Resist composition, laminate, pattern forming method, and method for producing resist composition

Abstract

The invention relates to a resist composition, a laminate, a pattern forming method, and a method for producing the resist composition. The present invention addresses the problem of providing a non-chemically amplified resist composition having excellent sensitivity and limit resolution in optical lithography using high-energy rays, a laminate using the resist composition, a pattern forming method, and a method for producing the resist composition. [Solution] The resist composition contains a hypervalent iodine compound, a carboxyl group-containing polymer, and a solvent. The resist composition is characterized in that the carboxyl group-containing polymer is a polymer containing a carboxylic acid derivative repeating unit represented by formula (1), and the dispersion degree (Mw / Mn) obtained from the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of the polymer measured by gel permeation chromatography is 1.30 or less.

Description

Technical Field

[0001] This invention relates to a resist composition, a laminate, a pattern forming method using the aforementioned resist composition, and a method for manufacturing the aforementioned resist composition. Background Technology

[0002] With the expansion of the IoT market, there is a growing demand for higher integration, higher speed, and lower power consumption in LSI (Light Silica) technology, 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 may not achieve the desired resolution.

[0008] As a method 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, which involves increasingly miniaturized processing dimensions. 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 ultimate resolution.

[0009] Patent Document 2 claims the use of a negative resist composition of tin compounds. This is because tin, which has high absorption under EUV light, is the main component, thus improving randomness and achieving high sensitivity and high resolution. However, such a metal resist has many problems, including insufficient solubility in the resist solvent, storage stability, and defects caused by etching residue. Furthermore, since the exposed portion of the metal resist is primarily a metal oxide, it becomes insoluble in the developer solution, requiring an additional inversion process when used for patterning contact holes, which also raises cost concerns.

[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.5039p1 (2003)

[0016] [Non-Patent Literature 2] SPIE Vol.6520p65203L-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 above circumstances, and aims to provide a non-chemically amplified resist composition with excellent sensitivity and limiting resolution in optical lithography using high-energy rays, especially in electron beam (EB) lithography and EUV lithography, as well as a method for forming a laminate and pattern using the resist composition.

[0019] [Methods for solving the problem]

[0020] To address the aforementioned issues, the present invention provides a resist composition comprising: a high-valent iodine compound, a carboxyl-containing polymer, and a solvent;

[0021] The aforementioned resist composition is characterized in that the aforementioned carboxyl-containing polymer is a polymer containing repeating units of carboxylic acid derivatives represented by the following formula (1), and the dispersion Mw / Mn obtained from the weight-average molecular weight Mw and number-average molecular weight Mn of the polymer by gel permeation chromatography is less than 1.30.

[0022] [Chemistry 1]

[0023]

[0024] In the formula, 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, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the polymer backbone.

[0025] If the resist composition of this invention is used, it will become a non-chemically amplified resist composition with excellent sensitivity and limiting resolution in optical lithography using high-energy rays, especially in electron beam (EB) lithography and EUV lithography. In particular, by using a resist composition containing polymers with narrow dispersion (molecular weight distribution), the roughness is small, the solubility is uniform, and the polymer swelling is minimal. It can also prevent the reduction in resolution caused by pattern collapse of line and spacing patterns, or the blockage between patterns of contact hole patterns.

[0026] At this time, the aforementioned high-valent iodine compound should preferably be at least one selected from the group consisting of high-valent iodine compounds represented by the following formulas (2) to (11).

[0027] [Chemistry 2]

[0028]

[0029] 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, n8 is 1, 2, 3, or 4, and 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, and 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, and 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, and 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 0, 1, 2, 3, 4, 5, or 6; n15 and n16 are 0, 1, 2, or 3; and 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; and 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, and 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. R 1 ~R 22 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 1 and R 2 R 3 and R 4 R 5 and R 6 R 7 and R 8 R 9 and R 10R 11 and R 12 R 13 and R 14 R 15 and R 16 R 17 and R 18 、or R 19 and R 20 They can also bond to each other and form a ring together with the carbonyl oxygen groups they are bonded to and the atoms between the carbonyl oxygen groups, R 21 and R 22 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 31 ~R 34 R 37 R 39 ~R 46 R 49 R 50 Each R is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms. When n2 is 2 or more, each R 31 They can be the same or different, and there are multiple Rs. 31 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 32 They can be the same or different, and there are multiple Rs. 32 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 33 They can be the same or different, and there are multiple Rs. 33 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 34 They can be the same or different, and there are multiple Rs. 34 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 37 They can be the same or different, and there are multiple Rs. 37 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 39 They can be the same or different, and there are multiple Rs. 39 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 40 They can be the same or different, and there are multiple Rs. 40 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 41 They can be the same or different, and there are multiple Rs. 41They 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 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 n14 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 n15 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 n16 is 2 or more, each R 45 They can be the same or different, and there are multiple Rs. 45 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 46 They can be the same or different, and there are multiple Rs. 46 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 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 n19 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. R 35 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 35 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thioketone bond. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 34 and R 35 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 36 A hydrocarbon group consisting of 1 to 10 carbon atoms, which may also contain heteroatoms. R 38 It is a carbonyl group, or a hydrocarbon group with 1 to 10 carbon atoms that may also contain heteroatoms. *1 and *2 represent atomic bonds of the carbon atoms in the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms on the aromatic ring. L1 is unbonded, a single bond, -O-, -S-, -NH-, or -CH2-, R 47It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms. X is nitrogen or sulfur, and when it is nitrogen, it may also have R. 48 R 48 It consists of a hydrocarbon group with 1 to 20 carbon atoms, which may be hydrogen atoms, halogen atoms, or heteroatoms.

[0030] The high-valent iodine compound contained in the resist composition of the present invention is preferably a tricoordinate high-valent iodine compound represented by the above formula. Such a tricoordinate iodine(III) compound having aryl and carboxylic acid ligands readily undergoes an equilibrium reaction with the carboxyl-containing compound through mixing. At this time, by removing the original carboxylic acid ligands from the reaction system, the equilibrium will shift towards the formation of a high-valent iodine compound with new ligands for ligand exchange. Thus, the carboxyl-containing compound becomes a polymer crosslinked with the high-valent iodine compound.

[0031] Furthermore, the present invention provides a laminate characterized by comprising: a substrate, and a resist film of the resist composition located on the substrate.

[0032] In a laminate containing a resist film derived from the resist composition of the present invention, the resist film of the film-forming body of the above-mentioned resist composition has high sensitivity and exhibits excellent limiting resolution, which is effective for precision micro-processing and can be applied to the formation of any pattern, whether positive or negative. Therefore, it has a wide range of applications and is highly useful in resist manufacturing technology.

[0033] At this point, a lower resist film may be provided between the aforementioned substrate and the aforementioned resist film. Furthermore, the aforementioned resist film preferably contains the ligand exchange reaction product of the aforementioned high-valent iodine compound and the carboxyl-containing polymer.

[0034] The laminate of the present invention can be configured as needed.

[0035] Furthermore, the present invention provides a pattern forming method, characterized by comprising the following steps:

[0036] A resist film is formed on a substrate or on the resist underlayer film of a substrate having a resist underlayer film laminated thereon using the above-described resist composition.

[0037] The aforementioned resist film was exposed using high-energy rays, and

[0038] The previously exposed resist film was developed using a developer.

[0039] If the pattern forming method of the present invention is used, it is useful for forming finer patterns because it uses a resist composition with excellent sensitivity and resolution in optical lithography using high-energy rays, especially in electron beam (EB) lithography and EUV lithography.

[0040] At this time, the aforementioned high-energy rays should preferably be i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet rays.

[0041] The pattern forming method of the present invention can form finer patterns by using such high-energy rays.

[0042] Furthermore, the present invention provides a method for manufacturing a resist composition, which is a method for manufacturing the above-mentioned resist composition, characterized by comprising the following steps:

[0043] The aforementioned carboxyl-containing polymer was synthesized by living radical polymerization using a free radical initiator and a reversible addition cleavage chain transfer agent (RAFT agent) represented by formula (R-1) or (R-2), and the resulting carboxyl-containing polymer, the aforementioned high-valent iodine compound, and the aforementioned solvent were mixed.

[0044] [Chemistry 3]

[0045]

[0046] In the formula, R X1 and R X3 They are, independently, saturated hydrocarbon thiols with 3 to 20 carbon atoms, aralkyl thiols with 7 to 20 carbon atoms, heterocyclic groups with 5 to 20 carbon atoms, and -N(Z) groups. A (Z) B -COOZ A -OCOZ A -CON(Z) A (Z) B -P(=O)(OZ) A )2 or -OP(=O)(Z A (Z) B Z A and Z B Each is independently a saturated hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and Z A and Z B In this process, some or all of the hydrogen atoms bonded to its carbon atoms can be replaced by cyano groups, carboxyl groups, etc. R X2 and R X4 Each can be independently a saturated hydrocarbon group with 2 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms, which may also contain heteroatoms.

[0047] By synthesizing the above-mentioned carboxyl-containing polymer in this manner, a narrowly dispersed polymer can be obtained, and the resist composition of the present invention containing it can be manufactured with high productivity.

[0048] [The effects of the invention]

[0049] The resist composition of the present invention exhibits high sensitivity to high-energy rays, particularly i-rays, KrF excimer lasers, ArF excimer lasers, EB lithography, and EUV lithography, while also providing excellent roughness and ultimate resolution, and is extremely useful in forming fine patterns. Detailed Implementation

[0050] After repeated and in-depth explorations to achieve the aforementioned objectives, the inventors have obtained the following insights, and thus completed this invention: a resist composition mainly composed of high-valent iodine compounds and predetermined carboxyl-containing polymers can provide a resist film with high sensitivity, low roughness, and excellent limiting resolution, which is extremely effective in precision micromachining.

[0051] That is, the present invention is a resist composition characterized by containing: a high-valent iodine compound, a carboxyl-containing polymer and a solvent; the aforementioned carboxyl-containing polymer is a polymer containing repeating units of carboxylic acid derivatives represented by the following formula (1), and the dispersity Mw / Mn obtained by gel permeation chromatography (GPC) of the polymer is 1.30 or less.

[0052] [Chemistry 4]

[0053]

[0054] In the formula, 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, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the polymer backbone.

[0055] The present invention will now be described in detail, but it is not limited thereto. Furthermore, in this specification, the endpoints of a numerical range are defined as encompassing all values ​​contained within that range (for example, "0 to 3" includes 0, 1, 2, and 3).

[0056] [Resist Composition]

[0057] The resist composition of the present invention contains a high-valent iodine compound and a predetermined carboxyl-containing polymer as the main components.

[0058] [High-valent iodine compounds]

[0059] The aforementioned high-valent iodine compounds are tricoordinate high-valent iodine compounds represented by the following formulas (2) to (11).

[0060] [Chemistry 5]

[0061]

[0062] 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, n8 is 1, 2, 3, or 4, and 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, and 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, and 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, and 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 0, 1, 2, 3, 4, 5, or 6; n15 and n16 are 0, 1, 2, or 3; and 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; and 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, and 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. R 1 ~R 22 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 1 and R 2 R 3 and R 4 R 5 and R 6 R7 and R 8 R 9 and R 10 R 11 and R 12 R 13 and R 14 R 15 and R 16 R 17 and R 18 、or R 19 and R 20 They can also bond to each other and form a ring together with the carbonyl oxygen groups they are bonded to and the atoms between the carbonyl oxygen groups, R 21 and R 22 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 31 ~R 34 R 37 R 39 ~R 46 R 49 R 50 Each R is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms. When n2 is 2 or more, each R 31 They can be the same or different, and there are multiple Rs. 31 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 32 They can be the same or different, and there are multiple Rs. 32 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 33 They can be the same or different, and there are multiple Rs. 33 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 34 They can be the same or different, and there are multiple Rs. 34 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 37 They can be the same or different, and there are multiple Rs. 37 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 39 They can be the same or different, and there are multiple Rs. 39 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 40 They can be the same or different, and there are multiple Rs. 40 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 41They 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 n13 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 n14 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 n15 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 n16 is 2 or more, each R 45 They can be the same or different, and there are multiple Rs. 45 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 46 They can be the same or different, and there are multiple Rs. 46 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 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 n19 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. R 35 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 35 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thioketone bond. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 34 and R 35 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 36 A hydrocarbon group consisting of 1 to 10 carbon atoms, which may also contain heteroatoms. R 38It is a carbonyl group, or a hydrocarbon group with 1 to 10 carbon atoms that may also contain heteroatoms. *1 and *2 represent atomic bonds of the carbon atoms in the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms on the aromatic ring. L1 is unbonded, a single bond, -O-, -S-, -NH-, or -CH2-, R 47 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms. X is nitrogen or sulfur, and when it is nitrogen, it may also have R. 48 R 48 It consists of a hydrocarbon group with 1 to 20 carbon atoms, which may be hydrogen atoms, halogen atoms, or heteroatoms.

[0063] In equations (2) to (11), 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; 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 0, 1, 2, 3, 4, 5, or 6; n15 and n16 are 0, 1, 2, or 3; and 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; and 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, and 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. Additionally, when m1, m2, m3, m4, m5, m6, m7, and m8 are 0, the aromatic ring is a benzene ring.

[0064] In equations (2) to (4), (6) to (9), and (11), R 1 ~R 22 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 1 and R 2 R 3 and R4 R 5 and R 6 R 7 and R 8 R 9 and R 10 R 11 and R 12 R 13 and R 14 R 15 and R 16 R 17 and R 18 、or R 19 and R 20 They can also bond to each other and form a ring together with the carbonyl oxygen groups they are bonded to and the atoms between the carbonyl oxygen groups, R 21 and R 22 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.

[0065] R 1 ~R 22 Examples of halogen atoms that can be represented include: fluorine, chlorine, bromine, and iodine atoms. R 1 ~R 22 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, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, 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 22 It should be a hydrocarbon group with 1 to 4 carbon atoms.

[0066] In equations (2) to (11), R 31 ~R 34 R 37R 39 ~R 46 R 49 R 50 Each R is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms. When n2 is 2 or more, each R 31 They can be the same or different, and there are multiple Rs. 31 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 32 They can be the same or different, and there are multiple Rs. 32 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 33 They can be the same or different, and there are multiple Rs. 33 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 34 They can be the same or different, and there are multiple Rs. 34 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 37 They can be the same or different, and there are multiple Rs. 37 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 39 They can be the same or different, and there are multiple Rs. 39 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 40 They can be the same or different, and there are multiple Rs. 40 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 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 n13 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 n14 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 n15 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 n16 is 2 or more, each R 45 They can be the same or different, and there are multiple Rs. 45They 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 46 They can be the same or different, and there are multiple Rs. 46 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 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 n19 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.

[0067] R 31 ~R 34 R 37 R 39 ~R 46 R 49 R 50 Examples of halogen atoms that can be represented include: fluorine, chlorine, bromine, and iodine atoms. R 31 ~R 34 R 37 R 39 ~R 46 R 49 R 50 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, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, these groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.]

[0068] In equation (4), R 35R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 35 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thioketone bond. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 34 and R 35 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.

[0069] R 35 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 to 40 carbon atoms, alkenes with 2 to 40 carbon atoms, alkynes with 2 to 40 carbon atoms, cyclic saturated hydrocarbons with 3 to 40 carbon atoms, cyclic unsaturated hydrocarbons with 3 to 40 carbon atoms, and aromatic hydrocarbons with 6 to 40 carbon atoms.

[0070] Specific examples of alkanes with 1 to 40 carbon atoms include: methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[0071] 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.

[0072] 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.

[0073] Specific examples of the aforementioned cyclic saturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norcamphene, etc.

[0074] Specific examples of the aforementioned cyclic unsaturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropylene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norcamphene.

[0075] Specific examples of aromatic hydrocarbons with 6 to 40 carbon atoms mentioned above include: benzene, naphthalene, biphenyl, etc.

[0076] R 35 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.

[0077] R35 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 atoms, sulfur atoms, nitrogen atoms, 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 atoms, sulfur atoms, and nitrogen atoms, resulting in the presence of carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, carbamate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), etc.

[0078] In equation (5), R 36 A hydrocarbon group consisting of 1 to 10 carbon atoms, which may also contain heteroatoms. R 36 Specific examples of halogen atoms and hydrocarbon groups can be listed and illustrated as R. 1 ~R 22 The same examples represent halogen atoms and hydrocarbon groups.

[0079] In equation (5), R 38 It is a carbonyl group, or a hydrocarbon group with 1 to 10 carbon atoms that may contain heteroatoms. The aforementioned hydrocarbon groups with 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkylene groups with 1 to 10 carbon atoms, such as methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-2,3-diyl, butane-1,4-diyl, 2-methylpropane-1,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, and decane-1,10-diyl; cyclopentanediyl, cyclohexanediyl, norcamphenediyl, adamantanediyl, and tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms, such as decanediyl; vinylidene, propenide, etc., with 2 to 10 carbon atoms; arylene groups with 6 to 10 carbon atoms, such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, naphthylene; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, groups may contain hydroxyl, cyano, halogenated alkyl, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.]38 It is preferable to use a carbonyl group, a hydrocarbon group with 1 to 4 carbon atoms, or a fluorinated hydrocarbon group with 1 to 4 carbon atoms.

[0080] In equation (5), *1 and *2 represent the atomic bonds of the carbon atoms in the aromatic ring. However, *1 and *2 are bonded to adjacent carbon atoms on the aromatic ring. Such combinations of *1, *2, and m2 can be considered in the following 7 states.

[0081] [Chemistry 6]

[0082]

[0083] In the formula, n9 and R 37 and R 38 Same as above. The dashed line represents R. 36 -C(=O)-O- atomic bonds.

[0084] L1 can be unbonded (in which case the carbon atom on the aromatic ring is replaced by a hydrogen atom), single bond, -O-, -S-, -NH-, or -CH2-.

[0085] In equation (10), R 47 A hydrocarbon group consisting of 1 to 10 carbon atoms, which may also contain heteroatoms. R 47 Specific examples of halogen atoms and hydrocarbon groups can be listed and illustrated as R. 1 ~R 22 The same examples represent halogen atoms and hydrocarbon groups.

[0086] In equation (10), X is nitrogen or sulfur, and when it is nitrogen, it can also have R. 48 R 48 A hydrocarbon group consisting of 1 to 20 carbon atoms, which may be hydrogen atoms, halogen atoms, or heteroatoms. R 48 Specific examples of halogen atoms and hydrocarbon groups can be listed and illustrated as R. 1 ~R 22 The same examples represent halogen atoms and hydrocarbon groups.

[0087] Additionally, R 31 ~R 34 R 37 ~R 46 R 49 R 50 It can replace any position of the aromatic ring in the above formula.

[0088] Specific examples of high-valent iodine compounds represented by equation (2) are listed below, but are not limited thereto.

[0089] [Chemistry 7]

[0090]

[0091] [Chemistry 8]

[0092]

[0093] [Chemistry 9]

[0094]

[0095] [Chemistry 10]

[0096]

[0097] [Chemistry 11]

[0098]

[0099] [Chemistry 12]

[0100]

[0101] [Chemistry 13]

[0102]

[0103] [Chemistry 14]

[0104]

[0105] [Chemistry 15]

[0106]

[0107] [Chemistry 16]

[0108]

[0109] [Chemistry 17]

[0110]

[0111] [Chemistry 18]

[0112]

[0113] Specific examples of high-valent iodine compounds represented by equation (3) are listed below, but are not limited thereto.

[0114] [Chemistry 19]

[0115]

[0116] [Chemistry 20]

[0117]

[0118] [Chemistry 21]

[0119]

[0120] [Chemistry 22]

[0121]

[0122] Specific examples of high-valent iodine compounds represented by equation (4) are listed below, but are not limited thereto.

[0123] [Chemistry 23]

[0124]

[0125] [Chemistry 24]

[0126]

[0127] [Chemistry 25]

[0128]

[0129] [Chemistry 26]

[0130]

[0131] [Chemistry 27]

[0132]

[0133] [Chemistry 28]

[0134]

[0135] Specific examples of high-valent iodine compounds represented by formula (5) are shown below, but are not limited thereto. Additionally, in the following formula, Me represents a methyl group.

[0136] [Chemistry 29]

[0137]

[0138] [Chemistry 30]

[0139]

[0140] [Chemistry 31]

[0141]

[0142] [Chemistry 32]

[0143]

[0144] [Chemistry 33]

[0145]

[0146] [Chemistry 34]

[0147]

[0148] [Chemistry 35]

[0149]

[0150] [Chemistry 36]

[0151]

[0152] [Chemistry 37]

[0153]

[0154] [Chemistry 38]

[0155]

[0156] [Chemistry 39]

[0157]

[0158] [Chemistry 40]

[0159]

[0160] [Chemistry 41]

[0161]

[0162] [Chemistry 42]

[0163]

[0164] [Chemistry 43]

[0165]

[0166] [Chemistry 44]

[0167]

[0168] [Chemistry 45]

[0169]

[0170] [Chemistry 46]

[0171]

[0172] [Chemistry 47]

[0173]

[0174] [Chemistry 48]

[0175]

[0176] [Chemistry 49]

[0177]

[0178] [Transformation 50]

[0179]

[0180] [Chemistry 51]

[0181]

[0182] [Chemistry 52]

[0183]

[0184] [Chemistry 53]

[0185]

[0186] [Chemistry 54]

[0187]

[0188] [Chemistry 55]

[0189]

[0190] [Chemistry 56]

[0191]

[0192] [Chemistry 57]

[0193]

[0194] [Chem.58]

[0195]

[0196] [Chemistry 59]

[0197]

[0198] [Transformation 60]

[0199]

[0200] [Chemistry 61]

[0201]

[0202] [Chemistry 62]

[0203]

[0204] [Chemistry 63]

[0205]

[0206] [Chemistry 64]

[0207]

[0208] [Chemistry 65]

[0209]

[0210] [Chemistry 66]

[0211]

[0212] [Chemistry 67]

[0213]

[0214] [Chemistry 68]

[0215]

[0216] [Chemistry 69]

[0217]

[0218] [Chemistry 70]

[0219]

[0220] [Chemistry 71]

[0221]

[0222] [Chemistry 72]

[0223]

[0224] [Chemistry 73]

[0225]

[0226] [Chemistry 74]

[0227]

[0228] [Chemistry 75]

[0229]

[0230] [Chemistry 76]

[0231]

[0232] [Chemistry 77]

[0233]

[0234] [Chemistry 78]

[0235]

[0236] [Chemistry 79]

[0237]

[0238] [Chemistry 80]

[0239]

[0240] [Chemistry 81]

[0241]

[0242] [Chemistry 82]

[0243]

[0244] [Chemistry 83]

[0245]

[0246] [Chemistry 84]

[0247]

[0248] Specific examples of high-valent iodine compounds represented by equation (6) are listed below, but are not limited thereto.

[0249] [Chemistry 85]

[0250]

[0251] [Chemistry 86]

[0252]

[0253] [Chemistry 87]

[0254]

[0255] [Chemistry 88]

[0256]

[0257] [Chemistry 89]

[0258]

[0259] [Chemistry 90]

[0260]

[0261] [Chemistry 91]

[0262]

[0263] [Chemistry 92]

[0264]

[0265] [Chemistry 93]

[0266]

[0267] [Chemistry 94]

[0268]

[0269] [Chem. 95]

[0270]

[0271] [Chemistry 96]

[0272]

[0273] [Chemistry 97]

[0274]

[0275] [Chem. 98]

[0276]

[0277] [Chemistry 99]

[0278]

[0279] [Chemistry 100]

[0280]

[0281] Specific examples of high-valent iodine compounds represented by equation (7) are shown below, but are not limited thereto. Furthermore, in the following equation, L1 is the same as described above.

[0282] [Chemistry 101]

[0283]

[0284] [Chemistry 102]

[0285]

[0286] [Chemistry 103]

[0287]

[0288] [Chemistry 104]

[0289]

[0290] [Chemistry 105]

[0291]

[0292] [Chemistry 106]

[0293]

[0294] [Chemistry 107]

[0295]

[0296] [Chemistry 108]

[0297]

[0298] [Chemistry 109]

[0299]

[0300] [Chemical 110]

[0301]

[0302] [Chemistry 111]

[0303]

[0304] [Chemistry 112]

[0305]

[0306] [Chemistry 113]

[0307]

[0308] [Chemistry 114]

[0309]

[0310] [Chemistry 115]

[0311]

[0312] [Chemistry 116]

[0313]

[0314] Specific examples of high-valent iodine compounds represented by equation (8) are listed below, but are not limited thereto.

[0315] [Chemistry 117]

[0316]

[0317] [Chemistry 118]

[0318]

[0319] [Chemistry 119]

[0320]

[0321] [Chemistry 120]

[0322]

[0323] [Chemistry 121]

[0324]

[0325] [Chemistry 122]

[0326]

[0327] [Chemistry 123]

[0328]

[0329] [Chemistry 124]

[0330]

[0331] Specific examples of high-valent iodine compounds represented by equation (9) are listed below, but are not limited thereto.

[0332] [Chemistry 125]

[0333]

[0334] [Chemistry 126]

[0335]

[0336] [Chemistry 127]

[0337]

[0338] [Chemistry 128]

[0339]

[0340] [Chemistry 129]

[0341]

[0342] [Chemistry 130]

[0343]

[0344] [Chemistry 131]

[0345]

[0346] [Chemistry 132]

[0347]

[0348] Specific examples of high-valent iodine compounds represented by formula (10) are listed below, but are not limited thereto.

[0349] [Chemistry 133]

[0350]

[0351] [Chemistry 134]

[0352]

[0353] [Chemistry 135]

[0354]

[0355] [Chemistry 136]

[0356]

[0357] [Chemistry 137]

[0358]

[0359] [Chemistry 138]

[0360]

[0361] [Chemistry 139]

[0362]

[0363] [Chemistry 140]

[0364]

[0365] [Chemistry 141]

[0366]

[0367] [Chemistry 142]

[0368]

[0369] [Chemistry 143]

[0370]

[0371] [Chemistry 144]

[0372]

[0373] [Chemistry 145]

[0374]

[0375] [Chemistry 146]

[0376]

[0377] [Chemistry 147]

[0378]

[0379] [Chemistry 148]

[0380]

[0381] [Chemistry 149]

[0382]

[0383] Specific examples of high-valent iodine compounds represented by formula (11) are listed below, but are not limited thereto.

[0384] [Chemistry 150]

[0385]

[0386] [Chemistry 151]

[0387]

[0388] [Chemistry 152]

[0389]

[0390] [Chemistry 153]

[0391]

[0392] [Chemistry 154]

[0393]

[0394] [Chemistry 155]

[0395]

[0396] [Chemistry 156]

[0397]

[0398] [Chemistry 157]

[0399]

[0400] [Chemistry 158]

[0401]

[0402] [Chemistry 159]

[0403]

[0404] [Chemistry 160]

[0405]

[0406] [Chemistry 161]

[0407]

[0408] [Chemistry 162]

[0409]

[0410] [Chemistry 163]

[0411]

[0412] [Chemistry 164]

[0413]

[0414] [Chemistry 165]

[0415]

[0416] [Chemistry 166]

[0417]

[0418] [Chemistry 167]

[0419]

[0420] [Chemistry 168]

[0421]

[0422] [Chemistry 169]

[0423]

[0424] [Chemistry 170]

[0425]

[0426] [Chemistry 171]

[0427]

[0428] [Chemistry 172]

[0429]

[0430] [Chemistry 173]

[0431]

[0432] [Chemistry 174]

[0433]

[0434] [Chemistry 175]

[0435]

[0436] [Chemistry 176]

[0437]

[0438] [Chemistry 177]

[0439]

[0440] [Chemistry 178]

[0441]

[0442] [Chemistry 179]

[0443]

[0444] [Chemistry 180]

[0445]

[0446] [Chemistry 181]

[0447]

[0448] [Chemistry 182]

[0449]

[0450] [Chemistry 183]

[0451]

[0452] [Chemistry 184]

[0453]

[0454] [Chemistry 185]

[0455]

[0456] [Chemistry 186]

[0457]

[0458] [Chemistry 187]

[0459]

[0460] [Chem.188]

[0461]

[0462] [Chemistry 189]

[0463]

[0464] [Chemistry 190]

[0465]

[0466] [Chemistry 191]

[0467]

[0468] [Chemistry 192]

[0469]

[0470] [Chemistry 193]

[0471]

[0472] [Chemistry 194]

[0473]

[0474] [Chemistry 195]

[0475]

[0476] [Chemistry 196]

[0477]

[0478] [Chemistry 197]

[0479]

[0480] [Chemistry 198]

[0481]

[0482] [Chemistry 199]

[0483]

[0484] [Chemistry 200]

[0485]

[0486] [Chemical Engineering 201]

[0487]

[0488] [Chemical Engineering 202]

[0489]

[0490] [Chemical Engineering 203]

[0491]

[0492] [Carboxyl-containing polymers]

[0493] The carboxyl-containing polymer of the present invention is a polymer containing repeating units of a carboxylic acid derivative represented by the following formula (1), and the dispersity Mw / Mn obtained from the weight-average molecular weight Mw and number-average molecular weight Mn of the polymer measured by GPC is 1.30 or less. The theoretical lower limit of the aforementioned dispersity is 1, and the closer it is to 1, the more monodisperse it is.

[0494] In this invention, a narrow dispersion with a dispersibility Mw / Mn ratio of 1.30 or less is important to obtain a non-chemically amplified resist composition with excellent sensitivity and limiting resolution. If the dispersibility exceeds 1.30, the molecular weight distribution of the polymer becomes wider, resulting in increased roughness when used as a resist. The solubility also becomes uneven due to the wider molecular weight distribution, leading to concerns such as polymer swelling, pattern collapse in line and spacing patterns, or blockage between contact hole patterns. A dispersibility Mw / Mn ratio of 1.0 to 1.30 is preferable, and 1.0 to 1.1 is even better.

[0495] [Chemical 204]

[0496]

[0497] 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, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the polymer backbone.

[0498] Furthermore, in this invention, Mw and Mn are standard polystyrene conversion values ​​determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. Those skilled in the art know that GPC (also known as size exclusion chromatography (SEC)) can be used to determine the molecular weight distribution (dispersion) of polymers, and know which column, detector, and set temperature should be used to reliably determine Mw and Mn in accordance with the method of correcting GPC and the carboxyl-containing polymers of this invention, and how the dispersion of the polymer can be obtained with good reproducibility within the normal error range.

[0499] Specific examples of the repeating unit containing a carboxyl group represented by equation (1) are shown below, but are not limited thereto. Additionally, in the following equation, R... A Same as above.

[0500] [Chemical Engineering 205]

[0501]

[0502] [Chemical Engineering 206]

[0503]

[0504] Polymers containing carboxyl groups and repeating units represented by formula (1) may also contain repeating units other than those represented by formula (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 can be expected to have high etch resistance due to a rigid backbone, or repeating units containing a styrene backbone.

[0505] 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.

[0506] [Chemical 207]

[0507]

[0508] [Chemical Engineering 208]

[0509]

[0510] [Chemical Engineering 209]

[0511]

[0512] [Chemical 210]

[0513]

[0514] [Chemistry 211]

[0515]

[0516] [Chemistry 212]

[0517]

[0518] [Chemistry 213]

[0519]

[0520] [Chemistry 214]

[0521]

[0522] [Chemical 215]

[0523]

[0524] [Chemistry 216]

[0525]

[0526] [Chemistry 217]

[0527]

[0528] [Chemistry 218]

[0529]

[0530] [Chemistry 219]

[0531]

[0532] [Chem.220]

[0533]

[0534] [Chemistry 221]

[0535]

[0536] [Chemistry 222]

[0537]

[0538] [Chemistry 223]

[0539]

[0540] [Chemistry 224]

[0541]

[0542] [Chemistry 225]

[0543]

[0544] [Chemistry 226]

[0545]

[0546] [Chemistry 227]

[0547]

[0548] [Chemistry 228]

[0549]

[0550] [Chemistry 229]

[0551]

[0552] [Chemistry 230]

[0553]

[0554] [Chemistry 231]

[0555]

[0556] [Chemistry 232]

[0557]

[0558] [Chemistry 233]

[0559]

[0560] [Chemistry 234]

[0561]

[0562] [Chemistry 235]

[0563]

[0564] [Chemistry 236]

[0565]

[0566] The synthesis method of the aforementioned carboxyl-containing polymer is not particularly limited if satisfactory dispersion can be obtained, and it is preferable to use living radical polymerization using a free radical initiator and a reversible addition cleavage chain transfer agent (RAFT agent) for synthesis. That is, the present invention provides a method for manufacturing a resist composition, characterized by comprising the following steps: synthesizing the aforementioned carboxyl-containing polymer using living radical polymerization using a free radical initiator and a reversible addition cleavage chain transfer agent (RAFT agent) represented by formula (R-1) or (R-2), and mixing the obtained carboxyl-containing polymer, the aforementioned high-valent iodine compound, and the aforementioned solvent. Hereinafter, living radical polymerization using a RAFT agent will also be referred to as "RAFT polymerization".

[0567] Living polymerization is an effective polymerization method for synthesizing polymers with precisely controlled structures. It is known as a method for providing polymers with narrow dispersions, and living polymerization with different reaction mechanisms such as anionic, cationic, free radical, coordination, and ring-opening (metathesis) continues to be used to this day.

[0568] The carboxyl-containing polymer of the present invention is obtained by (co)polymerizing monomers containing repeating units of carboxyl-containing groups corresponding to the above formula (1) and monomers containing other repeating units as needed. In terms of the polymerization method for providing the carboxyl-containing polymer of the present invention with a dispersion Mw / Mn of 1.30 or less as measured by GPC, living radical polymerization is preferred, and RAFT polymerization is even more preferred.

[0569] RAFT polymerization itself is a well-known technique, as disclosed in Japanese Patent Application Publication Nos. 2007-520587, 2006-002096, and 2007-246588. However, known living radical polymerizations often suffer from insufficient performance of resist resins (see paragraph

[0007] of Japanese Patent Application Publication No. 2006-002096) because the RAFT reagent residues with unsaturated bonds in the structure have strong absorption bands in the ultraviolet region. Therefore, even though RAFT reagents are effective in controlling polymerization, it is known that there are often insufficient performance of resist resins (see paragraph

[0007] of Japanese Patent Application Publication No. 2006-002096). It is considered extremely difficult to obtain resist compositions with sensitivity and limit resolution exceeding those of the past in optical lithography using high-energy rays such as EUV. Despite this, surprisingly, in the present invention, if the resist composition contains high-valent iodine compounds, specific carboxyl-containing polymers and solvents, the above-mentioned problems do not occur, and a non-chemically amplified resist composition with excellent sensitivity and limiting resolution in EUV lithography and the like can be provided.

[0570] The following describes the RAFT aggregation method used in this invention.

[0571] [RAFT agent]

[0572] The aforementioned RAFT agent is preferably a reversible addition-crack chain transfer agent (RAFT agent) represented by the following formula (R-1) or (R-2).

[0573] [Chemistry 237]

[0574]

[0575] In the formula, R X1 and R X3 They are, independently, saturated hydrocarbon thiols with 3 to 20 carbon atoms, aralkyl thiols with 7 to 20 carbon atoms, heterocyclic groups with 5 to 20 carbon atoms, and -N(Z) groups. A (Z) B -COOZ A -OCOZ A -CON(Z) A (Z) B -P(=O)(OZ) A )2 or -OP(=O)(Z A (Z) B Z A and Z B Each is independently a saturated hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and Z A and Z B In this process, some or all of the hydrogen atoms bonded to the carbon atoms can be replaced by cyano groups, carboxyl groups, etc.

[0576] R X2 and R X4 Each can be independently a saturated hydrocarbon group with 2 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms, which may also contain heteroatoms.

[0577] The aforementioned RAFT agents are trithiocarbonate compounds and dithioester compounds, respectively. Specific examples of the aforementioned trithiocarbonate compounds include: 2-cyano-2-propyldodecyl trithiocarbonate, 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]pentaneic acid, cyanomethyldodecyl trithiocarbonate, and 2-(dodecylthiocarbonylthiothio)-2-methylpropionic acid, etc. Specific examples of the aforementioned dithioester compounds include: 1-ethoxycarbonyl-1-phenylmethylbenzodithioate, 2-phenyl-2-propylbenzodithioate, 4-cyano-4-(phenylthiocarbonylthio)pentaneic acid, and 2-cyano-2-propylbenzodithioate, etc.

[0578] Among the aforementioned RAFT agents, considering ease of acquisition, 2-cyano-2-propyldodecyl trithiocarbonate is preferred for trithiocarbonate compounds; and 1-ethoxycarbonyl-1-phenylmethylbenzodithioate is preferred for dithioester compounds.

[0579] The amount of the aforementioned RAFT agent used relative to 100 parts by mass of the total monomers should preferably be 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more. Furthermore, the upper limit of the aforementioned amount used relative to 100 parts by mass of the total monomers should preferably be 20 parts by mass or less, and more preferably 10 parts by mass or less. The aforementioned RAFT agent can be used alone or in combination of two or more.

[0580] In the aforementioned resist composition, the molar ratio of the aforementioned high-valent iodine compound to the aforementioned carboxyl-containing compound (when the aforementioned carboxyl-containing compound is a carboxyl-containing polymer, it is the molar ratio of the high-valent iodine compound to the repeating units containing carboxylic acids in the aforementioned polymer) is preferably high-valent iodine compound: carboxyl-containing compound = 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30. The aforementioned high-valent iodine compound can be used alone or in combination with two or more compounds having different compositional ratios, Mw, and / or Mw / Mn. The aforementioned carboxyl-containing polymer can be used alone or in combination with two or more compounds having different compositional ratios, Mw, and / or Mw / Mn.

[0581] In the aforementioned carboxyl-containing polymers, the molar ratio of carboxyl-containing repeating units to other repeating units should preferably be 10:90 to 90:10, more preferably 15:85 to 85:15, and even more preferably 20:80 to 80:20.

[0582] The weight-average molecular weight (Mw) of the aforementioned carboxyl-containing polymers is preferably between 1,000 and 500,000, and more preferably between 3,000 and 100,000. Furthermore, in this invention, Mw is a standard polystyrene conversion value determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0583] Living radical polymerization can be carried out by any of the following methods, if appropriate.

[0584] (1) A method in which all monomers, polymerization initiators and RAFT agents are added to the solvent at one time and dissolved in the reactor, and then the reactor is heated to start the reaction;

[0585] (2) A method for initiating a reaction by supplying a solution, in which the monomers, polymerization initiator, and RAFT agent have been dissolved in the solvent, to a preheated reactor containing a portion of the solvent; and

[0586] (3) A method of supplying a solution in which the monomers and polymerization initiator have been dissolved in the solvent to the reactor and starting the reaction in a reactor that has been fed with RAFT agent and a portion of solvent and preheated.

[0587] When using methods (2) and (3), the solutions of each monomer, initiator, and RAFT agent can be prepared as separate solutions and supplied to the reactor. It is possible that during standby time, free radicals generated from the initiator may cause the polymerization reaction to proceed and produce ultrapolymers. From a quality management perspective, at least the monomer solution and initiator solution should be prepared and added dropwise separately.

[0588] In the aforementioned living radical polymerization reaction, the reaction temperature is preferably 50–150℃, and more preferably 60–100℃. The reaction time is preferably 2–24 hours, and considering production efficiency, 2–12 hours is more preferable.

[0589] Following the aforementioned living radical polymerization steps, a purification step may be included, such as adding the reaction solution to a poor solvent and performing reprecipitation, depending on the requirements. The poor solvent used in this step can be appropriately selected according to the type of polymer. Representative examples include: hydrocarbons such as toluene, xylene, hexane, and heptane; ethers such as diethyl ether, tetrahydrofuran, and dibutyl ether; ketones such as acetone and 2-butanone; esters such as acetate ethers and butyl acetate; and water, but not limited to these. One of these solvents may be used alone, or two or more may be used in combination.

[0590] By adding a free radical generator and a thiol compound to the polymer-containing solution obtained after polymerization and then heating, the aforementioned terminal structures can be removed from the polymer backbone. Through this operation, the terminal structures of the polymer are replaced with hydrogen atoms. Furthermore, although undecomposed free radical generators from the free radical polymerization step may still be present, in order to efficiently replace the terminal structures with hydrogen atoms in a short time, it is advisable to simultaneously add the free radical generator when adding the thiol compound.

[0591] The free radical generator added after polymerization can be appropriately selected and used from the same examples exemplified during polymerization. The amount of free radical initiator used relative to 1 mole of the RAFT agent used during polymerization should preferably be 0.5 to 10 moles, and more preferably 0.5 to 2 moles.

[0592] In this invention, the thiol compound used after polymerization is preferably a compound represented by the following formula (SH-1) or (SH-2).

[0593] [Chemistry 238]

[0594]

[0595] In equation (SH-1), R SH1 It is an alkylene group with 1 to 3 carbon atoms. Specific examples of the aforementioned alkylene groups include: methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, etc.

[0596] In equation (SH-1), R SH2 It may also contain heteroatoms such as aliphatic hydrocarbon groups with 4 to 8 carbon atoms, aralkyl groups with 7 to 18 carbon atoms, or aryl groups with 6 to 18 carbon atoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms.

[0597] R SH2 The aliphatic hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, 3-pentyl, tert-pentyl, neopentyl, n-hexyl, 3-methylpentan-3-yl, 2,3-dimethylbutan-2-yl, n-heptyl, 2,3,4-trimethylpentan-3-yl, n-octyl, tetradecyl, hexadecyl, octadecyl, and other straight-chain or branched aliphatic hydrocarbon groups; cyclopentyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-vinylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-vinylcyclohexyl, norbornel, 1-methylnorbornel, cyclooctyl, cyclodecyl, cyclododecyl, 1-adamantyl, 2-adamantyl, 1-methyladamantyl, 1-ethyladamantyl, and other cyclic aliphatic hydrocarbon groups.

[0598] R SH2 Specific examples of aralkyl groups representing 7 to 18 carbon atoms include: benzyl, phenethyl, 4-methoxybenzyl, 9-anthraylmethyl, etc. SH2 Specific examples of aryl groups representing 6 to 18 carbon atoms include: phenyl, naphthyl, 4-methoxyphenyl, 2-anthrayl, 9-anthrayl, etc.

[0599] In equation (SH-2), R SH3 It may also contain a saturated hydrocarbon group with 6 to 20 carbon atoms, an aralkyl group with 7 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms.

[0600] R SH3 The saturated hydrocarbon group can be any of the following: straight-chain, branched, or cyclic. Specific examples include: n-hexyl, 3-methylpentyl, n-heptyl, n-octyl, 1-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 2,2,4,6,6-pentamethylheptane-4-yl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, 2,3,3,4,4,5-hexamethylhexane-2-yl, etc.

[0601] R SH3 Specific examples of aralkyl groups representing 7 to 18 carbon atoms include: benzyl, phenethyl, 4-methoxybenzyl, 9-anthraylmethyl, etc. SH3 Specific examples of aryl groups representing 6 to 18 carbon atoms include: phenyl, naphthyl, 4-methoxyphenyl, 2-anthrayl, 9-anthrayl, etc.

[0602] The compound represented by formula (SH-1) should preferably be one of the following.

[0603] [Chemistry 239]

[0604]

[0605] [Chemistry 240]

[0606]

[0607] The compound represented by formula (SH-2) should preferably be one of the following.

[0608] [Chemistry 241]

[0609]

[0610] The amount of thiol compound used after polymerization should preferably be 1–20 moles, more preferably 1–4 moles, relative to 1 mole of the RAFT agent used in the polymerization. The free radical initiator and thiol compound added after polymerization can be added separately to the polymer-containing solution, or they can be mixed and added simultaneously. From an operational efficiency perspective, it is preferable to add the mixture of initiator and thiol compound, dissolved in a solvent, to the polymer-containing solution. This is especially beneficial when the reaction solution has already undergone living radical polymerization in the solvent, followed by the addition of the mixed solution of initiator and thiol.

[0611] The reaction temperature after polymerization should preferably be 50–150℃, with 60–100℃ being more ideal. Furthermore, the reaction time after polymerization should preferably be 2–24 hours, but considering production efficiency, 2–5 hours is preferable.

[0612] Specific examples of organic solvents used in polymerization reactions 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-dimethylpentanone), 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%.

[0613] Polymers synthesized by living free radical polymerization have a narrow dispersion, resulting in lower roughness and more uniform solubility when used as photoresists. Consequently, the polymer swells less, making it effective in preventing pattern collapse of lines and spacing patterns or clogging between contact hole patterns.

[0614] 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.

[0615] [solvent]

[0616] The resist composition of the present invention contains a solvent. There are no particular limitations on the solvent being 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.

[0617] In the resist composition of the present invention, 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 the present invention, the 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.

[0618] [Other ingredients]

[0619] 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.

[0620] When the aforementioned resist composition contains the aforementioned surfactant, its content in the total solid components should preferably be 0.0001 to 2% by mass. The aforementioned surfactant may be used alone or in combination of two or more.

[0621] The aforementioned resist composition may also contain more free radical scavengers. By adding free radical scavengers, the photoresist reaction in optical lithography can be controlled, and the sensitivity can be adjusted.

[0622] 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.

[0623] When the aforementioned corrosion resist composition contains the aforementioned free radical scavenger, its content in the total solid components should preferably be 0.01 to 10% by mass. The aforementioned free radical scavenger can be used alone or in combination of two or more.

[0624] The aforementioned resist composition may also contain more crosslinking agents. By adding crosslinking agents, the crosslinking reaction in optical lithography can be promoted, the glass transfer points of the pattern can be improved, and patterns with excellent resolution at fine lines can be obtained.

[0625] 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 have 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.

[0626] When the aforementioned resist composition contains the aforementioned crosslinking agent, its content in the total solid components should preferably be 0.01 to 50% by mass. The aforementioned crosslinking agent can be used alone or in combination of two or more.

[0627] When the aforementioned resist composition contains the aforementioned crosslinking agent, it may also contain a photopolymerization initiator. The photopolymerization initiator can generate free radicals by irradiation with high-energy rays and promote the crosslinking of the aforementioned crosslinking agent.

[0628] 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-diphenylpropane... Oxime compounds such as trione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], acetone-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, 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.

[0629] 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 0.1% by mass or more, sufficient blending effect can be obtained.

[0630] As previously described, the aforementioned resist composition contains high-valent iodine compounds and carboxyl-containing compounds as main components. However, polymers containing acid-instable groups and photoacid generators, as found in conventional chemically amplified resist compositions, are not necessary. Nevertheless, the resist composition of the present invention, especially when exposed to EB or EUV, can still form positive patterns where the exposed portions are soluble in the developer, or negative patterns where the exposed portions are insoluble in the developer. The mechanism is not fully elucidated, but it is speculated, for example, as follows.

[0631] The ideal high-valent iodine compound in this invention is a tricoordinate high-valent iodine compound having aryl and carboxylic acid ligands. It is believed that by mixing such a tricoordinate iodine compound with a carboxyl-containing compound, the exchange of carboxylic acid ligands occurs in an equilibrium reaction. At this point, if the original carboxylic acid ligands can be removed by any method, a high-valent iodine compound with new ligands will be generated. For example, if 1-iodonaphthalene diacetate, which is a high-valent iodine compound, is mixed with a carboxyl-containing compound, and the resulting low-boiling acetic acid is removed, ligand exchange will be completed. Here, the carboxyl-containing compound becomes a polymer crosslinked with the high-valent iodine compound.

[0632] 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.

[0633] In the resist film obtained from the resist composition of the present invention, the high-valent iodine compound, as its main component, decomposes under light, thereby changing its polarity and forming a pattern using a development step. The mechanism is not fully elucidated, but it is speculated, for example, as follows.

[0634] The resist composition of this invention can be either positive or negative depending on the selection of its components. In the positive case, it contains a polymer bonded by hypervalent iodine compounds during film formation. This polymer decomposes under light, becoming a monovalent iodine compound, while the bonds between the carboxyl-containing compound and the hypervalent iodine compound break, resulting in a decrease in molecular weight. It is presumably the result of forming a positive pattern where the exposed areas are removed by organic solvents.

[0635] On the other hand, in the negative case, there is a polymer cross-linked with high-valent iodine compounds generated during film formation. This polymer decomposes 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 alkaline solution.

[0636] Based on the foregoing, it can be inferred that the resist composition of the present invention is a non-chemically amplified resist composition. Since the resist composition of the present invention does not necessarily contain acid-inhibiting polymers or photoacid generators as in known chemically amplified resist compositions, adverse effects caused by acid diffusion (e.g., image blurring) do not occur, and fine patterns can be resolved.

[0637] The resist composition of this invention is particularly effective in EUV lithography. This is due to iodine atoms, which have a high absorption capacity for EUV light. That is, it reduces shot noise and achieves higher resolution and lower LWR.

[0638] Regarding EUV resist compositions capable of forming fine patterns, there are 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 above, such metal resists suffer from many problems, including insufficient solvent solubility, poor storage stability, and defects caused by residues after etching due to the presence of metal elements. On the other hand, the resist composition of the present invention does not use metal elements, thus it is more advantageous than metal resists in terms of defects, and it also has no problems with solvent solubility. Furthermore, the resist composition of the present invention is applicable in both positive and negative modes, thus its applications are wide-ranging. For example, in the contact hole formation step, metal resists implemented with negative development require a reversal process after the pillar pattern is formed, but positive resists do not require such a step. Therefore, considering the viewpoint of ease of processing, the resist composition of the present invention can also be considered more useful than metal resists.

[0639] The thickness of the aforementioned resist film should preferably be 10–70 nm, with 20–50 nm being even better.

[0640] The aforementioned resist composition may also contain a photoacid generator. By including a photoacid generator in the resist composition of the present invention, positive patterns can be formed with high sensitivity compared to resist compositions without a photoacid generator. The mechanism is not fully elucidated, but it is speculated, for example, as follows.

[0641] In the resist composition of the present invention, by adding a photoacid generator, during the exposure step of the resist, the acid generated from the photoacid generator exchanges with the ligands of the hypervalent iodine compound and becomes a new ligand, thereby breaking the bond between the carboxyl-containing polymer and the hypervalent iodine compound. Therefore, it is presumed that in addition to the photo-induced IO bond cleavage, the polarity change or molecular weight reduction caused by the exchange of new ligands generated from the photoacid generator can be achieved by developing with organic solvents, thus enabling the formation of positive patterns with high sensitivity.

[0642] As can be inferred from the foregoing, the resist composition of the present invention is a non-chemically amplified resist composition containing a photoacid generator, and polymers containing acid-instable groups, as in known chemically amplified resist compositions, are not necessary. Therefore, the acid generated from the photoacid generator reacts with the ligands of the hypervalent iodine compound in the exposure zone, becoming a new ligand for the hypervalent iodine. That is, since it does not possess the amplification mechanism of reacting with acid-instable groups and regenerating acid as in chemically amplified resist compositions, the adverse effects caused by acid diffusion (e.g., image blurring) do not occur, and fine patterns can be resolved.

[0643] Specific examples of the aforementioned photoacid generators include the following onium salt compounds.

[0644] [Onium salt compounds]

[0645] The aforementioned onium salt compounds contain a sulfonium cation represented by formula (5-1) or a monazine cation represented by formula (5-2) as cations.

[0646] [Chemistry 242]

[0647]

[0648] In equations (5-1) and (5-2), R 61 ~R 65 Each is a hydrocarbon group with 1 to 30 carbon atoms, which may be independently composed of halogen atoms or may contain heteroatoms.

[0649] R 61 ~R 65 Specific examples of halogen atoms that can be represented include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0650] R 61 ~R 65The hydrocarbon group represented can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 30 carbon atoms such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 30 carbon atoms such as cyclohexenyl; aryl groups with 6 to 30 carbon atoms such as phenyl, naphthyl, and thiophene; aralkyl groups with 7 to 30 carbon atoms such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these, but preferably aryl. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- in the aforementioned hydrocarbon group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0651] Also, R 61 and R 62 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. Specific examples of the aforementioned ring structures can be shown in the following formulas, etc.

[0652] [Chemistry 243]

[0653]

[0654] In the formula, the dashed line represents R. 63 Atomic bonds.

[0655] Specific examples of sulfonium cations represented by formula (5-1) are listed below, but are not limited thereto.

[0656] [Chemistry 244]

[0657]

[0658] [Chemistry 245]

[0659]

[0660] [Chemistry 246]

[0661]

[0662] [Chemistry 247]

[0663]

[0664] [Chemistry 248]

[0665]

[0666] [Chemistry 249]

[0667]

[0668] [Chemistry 250]

[0669]

[0670] [Chemistry 251]

[0671]

[0672] [Chemistry 252]

[0673]

[0674] [Chemistry 253]

[0675]

[0676] [Chemistry 254]

[0677]

[0678] [Chemistry 255]

[0679]

[0680] [Chemistry 256]

[0681]

[0682] [Chemistry 257]

[0683]

[0684] [Chemistry 258]

[0685]

[0686] [Chemistry 259]

[0687]

[0688] [Chemistry 260]

[0689]

[0690] [Chemistry 261]

[0691]

[0692] [Chemistry 262]

[0693]

[0694] [Chemistry 263]

[0695]

[0696] [Chemistry 264]

[0697]

[0698] [Chemistry 265]

[0699]

[0700] [Chemistry 266]

[0701]

[0702] [Chemistry 267]

[0703]

[0704] [Chemistry 268]

[0705]

[0706] [Chemistry 269]

[0707]

[0708] [Chemistry 270]

[0709]

[0710] Specific examples of the molybdenum cation represented by formula (5-2) are listed below, but are not limited thereto.

[0711] [Chemistry 271]

[0712]

[0713] [Chemistry 272]

[0714]

[0715] The aforementioned onium salt compounds contain examples of halide ions, nitrate ions, hydrogen sulfate ions, bicarbonate ions, tetraphenylborate ions, or any of the following formulas (5-3) to (5-9) as anions.

[0716] [Chemistry 273]

[0717]

[0718] In equations (5-3) and (5-5), k1 and k2 are 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.

[0719] In equation (5-3), R 71 It consists of hydrogen atoms, halogen atoms, hydroxyl groups, or hydrocarbon groups with 1 to 50 carbon atoms that may also contain heteroatoms.

[0720] In equation (5-4), R 72 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 sulfonate group are replaced by fluorine atoms or fluoroalkyl groups.

[0721] In equation (5-5), R 81 It consists of hydrogen atoms, halogen atoms, hydroxyl groups, or hydrocarbon groups with 1 to 50 carbon atoms that may also contain heteroatoms.

[0722] In equation (5-6), R 82 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.

[0723] In equation (5-7), R 91 and R 92 Each can be an independent hydrocarbon group with 1 to 50 carbon atoms, which may also contain heteroatoms.

[0724] In equation (5-8), R 101 ~R 103 Each can be an independent hydrocarbon group with 1 to 50 carbon atoms, which may also contain heteroatoms.

[0725] In equation (5-9), R 111 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 112 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 111 and R 112 They can also bond to each other and form rings together with the atoms they are bonded to.

[0726] The anion of the aforementioned onium salt compound is preferably a halide ion, a nitrate ion, or an anion represented by any of formulas (5-3) to (5-9), and it is more preferable that it is a halide ion, a nitrate ion, or an anion represented by formulas (5-4), (5-6), or (5-8).

[0727] R 71 R 72 R 81 R 82 R 91 R 92 R 101 R 102 and R 103 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, norbornel, 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.]

[0728] R 111 The fluorinated hydrocarbon group representing 1 to 10 carbon atoms is a group formed by replacing some or all of the hydrogen atoms of a hydrocarbon group with 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. 71 R 72 R 81 R 82 R 91 R 92 R 101 R 102 and R 103Examples of hydrocarbon groups with 1 to 50 carbon atoms, where the carbon number is 1 to 10.

[0729] R 112 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. 71 R 72 R 81 R 82 R 91 R 92 R 101 R 102 and R 103 Examples of hydrocarbon groups with 1 to 50 carbon atoms, where the carbon number is 1 to 20.

[0730] The anion represented by any of formulas (5-3) to (5-9) may also contain polymerizable functional groups in its structure, and may also have hydrocarbon groups with 2 to 50 carbon atoms, which may contain heteroatoms. Specific examples are shown below, but are not limited thereto.

[0731] [Chemistry 274]

[0732]

[0733] [Chemistry 275]

[0734]

[0735] [Chemistry 276]

[0736]

[0737] [Chemistry 277]

[0738]

[0739] Specific examples of anions represented by equation (5-3) are shown below, but are not limited to these. Additionally, in the following equation, Ac represents an acetyl group, and Rf... 1 Same as above.

[0740] [Chemistry 278]

[0741]

[0742] [Chemistry 279]

[0743]

[0744] [Chemistry 280]

[0745]

[0746] [Chemistry 281]

[0747]

[0748] [Chemistry 282]

[0749]

[0750] [Chemistry 283]

[0751]

[0752] [Chemistry 284]

[0753]

[0754] [Chemistry 285]

[0755]

[0756] [Chemistry 286]

[0757]

[0758] [Chemistry 287]

[0759]

[0760] [Chemistry 288]

[0761]

[0762] [Chemistry 289]

[0763]

[0764] [Chemistry 290]

[0765]

[0766] Specific examples of anions represented by equation (5-4) are listed below, but are not limited to these.

[0767] [Chemistry 291]

[0768]

[0769] [Chemistry 292]

[0770]

[0771] [Chemistry 293]

[0772]

[0773] [Chemistry 294]

[0774]

[0775] [Chemistry 295]

[0776]

[0777] [Chemistry 296]

[0778]

[0779] Specific examples of anions represented by equation (5-5) are listed below, but are not limited to these.

[0780] [Chemistry 297]

[0781]

[0782] [Chemistry 298]

[0783]

[0784] Specific examples of anions represented by equations (5-6) are listed below, but are not limited to these.

[0785] [Chemistry 299]

[0786]

[0787] [Chemical 300]

[0788]

[0789] [Chemical Engineering 301]

[0790]

[0791] [Chemical 302]

[0792]

[0793] Specific examples of anions represented by equations (5-7) are listed below, but are not limited to these.

[0794] [Chemical 303]

[0795]

[0796] [Chemical 304]

[0797]

[0798] Specific examples of anions represented by equations (5-8) are listed below, but are not limited to these.

[0799] [Chemical 305]

[0800]

[0801] [Chemical 306]

[0802]

[0803] [Chemical 307]

[0804]

[0805] Specific examples of anions represented by equations (5-9) are listed below, but are not limited to these.

[0806] [Chemical 308]

[0807]

[0808] [Chemical 309]

[0809]

[0810] Specific examples of onium salts can be listed by any combination of the aforementioned anions and cations.

[0811] Onion salts can be used alone or in combination of two or more. When using two or more onion salts in combination, it is advisable to use photoacid generators with different acidity levels. The diffusion of acid generated in the exposed part of the resist to the unexposed part will be quenched by the photoacid generator with lower acidity, thus inhibiting diffusion and forming a high-resolution pattern.

[0812] In the resist composition of the present invention, the molar ratio of high-valent iodine compound to photoacid generator is preferably 1:1000 to 1000:1, and more preferably 1:500 to 500:1.

[0813] When the aforementioned onium salts introduce substituents with large molecular weights and large volumes, they are ideal for the formation of fine patterns because they eliminate large volumes and greatly suppress the diffusion of the generated acids.

[0814] When the aforementioned onium salt contains elements with high EUV light absorption such as fluorine atoms and iodine atoms, the amount of secondary electrons generated will increase, and the decomposition of cations will be promoted, making it ideal for the formation of high-sensitivity micro-patterns.

[0815] [Layered Body]

[0816] This invention provides a laminate characterized by comprising: a substrate, and a resist film formed from the aforementioned resist composition on the substrate. In such a laminate comprising a resist film derived from the non-chemically amplified resist composition of this invention, the resist film formed from the aforementioned resist composition exhibits extremely high sensitivity and excellent limiting resolution, making it highly effective for precision micro-machining. Furthermore, it is applicable to the formation of any pattern, whether positive or negative, thus having a wide range of uses and high usefulness in resist manufacturing technology.

[0817] At this time, a lower resist film may also be provided between the aforementioned substrate and the aforementioned resist film as needed.

[0818] Furthermore, in the laminate of the present invention, the resist film preferably contains the ligand exchange reaction product of the aforementioned high-valent iodine compound and a carboxyl-containing compound. That is, the laminate can be obtained by forming a resist film derived from the resist composition of the present invention on a substrate, and the aforementioned resist film preferably is formed by ligand exchange between the aforementioned high-valent iodine compound and a carboxyl-containing compound.

[0819] As described above, by removing the byproduct low-molecular-weight carboxylic acids during film formation and subsequent baking steps, the hypervalent iodine compound undergoes a ligand exchange reaction with the carboxyl-containing compound, forming a resist film containing the ligand exchange reaction products (i.e., providing the film-forming body). By completing the ligand exchange, the carboxyl-containing compound becomes a polymer cross-linked with the hypervalent iodine compound. It is preferable to complete the ligand exchange reaction simultaneously with the formation of the resist film in this way.

[0820] [Pattern Formation Method]

[0821] When the resist composition of the present invention is used in the manufacture of various integrated circuits, known photolithography techniques can be employed. For example, a patterning method may include the following steps:

[0822] A resist film is formed on a substrate or on a substrate having a resist underlayer layer laminated with the aforementioned resist composition.

[0823] The aforementioned resist film was exposed to high-energy rays, and

[0824] The previously exposed resist film was developed using a developer. Hereinafter, the underlying resist film will also be referred to as the "underlying film".

[0825] First, the resist composition of the present invention is coated onto a substrate for integrated circuit manufacturing, or onto the lower layer film of a substrate with a stacked lower layer film (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective film, etc.), or onto a substrate for mask circuit manufacturing, or onto the lower layer film of a substrate with a stacked lower layer film (Cr, CrO, CrON, MoSi2, SiO2, etc.), using a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or blade coating, with a coating film thickness of 0.01 to 2 μm. The substrate is then pre-baked on a hot plate, preferably at 60 to 200°C for 10 seconds to 30 minutes, and more preferably at 80 to 180°C for 30 seconds to 20 minutes, 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.

[0826] Then, the aforementioned photoresist film is exposed using 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 radiation, 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 for high-energy radiation. 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 used to form the desired pattern. 2 And preferably, it should be approximately 10–200 mJ / cm³. 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 to 5000 μC / cm. 2 The resist composition of the present invention is particularly suitable for fine patterning under high-energy radiation, such as EB or EUV.

[0827] 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°C for 10 to 30 seconds, or more preferably at 60–120°C for 30 to 20 seconds.

[0828] After exposure or PEB, develop the surface and pattern it using a developer. The developing solutions used at this time can include: alkaline aqueous solutions such as tetramethylammonium hydroxide aqueous solution and tetrabutylammonium hydroxide aqueous solution; 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, 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, propionic acid Organic solvents including ethyl acetate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl 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-trimethylhexanol, 2,6-dimethyl-4-heptanol, toluene, anisole, ε-caprolactone, etc. These developers can be used alone or in combination of two or more.

[0829] 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.

[0830] 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.

[0831] The resist composition of the present invention, as described above, utilizes the difference in solubility between exposed and unexposed areas during exposure to form positive or negative patterns. Therefore, a developer can be used that dissolves the exposed areas but not the unexposed areas, and vice versa. Thus, the 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.

[0832] Example

[0833] 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.

[0834] [1] Synthesis of carboxyl-containing polymers

[0835] The monomers used in the synthesis of carboxyl-containing polymers are described below.

[0836] [Chemical 310]

[0837]

[0838] [Chemistry 311]

[0839]

[0840] [Chemistry 312]

[0841]

[0842] [Synthesis Example 1-1] Preparation of Polymer P-1

[0843] Under nitrogen atmosphere, monomers a-1 (56g) and b-1 (36g) were dissolved in 100g of MEK, and degassing and nitrogen substitution were performed three times in a 20-minute cycle to obtain solution A. Separately, 2.90g of dimethyl 2,2'-azobisisobutyrate (I-1) was dissolved in 10.0g of MEK, and degassing and nitrogen substitution were performed three times in a 20-minute cycle to obtain solution B. Then, 8.79g of 2-cyano-2-propylbenzodithioate was dissolved in 20.0g of MEK, and degassing and nitrogen substitution were performed three times in a 20-minute cycle to obtain solution C. The reactor containing solution C was then heated to 80°C. Solutions A and B were added dropwise separately using a syringe pump over 2 hours. After the addition was complete, the polymerization solution was maintained at 80°C and stirred for 6 hours, then cooled to room temperature (this is referred to as step RM-1).

[0844] Then, 8.60 g of dimethyl 2,2'-azobisisobutyrate and 15.0 g of thioglycolic acid were dissolved in 33.3 g of MEK, and the mixture was subjected to degassing and nitrogen substitution under reduced pressure for 20 minutes three times in repeated cycles to obtain solution D. Solution D was then added dropwise to the reaction solution of step RM-1 using a syringe pump over 5 minutes. After the addition was complete, the reactor was reheated to 80°C, maintained at 80°C, and stirred for 2 hours, before cooling to room temperature.

[0845] The resulting polymer solution was then added dropwise to 4000g of hexane under vigorous stirring, and the precipitated polymer was separated by filtration. The obtained polymer was washed twice with 1200g of hexane and then dried under vacuum 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 1.11. Furthermore, Mw is the standard polystyrene conversion value determined by GPC using THF as a solvent. Details are as follows (the same applies below).

[0846] • Device: HLC-8320GPC

[0847] ■ Column: TSK guardcolumn

[0848] +TSKgel G4000HXL

[0849] +TSKgel G2000HXL

[0850] +TSKgel superH5000

[0851] ■ Pump and tubing constant temperature: 40℃

[0852] ■ Extraction solution: THF

[0853] ■ Detector: RI (Differential Refraction) Detector

[0854] ■Injection volume: 100μl

[0855] [Synthetic Examples 1-2 to 1-12] Synthesis of Polymers P-2 to P-12

[0856] 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 1-1.

[0857] [Synthetic Examples 1-13] Synthesis of Polymer P-13

[0858] 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 filtered and separated. 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-13 (yield 90g, 98% yield). The Mw of polymer P-13 was 8000, and the Mw / Mn ratio was 1.42. Additionally, Mw is the polystyrene conversion value determined by GPC using THF as a solvent.

[0859] [Synthetic Examples 1-14, 1-15] Synthesis of polymers P-14 and P-15

[0860] 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 Examples 1-13.

[0861] [Table 1]

[0862]

[0863] As shown in Table 1, using living radical polymerization with RAFT agent, narrowly dispersed polymers with small dispersion (Mw / Mn) can be obtained.

[0864] [2] Preparation of the resist composition

[0865] [Examples 2-1 to 2-20, Comparative Examples 2-1 to 2-4]

[0866] 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) according to the compositions shown in Table 2 below. The resulting solution was filtered through a 0.2 μm Teflon (registered trademark) filter to obtain photoresist compositions (R-01 to R-20, CR-01 to CR-02). Furthermore, polymers, photoacid generators, and sensitivity modifiers were dissolved in a solvent containing 0.01% by mass of a surfactant (PF-636, manufactured by OMNOVA) according to the compositions shown in Table 3 below. The resulting solution was filtered through a 0.2 μm Teflon (registered trademark) filter to obtain photoresist compositions (CR-03 to CR-04).

[0867] [Table 2]

[0868]

[0869]

[0870] [Table 3]

[0871]

[0872] In Tables 2 and 3, the high-valent iodine compounds I-1 to I-9, the photoacid generator PAG-1, the sensitivity modifier Q-1, and the solvent are as follows.

[0873] [Chemistry 313]

[0874]

[0875] [Chemical 314]

[0876]

[0877] [Chemical 315]

[0878]

[0879] ■ Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[0880] AcOH (acetic acid)

[0881] GBL (γ-butyrolactone)

[0882] [3] Evaluation of EUV lithography (line and spacing patterns)

[0883] [Examples 3-1 to 3-20, Comparative Examples 3-1 to 3-4]

[0884] Each resist composition (R-01 to R-20, CR-01 to CR-04) was spin-coated onto a Si substrate with a silicon-containing spin-coated hard mask SHB-A940 (43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., having a film 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.

[0885] The obtained resist pattern was evaluated as follows. The results are shown in Table 4.

[0886] [Sensitivity Evaluation]

[0887] The aforementioned LS pattern was observed using a Hitachi Advanced Technology Co., Ltd. (GAD) CG-6300 measuring SEM, 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.

[0888] [LWR Evaluation]

[0889] The dimensions of 10 points on an LS pattern obtained by exposure to the optimal amount of light along the length direction of the pitch width were measured using a 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 more uniform and less rough the pitch width pattern can be obtained.

[0890] [Ultimate Resolution Evaluation]

[0891] Using a Hitachi Advanced Technologies (AGT) CG-6300 long-range SEM, the limiting linewidth (nm) obtained by gradually increasing the exposure amount to form the aforementioned LS pattern from the optimal exposure amount was determined, and this value was designated as the limiting resolution (nm). The smaller this value, the better the limiting resolution, and the finer the pattern can be formed.

[0892] [Table 4]

[0893]

[0894]

[0895] Developer: nBA (Butyl acetate)

[0896] TMAH (2.38% by mass tetramethylammonium hydroxide aqueous solution)

[0897] As shown in Table 4, depending on the developer used, both positive and negative patterns can be formed. Furthermore, comparing the resist compositions of Comparative Examples 3-1 and 3-2 with the resist composition of the present invention, Examples 3-1 to 3-20 exhibit excellent sensitivity, resolution, and LWR. Comparing them with Comparative Examples 3-3 and 3-4, which are chemically amplified resist compositions using an acid catalyst reaction, the present invention also exhibits excellent sensitivity, resolution, and LWR. Therefore, it can be concluded that the resist composition of the present invention provides excellent sensitivity, resolution, and LWR during LS pattern formation under EUV exposure.

[0898] [4] Evaluation of EUV lithography (contact hole pattern)

[0899] [Examples 4-1 to 4-20, Comparative Examples 4-1 to 4-4]

[0900] Each resist composition (R-01 to R-20, CR-01 to CR-04) was spin-coated onto a Si substrate with a silicon-containing spin-coated hard mask SHB-A940 (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 5 using a heated plate to obtain a resist film with a thickness of 50 nm. The resist film was then exposed using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, 64 nm pitch, +20% offset aperture pattern mask on wafer). A PEB process was performed for 60 seconds at the temperatures listed in Table 5 using a heated plate, followed by 30 seconds of development using the developer listed in Table 5 to obtain an aperture pattern with a size of 32 nm.

[0901] The obtained resist patterns were evaluated as follows. The results are shown in Table 5.

[0902] [Sensitivity Evaluation]

[0903] The aforementioned contact hole pattern was observed using a Hitachi Advanced Technology Co., Ltd. (HIT) CG-6300 SEM, and the optimal exposure value Eop (mJ / cm²) for obtaining a hole pattern with a size of 22nm was determined. 2 And make it a sensitivity.

[0904] [CDU Evaluation]

[0905] The dimensions of 50 hole patterns obtained by irradiation with the optimal exposure were measured, and the standard deviation (σ) of the results was defined as three times the value of 3σ (CDU). The smaller this value, the more uniform the hole diameter of the pattern can be obtained.

[0906] [Ultimate Resolution Evaluation]

[0907] Using a Hitachi Advanced Technologies (AGT) CG-6300 long-range SEM, the limiting aperture diameter (nm) was determined by progressively decreasing the exposure amount to form the aforementioned aperture pattern from the optimal exposure amount. This value is then defined as the limiting resolution (nm). The smaller this value, the better the limiting resolution, and the more finer the aperture pattern can be formed.

[0908] [Table 5]

[0909]

[0910]

[0911] As shown in Table 5, depending on the developer used, both positive and negative patterns can be formed. Furthermore, comparing the resist compositions of Comparative Examples 4-1 and 4-2 with the resist composition of the present invention, Examples 4-1 to 4-20 exhibit excellent sensitivity, resolution, and CDU. Comparing them with Comparative Examples 4-3 and 4-4, which are chemically amplified resist compositions using an acid catalyst reaction, the present invention also exhibits excellent sensitivity, resolution, and CDU. Therefore, it can be concluded that the resist composition of the present invention exhibits excellent sensitivity, resolution, and CDU when forming CH patterns under EUV exposure.

[0912] This specification contains the following specifications.

[0913] [1]: A corrosion resist composition comprising: a high-valent iodine compound, a carboxyl-containing polymer, and a solvent;

[0914] The aforementioned resist composition is characterized in that the aforementioned carboxyl-containing polymer is a polymer containing repeating units of carboxylic acid derivatives represented by the following formula (1), and the dispersion Mw / Mn obtained by gel permeation chromatography of the polymer is less than 1.30.

[0915] [Chemistry 316]

[0916]

[0917] In the formula, 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, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the polymer backbone.

[0918] [2]: The resist composition of [1], wherein the aforementioned high-valent iodine compound is selected from at least one of the group consisting of high-valent iodine compounds represented by the following formulas (2) to (11).

[0919] [Chemistry 317]

[0920]

[0921] 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, n8 is 1, 2, 3, or 4, and 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, and 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, and 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, and 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 0, 1, 2, 3, 4, 5, or 6; n15 and n16 are 0, 1, 2, or 3; and 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; and 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, and 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. R 1 ~R 22 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 1 and R 2 R 3 and R 4 R 5 and R 6 R 7 and R 8 R 9 and R 10R 11 and R 12 R 13 and R 14 R 15 and R 16 R 17 and R 18 、or R 19 and R 20 They can also bond to each other and form a ring together with the carbonyl oxygen groups they are bonded to and the atoms between the carbonyl oxygen groups, R 21 and R 22 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 31 ~R 34 R 37 R 39 ~R 46 R 49 R 50 Each R is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms. When n2 is 2 or more, each R 31 They can be the same or different, and there are multiple Rs. 31 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 32 They can be the same or different, and there are multiple Rs. 32 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 33 They can be the same or different, and there are multiple Rs. 33 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 34 They can be the same or different, and there are multiple Rs. 34 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 37 They can be the same or different, and there are multiple Rs. 37 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 39 They can be the same or different, and there are multiple Rs. 39 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 40 They can be the same or different, and there are multiple Rs. 40 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 41 They can be the same or different, and there are multiple Rs. 41They 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 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 n14 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 n15 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 n16 is 2 or more, each R 45 They can be the same or different, and there are multiple Rs. 45 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 46 They can be the same or different, and there are multiple Rs. 46 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 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 n19 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. R 35 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 35 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thioketone bond. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 34 and R 35 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 36 A hydrocarbon group consisting of 1 to 10 carbon atoms, which may also contain heteroatoms. R 38 It is a carbonyl group, or a hydrocarbon group with 1 to 10 carbon atoms that may also contain heteroatoms. *1 and *2 represent atomic bonds of the carbon atoms in the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms on the aromatic ring. L1 is unbonded, a single bond, -O-, -S-, -NH-, or -CH2-, R 47It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms. X is nitrogen or sulfur, and when it is nitrogen, it may also have R. 48 R 48 It consists of a hydrocarbon group with 1 to 20 carbon atoms, which may be hydrogen atoms, halogen atoms, or heteroatoms.

[0922] [3]: A laminate characterized by having: a substrate, and a resist film of a resist composition such as [1] or [2] located on the substrate.

[0923] [4]: As in [3], a laminated body, wherein a lower resist film is provided between the aforementioned substrate and the aforementioned resist film.

[0924] [5]: such as [3] or [4], wherein the aforementioned resist film contains the ligand exchange reaction product of the aforementioned high-valent iodine compound and the carboxyl-containing polymer.

[0925] [6]: A pattern forming method, characterized by comprising the following steps:

[0926] A resist film is formed on a substrate or on a substrate having a resist underlayer film stacked thereon using a resist composition such as [1] or [2].

[0927] The aforementioned resist film was exposed using high-energy rays, and

[0928] The previously exposed resist film was developed using a developer.

[0929] [7]: The pattern forming method as in [6], wherein i-rays, KrF excimer lasers, ArF excimer lasers, electron beams or extreme ultraviolet rays are used as the aforementioned high-energy rays.

[0930] [8]: A method for manufacturing a resist composition, which is a method for manufacturing a resist composition such as [1] or [2], characterized by comprising the following steps:

[0931] The aforementioned carboxyl-containing polymer was synthesized by living radical polymerization using a free radical initiator and a reversible addition cleavage chain transfer agent (RAFT agent) represented by formula (R-1) or (R-2), and the resulting carboxyl-containing polymer, the aforementioned high-valent iodine compound, and the aforementioned solvent were mixed.

[0932] [Chemistry 318]

[0933]

[0934] In the formula, R X1 and R X3They are, independently, saturated hydrocarbon thiols with 3 to 20 carbon atoms, aralkyl thiols with 7 to 20 carbon atoms, heterocyclic groups with 5 to 20 carbon atoms, and -N(Z) groups. A (Z) B -COOZ A -OCOZ A -CON(Z) A (Z) B -P(=O)(OZ) A )2 or -OP(=O)(Z A (Z) B Z A and Z B Each is independently a saturated hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and Z A and Z B In this process, some or all of the hydrogen atoms bonded to its carbon atoms can be replaced by cyano groups, carboxyl groups, etc. R X2 and R X4 Each can be independently a saturated hydrocarbon group with 2 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms, which may also contain heteroatoms.

[0935] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative examples, and those having substantially the same structure and performing the same effects as the technical concept described in the claims of the present invention are intended to be included within the technical scope of the present invention.

Claims

1. A resist composition comprising: a high-valent iodine compound, a carboxyl-containing polymer, and a solvent; The resist composition is characterized in that the carboxyl-containing polymer is a polymer containing repeating units of carboxylic acid derivatives represented by the following formula (1), and the dispersion Mw / Mn obtained by gel permeation chromatography of the polymer is less than 1.

30. In the formula, R A It is 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 hydroxyl groups, ether bonds, ester bonds, or lactone rings; * indicates an atomic bond with carbon atoms in the polymer backbone.

2. The resist composition according to claim 1, wherein, The high-valent iodine compound is selected from at least one of the group consisting of high-valent iodine compounds represented by the following formulas (2) to (11); 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, and n6 is 0, 1, 2, 3, or 4. And 1≤n5+n6≤5; n7 is 0, 1, 2, 3 or 4, 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 The value of 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, and 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 0, 1, 2, 3, 4, 5 or 6; n15 and n16 are 0, 1, 2 or 3, where 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, and m6 is 2. When 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, m8 is 0, 1, or 2; when m8 is 0, n19 is 0, 1, 2, or 3, n20 is 0 or 1; when m8 is 1, n19 is 0, 1, 2, 3, 4, or 5, n20 is 0 or 1; when m8 is 2, n19 is 0, 1, 2, 3, 4, 5, 6, or 7, n20 is 0 or 1, R 1 ~R 22 Each of the following groups is a hydrocarbon group consisting of 1 to 10 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms; furthermore, R 1 and R 2 R 3 and R 4 R 5 and R 6 R 7 and R 8 R 9 and R 10 R 11 and R 12 R 13 and R 14 R 15 and R 16 R 17 and R 18 、or R 19 and R 20 They can also bond to each other and form a ring together with the carbonyl oxygen groups they are bonded to and the atoms between the carbonyl oxygen groups, R 21 and R 22 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 31 ~R 34 R 37 R 39 ~R 46 R 49 R 50 Each R is an independent hydrocarbon group with 1 to 40 carbon atoms, or may contain heteroatoms; when n2 is 2 or more, each R 31 They can be the same or different, and there are multiple Rs. 31 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 32 They can be the same or different, and there are multiple Rs. 32 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 33 They can be the same or different, and there are multiple Rs. 33 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 34 They can be the same or different, and there are multiple Rs. 34 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 37 They can be the same or different, and there are multiple Rs. 37 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 39 They can be the same or different, and there are multiple Rs. 39 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 40 They can be the same or different, and there are multiple Rs. 40 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 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 n13 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 n14 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 n15 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 n16 is 2 or more, each R 45 They can be the same or different, and there are multiple Rs. 45 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 46 They can be the same or different, and there are multiple Rs. 46 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 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 n19 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; R 35 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 35 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thioketone bond; furthermore, part or all of the hydrogen atoms of the (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 34 and R 35 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 36 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms; R 38 It is a carbonyl group, or a hydrocarbon group with 1 to 10 carbon atoms that may also contain heteroatoms; *1 and *2 represent atomic bonds of the carbon atoms in the aromatic ring in the formula; however, *1 and *2 are bonded to adjacent carbon atoms on the aromatic ring; L1 is unbonded, a single bond, -O-, -S-, -NH-, or -CH2-, R 47 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms; X is nitrogen or sulfur, and when it is nitrogen, it may also have R. 48 ;R 48 It consists of a hydrocarbon group with 1 to 20 carbon atoms, which may be hydrogen atoms, halogen atoms, or heteroatoms.

3. A laminate, characterized in that it comprises: a substrate, and a resist film of a resist composition according to claim 1 or 2 located on the substrate.

4. The laminated body according to claim 3, wherein, A lower resist film is provided between the substrate and the resist film.

5. The laminated body according to claim 3, wherein, The resist film contains the ligand exchange reaction product of the high-valent iodine compound and the carboxyl-containing polymer.

6. A method for forming a pattern, characterized by comprising the following steps: A resist film is formed on a substrate or on a substrate having a resist underlayer film laminated with the resist composition according to claim 1 or 2. The resist film was exposed using high-energy rays, and The exposed resist film was developed using a developer.

7. The pattern forming method according to claim 6, wherein, The high-energy ray can be i-ray, KrF excimer laser, ArF excimer laser, electron beam or extreme ultraviolet light.

8. A method for manufacturing a resist composition, comprising the steps described in claim 1: The carboxyl-containing polymer was synthesized by living radical polymerization using a free radical initiator and a reversible addition cleavage chain transfer agent (RAFT agent) represented by formula (R-1) or (R-2), and the resulting carboxyl-containing polymer, the high-valent iodine compound, and the solvent were mixed. In the formula, R X1 and R X3 They are, independently, saturated hydrocarbon thiols with 3 to 20 carbon atoms, aralkyl thiols with 7 to 20 carbon atoms, heterocyclic groups with 5 to 20 carbon atoms, and -N(Z) groups. A (Z) B -COOZ A -OCOZ A -CON(Z) A (Z) B -P(=O)(OZ) A )2 or -OP(=O)(Z A (Z) B );Z A and Z B Each is independently a saturated hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and Z A and Z B In this process, some or all of the hydrogen atoms bonded to the carbon atom can be replaced by cyano, carboxyl, or other groups; R X2 and R X4 Each can be independently a saturated hydrocarbon group with 2 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms, which may also contain heteroatoms.

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