 20,000. Furthermore, in this invention, Mw and number-average molecular weight (Mn) are converted values ​​of standard polystyrene obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and the molecular weight distribution (Mw / Mn) is a value obtained from them. GPC measurements are typically performed at room temperature around 23 degrees Celsius, but can also be performed at higher or lower temperatures.

[1202] Furthermore, in the aforementioned carboxyl-containing polymers, when the Mw / Mn ratio is wide, the presence of both low and high molecular weight polymers raises concerns about the observation of foreign matter and deterioration of the pattern shape after exposure. Therefore, as the pattern becomes more regular and refined, the influence of Mw and Mw / Mn tends to increase. Thus, in order to obtain a resist composition that can be ideally used for fine pattern sizes, the aforementioned carboxyl-containing polymers should preferably have a narrow dispersion of Mw / Mn of 1.0 to 2.0.

[1203] Examples of methods for synthesizing the aforementioned carboxyl-containing polymers include: polymerizing a monomer that provides the aforementioned repeating unit in an organic solvent by adding a free radical polymerization initiator and heating it.

[1204] Specific examples of organic solvents used in the polymerization reaction include: toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, cyclopentanone, cyclohexanone, methyl ethyl ketone (MEK), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), etc. 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, lauroyl peroxide, etc. The amount of the aforementioned polymerization initiator added, relative to the total amount of monomers used to polymerize, should preferably be 0.01~25 mol%. The reaction temperature should preferably be 50~150℃, preferably 60~100℃. The reaction time should ideally be 2 to 24 hours, but from a production efficiency perspective, 2 to 12 hours is even better.

[1205] The aforementioned polymerization initiator can be added to the monomer solution and supplied to the reactor, or an initiator solution different from the monomer solution can be prepared and supplied to the reactor separately. Since there is a possibility that polymerization may proceed and generate ultrapolymers due to the generation of free radicals from the initiator during the waiting time, from a quality management perspective, the monomer solution and initiator solution should preferably be prepared separately and added dropwise. Furthermore, to adjust the molecular weight, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can also be used in combination. In this case, the amount of the aforementioned chain transfer agent added, relative to the total amount of monomers used to polymerize, should preferably be 0.01 to 20 mol%.

[1206] In addition, the amount of each monomer in the aforementioned monomer solution can be appropriately set, for example, in a manner that makes it an ideal content ratio for the aforementioned repeating units.

[1207] In the aforementioned resist composition, the molar ratio of the aforementioned high-valent iodine compound to the aforementioned carboxyl-containing compound (or, when the aforementioned carboxyl-containing compound is a carboxyl-containing polymer, the molar ratio of the high-valent iodine compound to the repeating carboxylic acid-containing unit in the aforementioned polymer) is preferably high-valent iodine compound: carboxyl-containing compound = 10:90~90:10, more preferably 20:80~80:20, and even more preferably 30:70~70:30. The aforementioned high-valent iodine compound can be used alone or in combination of two or more. The aforementioned carboxyl-containing polymer can be used alone or in combination of two or more with different composition ratios, Mw, and / or Mw / Mn. The carboxylic acid compound represented by formula (a-2) can be used alone or in combination of two or more. Either the aforementioned carboxyl-containing polymer or the carboxylic acid compound represented by formula (a-2) can be used, or they can be used in combination.

[1208] In the total solid components of the resist composition of the present invention, the total amount of the aforementioned high-valent iodine compound and the carboxyl-containing compound is preferably 30-100% by mass, more preferably 50-100% by mass, even more preferably 80-100% by mass, even more preferably 90-100% by mass, even more preferably 95-100% by mass, and most preferably 98-100% by mass.

[1209] [solvent]

[1210] The aforementioned resist composition contains a solvent. There are no particular limitations on the solvent if it is capable of dissolving the aforementioned high-valent iodine compounds, carboxyl-containing compounds, and other components described below, and forming a film. Such a solvent is preferably an organic solvent, and specific examples include: ketones such as cyclohexanone, methyl-2-n-pentyl ketone, and methyl isopentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, 4-methyl-2-pentanol, and methyl 2-hydroxyisobutyrate; and propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. Ethers such as glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; carboxylic acids such as formic acid, acetic acid, and propionic acid; lactones such as γ-butyrolactone; and their mixed solvents, etc.

[1211] In the aforementioned resist composition, the content of the aforementioned solvent is preferably such that the concentration of the solid component in the resist composition is 0.1% to 20% by mass, more preferably 0.1% to 15% by mass, and even more preferably 0.1% to 10% by mass. Furthermore, in this invention, "solid component" refers to all components of the resist composition other than the solvent. The aforementioned solvent may be used alone or in combination of two or more.

[1212] [Other ingredients]

[1213] The aforementioned resist composition may also contain a surfactant. The surfactant is preferably a fluorinated and / or polysiloxane surfactant. Examples of such surfactants include those described in paragraph

[0276] of U.S. Patent Application Publication 2008 / 0248425. Alternatively, surfactants other than those described in paragraph

[0280] of U.S. Patent Application Publication 2008 / 0248425 may also be used.

[1214] When the aforementioned resist composition contains the aforementioned surfactant, its content in the total solid components should preferably be 0.0001~2% by mass. The aforementioned surfactant may be used alone or in combination of two or more.

[1215] The aforementioned resist composition may also contain free radical scavengers. By adding free radical scavengers, the photoresist reaction in optical lithography can be controlled, and the sensitivity can be adjusted.

[1216] The aforementioned free radical scavengers include hindered phenols, quinones, hindered amines, and thiols. Specifically, hindered phenols include butylated hydroxytoluene (BHT) and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). Quinones include 4-methoxyphenol (MEHQ) and hydroquinone. Hindered amines include 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethylpiperidine-N-oxy radical. Thiols include dodecyl mercaptan and hexadecyl mercaptan.

[1217] When the aforementioned corrosion resist composition contains the aforementioned free radical scavenger, its content in the total solid components should preferably be 0.01~10% by mass. The aforementioned free radical scavenger can be used alone or in combination of two or more.

[1218] The aforementioned resist composition may also contain a crosslinking agent. By adding a crosslinking agent, the crosslinking reaction in optical lithography can be promoted, the glass transition point of the pattern can be improved, and patterns with excellent resolution at fine lines can be obtained.

[1219] The aforementioned crosslinking agents can include compounds with carbon-carbon unsaturated bonds as functional groups, such as vinyl, (meth)acrylate, allyl, alkynyl, and aromatic rings. Specifically, compounds with vinyl groups can include: chain alkenes, branched alkenes, cyclic alkenes, etc., which may also have substituents. Compounds with (meth)acrylate groups can include: acrylic acid, methacrylic acid, acrylates, methacrylates, etc., which may also have substituents. Compounds with allyl groups can include: allyl alcohols, allyl ethers, allyl esters, allyl amides, allylamines, isocyanurates containing allyl groups, etc. Compounds with alkynyl groups can include: chain alkynes, branched alkynes, cyclic alkynes, alkynyl alcohols, alkynyl ethers, alkynyl esters, alkynyl amides, alkynylamines, isocyanurates containing alkynyl groups, etc. Compounds with aromatic rings can include: aromatic hydrocarbons, heteroaromatic hydrocarbons, styrene, stilbene, phenylacetylene, acenaphthene, chalcone, etc., which may also have substituents. The crosslinking agent may contain only one or more of the above-mentioned functional groups. The number of the above-mentioned functional groups contained in the crosslinking agent is preferably 1 or more and 10 or less, and more than 2 or 8 or less.

[1220] When the aforementioned resist composition contains the aforementioned crosslinking agent, its content in the total solid components should preferably be 0.01~50% by mass. The aforementioned crosslinking agent can be used alone or in combination of two or more.

[1221] When the aforementioned resist composition contains the aforementioned crosslinking agent, it may also contain a photopolymerization initiator (photoradical generator). The photopolymerization initiator can generate free radicals by irradiation with high-energy rays and promote the crosslinking of the aforementioned crosslinking agent.

[1222] Specific examples of the aforementioned photopolymerization initiators include: benzophenone, methyl O-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, and other benzophenone derivatives; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)-benzyl]-phenyl}-2-methylpropane-1-one, methyl phenylglyoxylate, and other acetophenone derivatives; thioxanthone, 2-methylthiophene... Thioxanone derivatives such as 2-isopropylthioxanone, 4-isopropylthioxanone, 2-chlorothioxanone, and diethylthioxanone; benzoyl derivatives such as benzoyl, benzoyl dimethyl ketal, and benzoyl-β-methoxyethyl acetal; benzoylin derivatives such as benzoylinium, benzoylinium methyl ether, and 2-hydroxy-2-methyl-1-phenylpropane-1-one; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, and 1,3-diphenylpropanedione-2-(O-benzoyl)oxime. Oxime compounds such as alkyltrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)] ethyl ketone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime); α-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)-benzyl]phenyl}-2-methylpropane, etc. Hydroxyketone compounds; α-aminoalkylphenyl ketone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butane-1-one; phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and 2,4,6-trimethylbenzoyl diphenylphosphine oxide; and titanoceramic compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium.

[1223] When the aforementioned photopolymerization initiator is present in the aforementioned photoresist composition, its content in the total solid components should preferably be 0.1-10% by mass, more preferably 0.1-5% by mass, and optimally 0.1-1% by mass. If it is above 0.1% by mass, sufficient blending effect can be obtained.

[1224] The aforementioned photoresist composition contains high-valent iodine compounds and carboxyl-containing compounds as main components, but does not contain polymers with acid-instable groups or photoacid generators as found in conventional chemically amplified photoresist compositions. However, the aforementioned photoresist composition, especially when exposed to EB or EUV, can still form positive patterns where the exposed portion is soluble in the developer or negative patterns where the exposed portion is insoluble in the developer. The mechanism is not fully understood, but it is hypothesized, for example, as follows.

[1225] High-valent iodine compounds are tricoordinate compounds with aryl and carboxylate ligands. It is believed that when such tricoordinate iodine compounds are mixed with carboxyl-containing compounds, the exchange of carboxylate ligands occurs in an equilibrium reaction. If the original carboxylate ligands can be removed by any method, a high-valent iodine compound with new ligands will be generated. For example, if 1-iodonaphthalene diacetate, a high-valent iodine compound, is mixed with a carboxyl-containing compound, and the resulting low-boiling acetic acid is removed, the ligand exchange will be completed. This results in a polymer formed by the cross-linking of the carboxyl-containing compound with the high-valent iodine compound.

[1226] Polymers crosslinked with high-valent iodine compounds are formed during film formation. This is because even if such crosslinked polymers are synthesized beforehand, they are insoluble in most organic solvents, making solution preparation impossible. It is speculated that this is because the high-valent iodine compounds, which originally have high polarization and low solvent solubility, use carboxyl-containing compounds as ligands, further worsening their solubility. Therefore, it is advisable to remove the original low-molecular-weight carboxylic acid components during film formation and the subsequent baking step, thereby completing the ligand exchange reaction and simultaneously forming the resist film.

[1227] In the resist film derived from the aforementioned resist composition, the high-valent iodine compound, as its main component, decomposes under light, thereby changing its polarity and forming a pattern using the development step. The mechanism is not yet fully elucidated, but it is speculated, for example, as follows.

[1228] The aforementioned resist composition contains polymers cross-linked with high-valent iodine compounds generated during film formation. Therefore, it will decompose under light, causing cross-linking or bond exchange, and resulting in increased molecular weight and polarity reversal. It is speculated that this will result in a negative pattern where the unexposed areas are removed by the developer containing organic acids.

[1229] Even when developed with an alkaline aqueous solution, the aforementioned resist composition can still be negative. However, the alkaline aqueous solution may cause slight decomposition of new crosslinks formed in the exposed area, or of bonds formed after crosslinking exchange, making it easy for the exposed area to swell in the developer. On the other hand, it is believed that by using a developer containing organic acids in this invention, swelling can be prevented and patterns with good resolution can be formed.

[1230] Based on the foregoing, the aforementioned resist composition can be considered a non-chemically amplified resist composition. Because this resist composition does not require polymers containing acid-instable groups or photoacid generators as in known chemically amplified resist compositions, it avoids the adverse effects of acid diffusion (such as image blurring) and allows for the resolution of fine patterns.

[1231] The aforementioned resist composition is particularly effective in EUV lithography. This is due to iodine atoms, which have a high absorption capacity for EUV light. In other words, it reduces shot noise and achieves higher resolution and lower LWR.

[1232] Regarding resist compositions for EUV lithography capable of forming fine patterns, there have been reports of metal resists with tin compounds as the main component, which have a similar high absorption capacity for EUV light as iodine atoms (e.g., Patent Document 2). However, as mentioned earlier, such metal resists suffer from many problems, including insufficient solvent solubility, poor storage stability, and defects caused by etching residues due to the presence of metal elements. On the other hand, the aforementioned resist composition, since it does not use metal elements, is more advantageous than metal resists in terms of defects and does not have the problem of solvent solubility. Furthermore, the aforementioned resist composition is applicable to positive patterns, thus having a wide range of applications. For example, in the contact hole formation step, metal resists implemented with negative development require a reversal process after the pillar pattern is formed, while positive resists do not require such a step. Therefore, considering the simplicity of the process, the aforementioned resist composition can be considered more useful than metal resists.

[1233] [Resist Pattern Formation Method]

[1234] The resist pattern forming method of the present invention includes the following steps (i) to (iii):

[1235] (i) A resist film is formed on a substrate or on the lower layer of a substrate having a lower layer film, using a resist composition containing a high-valent iodine compound, a carboxyl-containing compound, and a solvent.

[1236] (ii) Expose the aforementioned resist film to high-energy radiation, and

[1237] (iii) The previously exposed resist film is developed using a developer containing organic acid to form a negative pattern.

[1238] [Step (i)]

[1239] Step (i) is the step of forming a resist film on a substrate or on the lower layer film of a substrate with a stacked lower layer film using the aforementioned resist composition. Specifically, the aforementioned resist composition is applied using appropriate coating methods such as spin coating, roll coating, flow coating, dip coating, spray coating, or blade coating to a substrate for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.), or on the lower layer film of a substrate for integrated circuit manufacturing with a stacked lower layer film, or on a substrate for mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.), or on the lower layer film of a substrate for mask circuit manufacturing with a stacked lower layer film, with a film thickness of 0.01~2μm. The substrate is pre-baked on a hot plate at a temperature preferably 60-200°C for 10-30 seconds, and more preferably 80-180°C for 30-20 seconds, to form a resist film. Furthermore, the lower layer film refers to the film formed between the substrate and the resist film in a multilayer resist process. There are no particular limitations on the aforementioned lower layer film, and known types can be used.

[1240] The thickness of the aforementioned resist film should preferably be 10~70nm, and 20~50nm is even better.

[1241] [Step (ii)]

[1242] Step (ii) involves exposing the aforementioned resist film to high-energy radiation. Examples of such high-energy radiation include: ultraviolet rays (gamma rays (436 nm), h-rays (405 nm), i-rays (365 nm), etc.), far ultraviolet rays, EB, EUV, X-rays, soft X-rays, excimer lasers (KrF excimer lasers, ArF excimer lasers, etc.), gamma rays, and synchrotron radiation. I-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet radiation are preferred. When using ultraviolet rays, far ultraviolet rays, EUV, X-rays, soft X-rays, excimer lasers, gamma rays, or synchrotron radiation, the exposure dose should be approximately 1~300 mJ / cm², either directly or using a mask to form the desired pattern. 2 And preferably, it should be approximately 10~200 mJ / cm 2 Irradiation is performed in a manner that allows for direct exposure or by using a mask to form the desired pattern. When using EB (Extracorporeal Electrode) for high-energy radiation, the exposure should be approximately 0.1–8000 μC / cm². 2 And preferably, it is about 0.5~5000 μC / cm 2The aforementioned resist composition is particularly suitable for fine patterning using EB or EUV, especially in high-energy radiation.

[1243] After exposure, PEB should be applied as needed. In this case, it is advisable to apply the PEB on a heated plate or in an oven at 30~200℃ for 10 seconds to 30 minutes, or more preferably at 60~180℃ for 30 seconds to 20 minutes.

[1244] [Step (iii)]

[1245] Step (iii) is to develop the previously exposed resist film using a developer containing organic acid, thereby forming a negative pattern.

[1246] The organic acid contained in the aforementioned developer solution shall preferably include at least one compound selected from any one of (b-1) to (b-7).

[1247] [Chem. 529]

[1248]

[1249] In equations (b-1) and (b-3), k is independently 1, 2, 3, or 4, respectively. Rf 1 and Rf 2 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms, but all Rf 1 and Rf 2 It cannot be both hydrogen atoms at the same time.

[1250] In equation (b-1), R b1 It consists of a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group with 1 to 50 carbon atoms that may also contain heteroatoms.

[1251] In equation (b-2), R b2 It is a hydrocarbon group with 1 to 50 carbon atoms, consisting of hydrogen atoms, halogen atoms, hydroxyl groups, or heteroatoms. However, this excludes cases where the hydrogen atoms at the α and β positions of the sulfonic acid group are replaced by fluorine atoms or fluoroalkyl groups.

[1252] In equation (b-3), R b3 It consists of a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group with 1 to 50 carbon atoms that may also contain heteroatoms.

[1253] In equation (b-4), R b4 It is a hydrocarbon group with 1 to 50 carbon atoms, consisting of hydrogen atoms, halogen atoms, hydroxyl groups, or heteroatoms. However, this excludes cases where the hydrogen atoms at the α and β positions of the carboxyl group are replaced by fluorine atoms or fluoroalkyl groups.

[1254] In equation (b-5), R b5 and R b6Each can be an independent hydrocarbon group with 1 to 50 carbon atoms, which may also contain heteroatoms.

[1255] In equation (b-6), R b7 ~R b9 Each can be an independent hydrocarbon group with 1 to 50 carbon atoms, which may also contain heteroatoms.

[1256] In equation (b-7), R b10 It is a fluorine atom or a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and the fluorinated hydrocarbon group may also contain a hydroxyl group, an ether bond, or an ester bond. R b11 It consists of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and this hydrocarbon group may also contain a hydroxyl group, an ether bond, or an ester bond. Also, R b10 and R b11 They can also bond to each other and form rings together with the atoms they are bonded to.

[1257] R b1 R b2 R b3 R b4 R b5 R b6 R b7 R b8 and R b9 The hydrocarbon groups representing 1 to 50 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 50 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 50 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; alkenyl groups with 2 to 30 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 30 carbon atoms, such as cyclohexenyl; aryl groups with 6 to 50 carbon atoms, such as phenyl, naphthyl, and anthracene; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group constituting the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.]

[1258] R b10The fluorinated hydrocarbon group representing 1 to 10 carbon atoms is a group in which some or all of the hydrogen atoms of the hydrocarbon group with 1 to 10 carbon atoms are replaced by fluorine atoms. The aforementioned hydrocarbon group with 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given as R. b1 R b2 R b3 R b4 R b5 R b6 R b7 R b8 and R b9 Examples of hydrocarbon groups with 1 to 50 carbon atoms, where the carbon number is 1 to 10.

[1259] R b11 The hydrocarbon group representing 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples can be given as R. b1 R b2 R b3 R b4 R b5 R b6 R b7 R b8 and R b9 Examples of hydrocarbon groups with 1 to 50 carbon atoms, where the carbon number is 1 to 20.

[1260] Specific examples of compounds represented by formula (b-1) are shown below, but are not limited thereto. Additionally, in the following formula, Ac represents an acetyl group, and Rf... 1 Same as above.

[1261] [Chem.530]

[1262]

[1263] [Chemistry 531]

[1264]

[1265] [Chemistry 532]

[1266]

[1267] [Chem.533]

[1268]

[1269] [Chemistry 534]

[1270]

[1271] [Chem.535]

[1272]

[1273] [Chemistry 536]

[1274]

[1275] [Chemistry 537]

[1276]

[1277] [Chem.538]

[1278]

[1279] [Chemistry 539]

[1280]

[1281] [Chem.540]

[1282]

[1283] [Chemistry 541]

[1284]

[1285] [Chemistry 542]

[1286]

[1287] Specific examples of compounds represented by formula (b-2) are listed below, but are not limited thereto.

[1288] [Chemistry 543]

[1289]

[1290] [Chemistry 544]

[1291]

[1292] [Chem.545]

[1293]

[1294] [Chemistry 546]

[1295]

[1296] [Chemistry 547]

[1297]

[1298] [Chem.548]

[1299]

[1300] Specific examples of the compound represented by formula (b-3) include the compounds shown below, but are not limited thereto.

[1301] [Chem. 549]

[1302]

[1303] [Chem. 550]

[1304]

[1305] Specific examples of the compound represented by formula (b-4) include the compounds shown below, but are not limited thereto.

[1306] [Chem. 551]

[1307]

[1308] [Chem. 552]

[1309]

[1310] [Chem. 553]

[1311]

[1312] [Chem. 554]

[1313]

[1314] Specific examples of the compound represented by formula (b-5) include the compounds shown below, but are not limited thereto.

[1315] [Chem. 555]

[1316]

[1317] [Chem. 556]

[1318]

[1319] Specific examples of the compound represented by formula (b-6) include the compounds shown below, but are not limited thereto.

[1320] [Chem. 557]

[1321]

[1322] [Chem. 558]

[1323]

[1324] [Chem. 559]

[1325]

[1326] Specific examples of compounds represented by formula (b-7) are listed below, but are not limited thereto.

[1327] [Transformation 560]

[1328]

[1329] [Chem.561]

[1330]

[1331] The organic acid content of the aforementioned developer should preferably be 0.01 to 100% by mass in the total developer solution. If it is 0.01% by mass or higher, sufficient blending effect can be obtained.

[1332] The aforementioned developing solution may also contain water or organic solvents. Examples of such organic solvents include: 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, 5-methyl-2-hexanone, methylcyclohexanone, acetophenone, methyl acetophenone, isopropanol, isoamyl alcohol, n-butanol, tert-butanol, tert-amyl alcohol, n-amyl alcohol, cyclohexanol, formic acid, acetic acid, propionic acid, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butyl acetate, isoamyl acetate, cyclohexyl acetate, 4-tert-butylcyclohexyl acetate, octyl acetate, isoborneol acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl valerate, methyl valerate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, emulsion... Organic solvents such as methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, ethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, 1-propanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methyl-1-butanol, diacetone alcohol, 4-methyl-2-pentanol, 3-methylcyclohexanol, 3,5,5-trimethylhexyl alcohol, 2,6-dimethyl-4-heptanol, toluene, anisole, and ε-caprolactone are permitted. These organic solvents can be used alone or in combination of two or more.

[1333] The water in the aforementioned developer is added to dissolve the non-liquid organic acid. The water content should preferably be 0-30% by mass, and 0-5% by mass is even better.

[1334] The organic solvent in the aforementioned developer is added to dissolve the non-liquid organic acid. The content of the organic solvent should preferably be 0-30% by mass, more preferably 0-10% by mass, and optimally 0-5% by mass.

[1335] After development, rinsing should be performed as needed. The rinsing solution should be a solvent that is miscible with the developer and does not dissolve the resist film. Ideal solvents to use include: alcohols with 3 to 10 carbon atoms, ether compounds with 8 to 12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents with 6 to 12 carbon atoms.

[1336] By performing rinsing, the collapse of the resist pattern and the occurrence of defects can be reduced. Furthermore, rinsing is not necessary; by not performing rinsing, the amount of solvent used can be reduced.

[1337] As described above, the resist composition utilizes the difference in solubility between exposed and unexposed areas during exposure to form positive or negative patterns. Therefore, a developer that dissolves the exposed areas but not the unexposed areas can be used, and vice versa. Thus, the resist pattern forming method of the present invention, by appropriately selecting the developer, can form positive or negative patterns, and is therefore widely applicable to the formation of various fine patterns.

[1338] Example

[1339] The present invention will be specifically described below with examples of synthesis, embodiments and comparative examples, but the present invention is not limited to the following embodiments.

[1340] [1] Synthesis of carboxyl-containing polymers

[1341] The monomers a-1~a-3, b-1~b-4, c-1 and c-2 used in the synthesis of carboxyl-containing polymers are described below.

[1342] [Chem.562]

[1343]

[1344] [Chem.563]

[1345]

[1346] [Chem.564]

[1347]

[1348] [Synthetic Example 1] Synthesis of Polymer P-1

[1349] Under nitrogen atmosphere, monomer a-1 (56g), monomer b-1 (36g), V-601 (manufactured by Fujifilm and Koei Tecmo Chemicals), 5.4g, and MEK (180g) were measured in a flask to prepare a monomer-polymerization initiator solution. In another flask conditioned under nitrogen atmosphere, 55g of MEK was measured, and the mixture was heated to 80°C with stirring. The aforementioned monomer-polymerization initiator solution was then added dropwise over 4 hours. After the addition was complete, the polymerization solution was stirred continuously at 80°C for 2 hours, and then cooled to room temperature. The resulting polymerization solution was added dropwise to 4000g of vigorously stirred hexane, and the precipitated polymer was separated by filtration. The obtained polymer was washed twice with hexane (1200g) and then vacuum dried at 50°C for 20 hours to obtain a white powder polymer P-1 (yield 90g, 98% yield). The Mw of polymer P-1 was 8000, and the Mw / Mn ratio was 1.42. In addition, Mw and Mn are the converted values ​​of standard polystyrene measured by GPC using THF as a solvent. The measurements were performed under the following conditions (the same applies below).

[1350] • Device: HLC-8320GPC

[1351] • Column: TSK guardcolumn

[1352] +TSKgel G4000HXL

[1353] +TSKgel G2000HXL

[1354] +TSKgel superH5000

[1355] • Pump and tubing constant temperature: 40℃

[1356] • Elution buffer: THF

[1357] • Detector: RI (Differential Refraction) detector

[1358] Injection volume: 100μL

[1359] [Chem.565]

[1360]

[1361] [Synthetic Examples 2-13] Synthesis of Polymers P-2-P-13

[1362] By changing the types and blending ratios of the monomers, the polymers shown in Table 1 below were synthesized using the same method as in Synthesis Example 1.

[1363] [Table 1]

[1364]

[1365] [2] Preparation of the resist composition

[1366] [Examples 1-1 to 1-30, Comparative Examples 1-1 to 1-2]

[1367] Using the compositions shown in Table 2 below, high-valent iodine compounds and carboxyl-containing compounds were dissolved in a solvent containing 0.01% by mass of a surfactant (PF-636, manufactured by OMNOVA), and the resulting solution was filtered through a 0.2 μm Teflon (registered trademark) filter to prepare resist compositions (R-01 to R-30). Furthermore, using the compositions shown in Table 3 below, polymers, photoacid generators, and sensitivity modifiers were dissolved in a solvent containing 0.01% by mass of a surfactant (PF-636, manufactured by OMNOVA), and the resulting solution was filtered through a 0.2 μm Teflon (registered trademark) filter to prepare resist compositions (CR-01 to CR-02).

[1368] [Table 2]

[1369]

[1370] [Table 3]

[1371]

[1372] In Tables 2 and 3, the high-valent iodine compounds I-1 to I-13, carboxylic acid compounds m-1 to m-5, photoacid generator PAG-1, sensitivity modifier Q-1, and solvent are as follows.

[1373] [Chem.566]

[1374]

[1375] [Chem.567]

[1376]

[1377] [Chem.568]

[1378]

[1379] [Chem.569]

[1380]

[1381] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[1382] AcOH (acetic acid)

[1383] GBL (γ-butyrolactone)

[1384] [3] Evaluation of EUV lithography (line and spacing patterns)

[1385] [Examples 2-1 to 2-37, Comparative Examples 2-1 to 2-3]

[1386] Each resist composition (R-01~R-30, CR-01~CR-02) was spin-coated onto a Si substrate with a silicon-containing spin-coated hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., having been formed to a thickness of 20 nm. A pre-baking (PAB) process was then performed for 60 seconds at the temperatures listed in Table 4 using a heated plate to obtain a resist film with a thickness of 40 nm. The resist film was then exposed to a 36 nm line-to-spacing (LS) 1:1 pattern using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9, 90-degree dipole illumination). A PEB process was then performed on the heated plate at the temperatures listed in Table 4 for 60 seconds, followed by development for 30 seconds using the developer listed in Table 4, forming an LS pattern with a spacing width of 18 nm and a pitch of 36 nm. The acids in the developer listed in Table 4 are as described in Table 5.

[1387] The obtained resist pattern was evaluated as follows. The results are shown in Table 4.

[1388] [Sensitivity Evaluation]

[1389] The aforementioned LS pattern was observed using a Hitachi Advanced Technology Co., Ltd. critical dimension SEM (CG-6300), and the optimal exposure Eop (mJ / cm²) for obtaining an LS pattern with a spacing width of 18nm and a pitch of 36nm was determined. 2 ), and make it a sensitivity.

[1390] [LWR Evaluation]

[1391] The dimensions of 10 points on an LS pattern obtained by exposure to the optimal amount of light along the length of the pitch width were measured using a critical dimension SEM (CG-6300) manufactured by Hitachi Advanced Technology Co., Ltd. The LWR was defined as three times the standard deviation (σ) obtained from the results (3σ). The smaller this value, the smaller and more uniform the pitch width of the pattern can be obtained.

[1392] [Limited Resolution Evaluation]

[1393] Using a Hitachi Advanced Technology Co., Ltd. critical dimension SEM (CG-6300), the limiting linewidth (nm) that can be resolved when forming a pattern by gradually increasing the exposure amount in small increments from the optimal exposure amount for forming the aforementioned LS pattern is determined, and this value is defined as the limiting resolution (nm). The smaller this value, the better the limiting resolution and the more fine the pattern can be formed.

[1394] [Table 4]

[1395]

[1396] [Table 5]

[1397]

[1398] Developer: PGEE (Propylene Glycol Ether)

[1399] PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[1400] TMAH (2.38% by mass tetramethylammonium hydroxide aqueous solution)

[1401] As shown in Table 4, negative patterns are formed by using a developer containing organic acids. Furthermore, compared to Comparative Example 2-1, higher resolution is achieved compared to development using TMAH, and excellent sensitivity and resolution are still obtained even when compared to chemically amplified resist compositions using acid catalysts, namely Comparative Examples 2-1 and 2-2. Therefore, it can be concluded that the aforementioned resist composition exhibits excellent resolution in LS pattern formation under EUV exposure.

[1402] [4] Evaluation of EUV lithography (contact hole pattern)

[1403] [Examples 3-1 to 3-37, Comparative Examples 3-1 to 3-3]

[1404] Each resist composition (R-01~R-30, CR-01~CR-02) was spin-coated onto a Si substrate with a silicon-containing spin-coated hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., having a film thickness of 20 nm. A PAB process was then performed for 60 seconds at the temperatures listed in Table 6 using a heated plate to obtain a resist film with a thickness of 50 nm. Next, the resist film was exposed using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, mask with a wafer-sized hole pattern of 64 nm pitch and +20% offset). A PEB process was then performed for 60 seconds at the temperatures listed in Table 6 using a heated plate, followed by 30 seconds of development using the developer listed in Table 6 to obtain a hole pattern with a size of 32 nm.

[1405] The obtained resist patterns were evaluated as follows. The results are shown in Table 6.

[1406] [Sensitivity Evaluation]

[1407] The aforementioned contact hole pattern was observed using a Hitachi Advanced Technology Co., Ltd. critical dimension SEM (CG-6300), and the optimal exposure value Eop (mJ / cm²) for obtaining a hole pattern with a size of 32nm was determined.2 ), and make it a sensitivity.

[1408] [CDU Evaluation]

[1409] The dimensions of 50 hole patterns obtained by irradiation with the optimal exposure were measured, and the standard deviation (σ) of the results was set as CDU (3σ). The smaller this value, the more uniform the hole diameter pattern can be obtained.

[1410] [Limited Resolution Evaluation]

[1411] Using a Hitachi Advanced Technology Co., Ltd. critical dimension SEM (CG-6300), the limiting aperture diameter (nm) that can be resolved by gradually reducing the exposure amount from the optimal exposure amount to form the aforementioned aperture pattern is determined, and this value is set as the limiting resolution (nm). The smaller this value, the better the limiting resolution, and the more fine the aperture diameter pattern can be formed.

[1412] [Table 6]

[1413]

[1414] As shown in Table 6, negative patterns are formed when a developer containing organic acids is used for development. Furthermore, a comparison with Comparative Examples 3-3 shows that higher resolution is achieved compared to development using TMAH, and excellent sensitivity and resolution are still obtained even when compared to chemically amplified resist compositions using acid catalysts, namely Comparative Examples 3-1 and 3-2. Therefore, it is evident that the resist composition of the present invention exhibits excellent resolution in the formation of hole patterns during EUV exposure.

Claims

1. A method for forming a resist pattern, comprising the following steps: (i) A resist film is formed on a substrate or on the lower layer of a substrate having a lower layer film, using a resist composition containing a high-valent iodine compound, a carboxyl-containing compound, and a solvent. (ii) Expose the resist film to high-energy radiation, and (iii) The exposed resist film is developed using a developer containing organic acid to form a negative pattern.

2. The method for forming a resist pattern according to claim 1, wherein, The high-valent iodine compound comprises at least one compound selected from any of the following formulas (1) to (16); In the formula, m1 is 0, 1, or 2; when m1 is 0, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, or 5, and 1≤n1+n2≤6; when m1 is 1, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≤n1+n2≤8; when m1 is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1≤n1+n2≤10; n3 is 1 or 2, n4 is 0, 1, 2, 3 or 4, and 1≤n3+n4≤5; n5 is 1 or 2, n6 is 0, 1, 2, 3 or 4, and 1≤n5+n6≤5; n7 is 0, 1, 2, 3 or 4, and n8 is 1, 2, 3 or 4; m2 is 0, 1, or 2; when m2 is 0, n9 is 0, 1, 2, 3, or 4; when m2 is 1, n9 is 0, 1, 2, 3, 4, 5, or 6; when m2 is 2, n9 is 0, 1, 2, 3, 4, 5, 6, 7, or 8. m3 is 0, 1, or 2; when m3 is 0, n10 is 0, 1, 2, 3, or 4; when m3 is 1, n10 is 0, 1, 2, 3, 4, 5, or 6; when m3 is 2, n10 is 0, 1, 2, 3, 4, 5, 6, 7, or 8. m4 is 0 or 1; when m4 is 0, n11 is 0, 1, 2, 3 or 4; when m4 is 1, n11 is 0, 1, 2, 3, 4, 5 or 6. m5 is 0 or 1; when m5 is 0, n12 is 0, 1, 2, 3 or 4; when m5 is 1, n12 is 0, 1, 2, 3, 4, 5 or 6. n13 and n14 are independently 0, 1, 2, 3, 4, 5 or 6; n15 and n16 are independently 0, 1, 2 or 3; m6 is 0, 1, or 2; when m6 is 0, n17 is 0, 1, 2, 3, or 4; when m6 is 1, n17 is 0, 1, 2, 3, 4, 5, or 6; when m6 is 2, n17 is 0, 1, 2, 3, 4, 5, 6, 7, or 8. m7 is 0, 1, or 2; when m7 is 0, n18 is 0, 1, 2, or 3; when m7 is 1, n18 is 0, 1, 2, 3, 4, or 5; when m7 is 2, n18 is 0, 1, 2, 3, 4, 5, 6, or 7. When m8 is 0, 1, or 2; when m8 is 0, n19 is 0, 1, 2, or 3, and n20 is 0 or 1; when m8 is 1, n19 is 0, 1, 2, 3, 4, or 5, and n20 is 0 or 1; when m8 is 2, n19 is 0, 1, 2, 3, 4, 5, 6, or 7, and n20 is 0 or 1. n21 is 0, 1, 2 or 3, n22 is 0, 1 or 2, n23 is 0, 1, 2, 3 or 4, n24 is 0, 1 or 2, n25 is 0 or 1, and n26 is 0, 1, 2 or 3. R 1 ~R 31 Each is an independent hydrocarbon group consisting of halogen atoms or may contain heteroatoms, having 1 to 10 carbon atoms; also, R 21 and R 22 They can also bond to each other and form rings together with the carbon atoms they are bonded to; R 41 ~R 44 R 47 R 49 ~R 56 R 59 R 60 and R 61 ~R 68 Each R is an independent hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms; when n2 is 2 or more, each R 41 They can be the same or different, and there are multiple Rs. 41 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n4 is 2 or more, each R 42 They can be the same or different, and there are multiple Rs. 42 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n6 is 2 or more, each R 43 They can be the same or different, and there are multiple Rs. 43 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n7 is 2 or more, each R 44 They can be the same or different, and there are multiple Rs. 44 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n9 is 2 or more, each R 47 They can be the same or different, and there are multiple Rs. 47 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n10 is 2 or more, each R 49 They can be the same or different, and there are multiple Rs. 49 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n11 is 2 or more, each R 50 They can be the same or different, and there are multiple Rs. 50 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n12 is 2 or more, each R 51 They can be the same or different, and there are multiple Rs. 51 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n13 is 2 or more, each R 52 They can be the same or different, and there are multiple Rs. 52 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n14 is 2 or more, each R 53 They can be the same or different, and there are multiple Rs. 53 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n15 is 2 or more, each R 54 They can be the same or different, and there are multiple Rs. 54 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n16 is 2 or more, each R 55 They can be the same or different, and there are multiple Rs. 55 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n17 is 2 or more, each R 56 They can be the same or different, and there are multiple Rs. 56 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n18 is 2 or more, each R 59 They can be the same or different, and there are multiple Rs. 59 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n19 is 2 or more, each R 60 They can be the same or different, and there are multiple Rs. 60 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n21 is 2 or more, each R 61 They can be the same or different, and there are multiple Rs. 61 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n22 is 2 or more, each R 63 They can be the same or different, and there are multiple Rs. 63 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n23 is 2 or more, each R 64 They can be the same or different, and there are multiple Rs. 64 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n24 is 2 or more, each R 65 They can be the same or different, and there are multiple Rs. 65 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n26 is 2 or more, each R 68 They can be the same or different, and there are multiple Rs. 68 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; R 45 When n8 is 1, 3, or 4, it is an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms; when n8 is 2, it is an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, thioketone bond, an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms; furthermore, part or all of the hydrogen atoms of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted by a group containing a heteroatom, and part of the -CH2- of the (n8) valent hydrocarbon group may also be substituted by a group containing a heteroatom, and R 44 and R 45 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms; R 48 It is a carbonyl group or may contain a hydrocarbon group with 1 to 10 carbon atoms; R 56 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms; R 57 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms; 1.

2.

3.

4.

5.

6. 7 and 8 represents the atomic bond of the carbon atom or heteroatom in the aromatic ring or heterocycle in the formula; however, 1 and 2. 3 and 4. 5 and 6 and 7 and 8. Adjacent atoms on an aromatic ring or adjacent atoms on a heterocyclic ring; L 1 It can be unbonded, single bond, -O-, -S-, -NH- or -CH2-; X is -S- or -N(R) 58 )-;R 58 It consists of a hydrogen atom, a halogen atom, or a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms; X 1 and X 2 Each independently -OX 11 -or -X 12 -C(=O)-;X 3 for -OX 11 -、 -SX 11 -or -X 12 -C(=O)-;X 11 It is a carbonyl group or may contain a hydrocarbon group with 1 to 10 carbon atoms; X 12 -S- or -N(R) 69 )-;R 69 It consists of a hydrocarbon group with 1 to 20 carbon atoms, which may be hydrogen atoms, halogen atoms, or heteroatoms.

3. The method for forming a resist pattern according to claim 1, wherein, The carboxyl-containing compound is a carboxyl-containing polymer containing a repeating unit represented by formula (a-1) or a carboxylic acid compound represented by formula (a-2); In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group; X A For single bonds, phenylene, naphthylene or -C(=O)-OX A1 -;X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring; This represents the atomic bonds between carbon atoms in the main chain; p is 1, 2, 3 or 4; R a1 When p is 1, 3, or 4, it is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms; when p is 2, it is an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms; furthermore, part or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group may be replaced by a group containing heteroatoms, and part of the -CH2- of the p-valent hydrocarbon group may also be replaced by a group containing heteroatoms; R a2 It is a single bond or a hydrocarbon group with 1 to 20 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group can be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group can also be replaced by a group containing a heteroatom; when p is 2, 3 or 4, each R a2 They can be the same or different.

4. The method for forming a resist pattern according to any one of claims 1 to 3, wherein, The organic acid comprises at least one compound selected from any of the following formulas (b-1) to (b-7); In the formula, k is 1, 2, 3 or 4; Rf 1 and Rf 2 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms, but all Rf 1 and Rf 2 It cannot simultaneously be a hydrogen atom; R b1 It consists of hydrogen atoms, halogen atoms, hydroxyl groups, or may also contain heteroatoms and hydrocarbon groups with 1 to 50 carbon atoms; R b2 It is a hydrocarbon group with 1 to 50 carbon atoms, consisting of hydrogen atoms, halogen atoms, hydroxyl groups, or heteroatoms; however, it excludes cases where the hydrogen atoms on the carbon atoms at the α and β positions of the sulfonic acid group are replaced by fluorine atoms or fluoroalkyl groups. R b3 It consists of hydrogen atoms, halogen atoms, hydroxyl groups, or may also contain heteroatoms and hydrocarbon groups with 1 to 50 carbon atoms; R b4 It is a hydrocarbon group with 1 to 50 carbon atoms, consisting of hydrogen atoms, halogen atoms, hydroxyl groups, or heteroatoms; however, it excludes cases where the hydrogen atoms at the α and β positions of the carboxyl group are replaced by fluorine atoms or fluoroalkyl groups. R b5 and R b6 Each can be an independent hydrocarbon group with 1 to 50 carbon atoms, which may also contain heteroatoms; R b7 ~R b9 Each can be an independent hydrocarbon group with 1 to 50 carbon atoms, which may also contain heteroatoms; R b10 It is a fluorine atom or a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and the fluorinated hydrocarbon group may also contain a hydroxyl group, an ether bond, or an ester bond; R b11 It is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and this hydrocarbon group may also contain a hydroxyl group, an ether bond, or an ester bond; also, R b10 With R b11 They can also bond to each other and form rings together with the atoms they are bonded to.

5. The method for forming a resist pattern according to any one of claims 1 to 3, wherein, The high-energy rays are i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet rays.

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