Resist composition, laminate, pattern forming method, and method for manufacturing a resist composition

Abstract

This invention provides a non-chemically amplified resist composition that exhibits excellent sensitivity and critical resolution in photolithography using high-energy rays, as well as a laminate and pattern formation method using the resist composition, and a method for manufacturing the resist composition. [Solution] A resist composition comprising a hypervalent iodine compound, a carboxyl group-containing polymer, and a solvent, wherein the carboxyl group-containing polymer is a polymer comprising repeating units of a carboxylic acid derivative represented by the following formula (1), and the degree of dispersion Mw / Mn, determined from the weight-average molecular weight Mw and number-average molecular weight Mn measured by gel permeation chromatography of the polymer, is 1.30 or less. [Formula 1] TIFF2026076726000327.tif36166

Description

[Technical Field]

[0001] The present invention relates to a resist composition, a laminate, a pattern formation method using the resist composition, and a method for manufacturing the resist composition. [Background technology]

[0002] With the expansion of the IoT market, there is an increasing demand for higher integration, higher speed, and lower power consumption in LSIs, leading to rapid miniaturization of pattern rules. Logic devices, in particular, are driving this miniaturization. As cutting-edge miniaturization technology, mass production of 10nm node devices is underway using double, triple, and quadruple patterning in ArF immersion lithography, and further research is progressing on 7nm node devices using next-generation 13.5nm extreme ultraviolet (EUV) lithography.

[0003] As miniaturization progresses, image blurring due to acid diffusion has become a problem (Non-Patent Literature 1). To ensure resolution in fine patterns with processing dimensions of 45 nm or more, it has been suggested that controlling acid diffusion is important, in addition to improving the dissolution contrast as has been conventionally proposed (Non-Patent Literature 2). However, since chemically amplified resist compositions increase sensitivity and contrast through acid diffusion, if acid diffusion is suppressed to the extreme by lowering the post-exposure bake (PEB) temperature or shortening the PEB time, sensitivity and contrast decrease significantly.

[0004] Adding an acid generator that produces bulky acids to suppress acid diffusion is effective. Therefore, copolymerizing an onium salt acid generator with a polymerizable olefin into a polymer has been proposed. However, for pattern formation of resist films with processing dimensions of 16 nm or more, chemically amplified resist compositions are considered insufficient from the standpoint of acid diffusion, and the development of non-chemically amplified resist compositions is desired.

[0005] Polymethyl methacrylate (PMMA) is an example of a material for non-chemically amplified resist compositions. PMMA is a positive-type resist material in which the main chain is cleaved by EUV irradiation, reducing its molecular weight and improving its solubility in organic solvents and developers.

[0006] Hydrogen silsesquioxane (HSQ) is a negative-type resist material that becomes insoluble in alkaline developers due to crosslinking caused by the condensation reaction of silanols induced by EUV irradiation. Chlorine-substituted calixarenes also function as negative-type resist materials. These negative-type resist materials have small molecular sizes before crosslinking and do not blur due to acid diffusion, resulting in low edge roughness and very high resolution. They are used as pattern transfer materials to demonstrate the resolution limit of exposure equipment. However, these materials have insufficient sensitivity and require further improvement.

[0007] One factor that makes material development for EUV lithography difficult is the low number of photons in EUV exposure. The energy of EUV is far higher than that of ArF excimer laser light, and the number of photons in EUV exposure is 1 / 14th of that of ArF exposure. Furthermore, the dimensions of patterns formed by EUV exposure are less than half those of ArF exposure. For this reason, EUV exposure is susceptible to variations in the number of photons. Variations in the number of photons in the ultrashort wavelength synchrotron radiation region are a physical phenomenon called shot noise, and this effect cannot be eliminated. For this reason, so-called stochastics is attracting attention. Although the effect of shot noise cannot be eliminated, how to reduce this effect is being discussed. In addition to increasing dimensional uniformity (CDU) and line width roughness (LWR) due to the effect of shot noise, a phenomenon of hole blockage has been observed with a probability of one in several million. When holes are blocked, it results in poor electrical conductivity and the transistor does not operate, so it negatively affects the overall performance of the device. When considering practical sensitivity, resist compositions primarily composed of PMMA or HSQ are significantly affected by stochastics and have not been able to achieve the desired resolution performance.

[0008] As a method to reduce the effects of shot noise on the resist side, the introduction of elements that strongly absorb EUV light has attracted attention. Patent Document 1 proposes a chemically amplified resist composition containing iodine atoms that strongly absorb EUV light. However, as mentioned above, chemically amplified resist compositions cannot achieve excellent resolution performance in EUV lithography, where processing dimensions will become increasingly miniaturized in the future. In particular, in line-and-space patterns, as the pattern dimensions become smaller, pattern distortion and breaks increase significantly, so reducing these will lead to an improvement in critical resolution.

[0009] Patent Document 2 proposes a negative-type resist composition using a tin compound. Because it mainly consists of tin, which has high absorption of EUV light, it improves stochastics and enables high sensitivity and high resolution. However, so-called metal resists of this type have many problems, such as insufficient solubility in resist solvents, storage stability, and defects due to etching residue. Furthermore, since metal resists are negative-type resists that are insoluble in developer solutions mainly because the exposed areas become metal oxides, an inversion process is required when applied to patterning contact holes, which raises concerns in terms of cost. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Publication No. 2018-5224 [Patent Document 2] Special Publication No. 2021-503482 [Non-patent literature]

[0011] [Non-Patent Document 1] SPIE Vol. 5039 p1 (2003) [Non-Patent Document 2] SPIE Vol. 6520 p65203L-1 (2007) [Overview of the project] [Problems that the invention aims to solve]

[0012] The present invention has been made in view of the above circumstances, and aims to provide a non-chemically amplified resist composition that is excellent in sensitivity and limiting resolution in photolithography using high-energy beams, particularly electron beam (EB) lithography and EUV lithography, as well as a laminate and pattern formation method using the resist composition. [Means for solving the problem]

[0013] To solve the above problems, the present invention provides a resist composition comprising a hypervalent iodine compound, a carboxyl group-containing polymer, and a solvent, The present invention provides a resist composition characterized in that the carboxyl group-containing polymer is a polymer containing repeating units of a carboxylic acid derivative represented by the following formula (1), and the degree of dispersion Mw / Mn, determined from the weight-average molecular weight Mw and number-average molecular weight Mn measured by gel permeation chromatography of the polymer, is 1.30 or less. [ka] (In the formula, R A X is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. A This refers to a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 - is X A1 This is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. (* represents a bond with a carbon atom of the polymer backbone.)

[0014] The resist composition of the present invention provides a non-chemically amplified resist composition with excellent sensitivity and critical resolution in photolithography using high-energy beams, particularly electron beam (EB) lithography and EUV lithography. In particular, by using a resist composition containing a polymer with a narrow dispersion (molecular weight distribution), roughness is reduced, solubility is uniform, polymer swelling is minimal, and phenomena such as pattern collapse in line-and-space patterns and blockage between contact hole patterns, which lead to a decrease in resolution, can be prevented.

[0015] In this case, it is preferable that the hypervalent iodine compound is at least one selected from the group consisting of hypervalent iodine compounds represented by the following formulas (2) to (11). [ka] (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, and when m3 is 1 When n10 is 0, 1, 2, 3, 4, 5, or 6, and 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, and 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, and when m5 is 1, n12 is 0, 1, 2, 3, 4, 5, or 6, and n13, n14 are 0, 1, 2, 3, 4, 5, or 6, and n15, n16 are 0 n17 is 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; 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 is each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a hetero atom. 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 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 may be bonded to each other to form a ring together with the carbonyl oxy group to which they are bonded and the atoms between the carbonyl oxy groups. R 21 and R 22 may be bonded to each other to form a ring together with the carbon atom to which they are bonded and the atoms between the carbon atoms. R 31 ~R 34 、R 37 、R 39 ~R 46 、R 49 、R 50 is each independently a halogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a hetero atom. When n2 is 2 or more, each R<0000​​​​​​However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 33 These may be the same or different from each other, and there may be multiple R 33 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 34 These may be the same or different from each other, and there may be multiple R 34 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n9 is 2 or more, each R 37 These may be the same or different from each other, and there may be multiple R 37 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n10 is 2 or more, each R 39 These may be the same or different from each other, and there may be multiple R 39 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n11 is 2 or more, each R 40 These may be the same or different from each other, and there may be multiple R 40 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n12 is 2 or more, each R 41 These may be the same or different from each other, and there may be multiple R 41 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n13 is 2 or more, each R 42 These may be the same or different from each other, and there may be multiple R 42 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n14 is 2 or more, each R 43 These may be the same or different from each other, and there may be multiple R 43 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n15 is 2 or more, each R 44 These may be the same or different from each other, and there may be multiple R 44 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n16 is 2 or more, each R 45These may be the same or different from each other, and there may be multiple R 45 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n17 is 2 or more, each R 46 These may be the same or different from each other, and there may be multiple R 46 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n18 is 2 or more, each R 49 These may be the same or different from each other, and there may be multiple R 49 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n19 is 2 or more, each R 50 These may be the same or different from each other, and there may be multiple R 50 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 35 R is a (n8) valent hydrocarbon group having 1 to 40 carbon atoms or a (n8) valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, 35 This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. Furthermore, some or all of the hydrogen atoms of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the (n8) valent hydrocarbon group may be substituted with a group containing a heteroatom, R 34 and R 35 However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms. 36 R is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 38 is a carbonyl group or a C1-C10 hydrocarbylene group which may contain a heteroatom. *1 and *2 represent the bonds with the carbon atoms of the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms of the aromatic ring. L1 is bondless, a single bond, -O-, -S-, -NH- or -CH2-, and R 47is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. X is nitrogen or sulfur, and in the case of nitrogen, R 48 It may have R 48 This is a hydrocarbyl group having 1 to 20 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom.

[0016] As the hypervalent iodine compound included in the resist composition of the present invention, a three-coordinate hypervalent iodine compound represented by the above formula is preferred. When such a three-coordinate iodine(III) compound having an aryl group and a carboxylate ligand is mixed with a carboxyl group-containing compound, the exchange between the compound and the carboxylate ligand is more likely to occur in an equilibrium reaction. At this time, by removing the original carboxylate ligand from the reaction system, the equilibrium shifts in the direction of generating a hypervalent iodine compound having a new ligand, and ligand exchange proceeds. In this way, the carboxyl group-containing compound becomes a polymer crosslinked by the hypervalent iodine compound.

[0017] Furthermore, the present invention provides a laminate characterized by comprising a substrate and a resist film which is a film formed of the above-mentioned resist composition on the substrate.

[0018] A laminate comprising a resist film obtained from the resist composition of the present invention exhibits high sensitivity and excellent limiting resolution in the resist film formed from the resist composition described above, making it effective for precise microfabrication. Furthermore, it can be applied to both positive and negative pattern formation, thus offering a wide range of applications and high utility in resist process technology.

[0019] In this case, a further resist underlayer film may be provided between the substrate and the resist film. Furthermore, it is preferable that the resist film contains ligand exchange reaction products between the hypervalent iodine compound and the carboxyl group-containing polymer.

[0020] The laminate of the present invention can be configured in such an embodiment as needed.

[0021] Furthermore, the present invention provides a pattern forming method characterized by comprising the steps of: forming a resist film on a substrate or on a resist underlayer of a substrate having a resist underlayer laminated on it using the above-mentioned resist composition; exposing the resist film with high-energy rays; and developing the exposed resist film using a developer.

[0022] The pattern formation method of the present invention is useful for forming even finer patterns because it uses a resist composition with excellent sensitivity and resolution in photolithography using high-energy beams, particularly electron beam (EB) lithography and EUV lithography.

[0023] In this case, it is preferable to use i-rays, KrF excimer laser light, ArF excimer laser light, electron beams, or extreme ultraviolet light as the high-energy beam.

[0024] The pattern formation method of the present invention enables the formation of finer patterns by using such high-energy rays.

[0025] Furthermore, the present invention relates to a method for producing the above-mentioned resist composition, The present invention provides a method for producing a resist composition, characterized by synthesizing the carboxyl group-containing polymer by living radical polymerization using a radical initiator and a reversible addition-cleavage chain transfer agent (RAFT agent) represented by the following formula (R-1) or (R-2), and mixing the obtained carboxyl group-containing polymer with the hypervalent iodine compound and the solvent. [ka] (In the formula, R X1 and R X3 These are, independently, a saturated hydrocarboxylthio group with 3 to 20 carbon atoms, an aralkylthio group with 7 to 20 carbon atoms, a heterocyclyl group with 5 to 20 carbon atoms, and -N(Z A )(Z B ), -COOZ A ,-OCOZ A , -CON(ZA )(Z B )、 -P(=O)(OZ A )2 or -O-P(=O)(Z A )(Z B ). Z A and Z B are each independently a saturated hydrocarbyl 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 are such that some or all of the hydrogen atoms bonded to the carbon atoms thereof may be substituted with a cyano group, a carboxy group or the like. R B X2 and R X4 are each independently a saturated hydrocarbyl group having 2 to 20 carbon atoms which may contain a hetero atom, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.).

[0026] By synthesizing the carboxy group-containing polymer in this way, a narrow-dispersion polymer can be obtained, and the resist composition of the present invention containing the same can be produced with high productivity.

Advantages of the Invention

[0027] The resist composition of the present invention has high sensitivity in high-energy rays, particularly i-line, KrF excimer laser, ArF excimer laser, EB lithography and EUV lithography, and achieves both excellent roughness and limit resolution, and is extremely useful for forming fine patterns.

Modes for Carrying Out the Invention

[0028] As a result of intensive studies to achieve the above object, the present inventors have found that a resist composition mainly composed of a hypervalent iodine compound and a predetermined carboxy group-containing polymer gives a resist film having high sensitivity, low roughness and excellent limit resolution, and is extremely effective for precise microfabrication, and thus have completed the present invention.

[0029] In other words, the present invention relates to a resist composition comprising a hypervalent iodine compound, a carboxyl group-containing polymer, and a solvent, wherein the carboxyl group-containing polymer is a polymer comprising repeating units of a carboxylic acid derivative represented by the following formula (1), and the degree of dispersion Mw / Mn, determined from the weight-average molecular weight Mw and number-average molecular weight Mn measured by gel permeation chromatography (GPC), is 1.30 or less. [ka] (In the formula, R A X is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. A This refers to a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 - is X A1 This is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. (* represents a bond with a carbon atom of the polymer backbone.)

[0030] The present invention will be described in detail below, but is not limited thereto. In this specification, when a numerical range is described with endpoints, it includes all values ​​within that range (for example, "0 to 3" includes 0, 1, 2, and 3).

[0031] [Resist composition] The resist composition of the present invention comprises a hypervalent iodine compound and a predetermined carboxyl group-containing polymer as its main components.

[0032] [Hypervalent iodine compounds] The aforementioned hypervalent iodine compound is a three-coordinate hypervalent iodine compound represented by the following formulas (2) to (11). [ka] (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, and when m3 is 1 When n10 is 0, 1, 2, 3, 4, 5, or 6, and 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, and 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, and when m5 is 1, n12 is 0, 1, 2, 3, 4, 5, or 6, and n13, n14 are 0, 1, 2, 3, 4, 5, or 6, and n15, n16 are 0 n17 is 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; 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 is each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a hetero atom. 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 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 may be bonded to each other to form a ring together with the carbonyl-oxy group to which they are bonded and the atoms between the carbonyl-oxy groups, and R 21 and R 22 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between the carbon atoms. R 31 ~R 34 、R 37 、R 39 ~R 46 、R 49 、R 50 is each independently a halogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a hetero atom; when n2 is 2 or more, each R 31 may be the same as or different from each other, and a plurality of R 31 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded; when n4 is 2 or more, each R 32 may be the same as or different from each other, and a plurality of R 32However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 33 These may be the same or different from each other, and there may be multiple R 33 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 34 These may be the same or different from each other, and there may be multiple R 34 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n9 is 2 or more, each R 37 These may be the same or different from each other, and there may be multiple R 37 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n10 is 2 or more, each R 39 These may be the same or different from each other, and there may be multiple R 39 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n11 is 2 or more, each R 40 These may be the same or different from each other, and there may be multiple R 40 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n12 is 2 or more, each R 41 These may be the same or different from each other, and there may be multiple R 41 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n13 is 2 or more, each R 42 These may be the same or different from each other, and there may be multiple R 42 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n14 is 2 or more, each R 43 These may be the same or different from each other, and there may be multiple R 43 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n15 is 2 or more, each R 44 These may be the same or different from each other, and there may be multiple R 44 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n16 is 2 or more, each R 45These may be the same or different from each other, and there may be multiple R 45 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n17 is 2 or more, each R 46 These may be the same or different from each other, and there may be multiple R 46 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n18 is 2 or more, each R 49 These may be the same or different from each other, and there may be multiple R 49 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n19 is 2 or more, each R 50 These may be the same or different from each other, and there may be multiple R 50 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 35 R is a (n8) valent hydrocarbon group having 1 to 40 carbon atoms or a (n8) valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, 35 This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. Furthermore, some or all of the hydrogen atoms of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the (n8) valent hydrocarbon group may be substituted with a group containing a heteroatom, R 34 and R 35 However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms. 36 R is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 38 is a carbonyl group or a C1-C10 hydrocarbylene group which may contain a heteroatom. *1 and *2 represent the bonds with the carbon atoms of the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms of the aromatic ring. L1 is bondless, a single bond, -O-, -S-, -NH- or -CH2-, and R 47is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. X is nitrogen or sulfur, and in the case of nitrogen, R 48 It may have R 48 This is a hydrocarbyl group having 1 to 20 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom.

[0033] In equations (2) to (11), m1 is 0, 1, or 2. When m1 is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1 ≤ n1 + n2 ≤ 6. When m1 is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1 ≤ n1 + n2 ≤ 8. When m1 is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1 ≤ n1 + n2 ≤ 10, n3 is 1 or 2, and 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, 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, 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; 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. Note that when m1, m2, and m3, m4, m5, m6, m7, and m8 are 0, the aromatic ring is a benzene ring.

[0034] In formulas (2) to (4), (6) to (9), and (11), R 1 ~R 22 Each of these is independently a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 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 However, they may bond to each other and form a ring together with the carbonyloxy groups to which they are bonded and the atoms between the carbonyloxy groups, R 21 and R 22 However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms.

[0035] R 1 ~R 22 Examples of halogen atoms represented by R include fluorine, chlorine, bromine, and iodine atoms. 1 ~R 22The C1-C10 hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include C1-C10 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.0 2,6 Examples include cyclic saturated hydrocarbyl groups having 3 to 10 carbon atoms, such as decyl groups and adamantyl groups; alkenyl groups having 6 to 10 carbon atoms, such as vinyl groups and allyl groups; aryl groups having 6 to 10 carbon atoms, such as phenyl groups and naphthyl groups; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- groups of the hydrocarbyl group may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, the group may contain hydroxyl groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, carbamate bonds, lactone rings, sultone rings, carboxylic acid anhydrides (-C(=O)-OC(=O)-), etc. 1 ~R 22 A hydrocarbyl group having 1 to 4 carbon atoms is preferred.

[0036] In formulas (2) to (11), R 31 ~R 34 , R 37 , R 39 ~R 46 , R 49 , R 50 Each of these is a hydrocarbyl group having 1 to 40 carbon atoms, which may each contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 31 These may be the same or different from each other, and there may be multiple R31 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 32 These may be the same or different from each other, and there may be multiple R 32 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 33 These may be the same or different from each other, and there may be multiple R 33 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 34 These may be the same or different from each other, and there may be multiple R 34 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n9 is 2 or more, each R 37 These may be the same or different from each other, and there may be multiple R 37 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n10 is 2 or more, each R 39 These may be the same or different from each other, and there may be multiple R 39 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n11 is 2 or more, each R 40 These may be the same or different from each other, and there may be multiple R 40 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n12 is 2 or more, each R 41 These may be the same or different from each other, and there may be multiple R 41 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n13 is 2 or more, each R 42 These may be the same or different from each other, and there may be multiple R 42 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n14 is 2 or more, each R 43 These may be the same or different from each other, and there may be multiple R 43 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n15 is 2 or more, each R 44These may be the same or different from each other, and there may be multiple R 44 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n16 is 2 or more, each R 45 These may be the same or different from each other, and there may be multiple R 45 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n17 is 2 or more, each R 46 These may be the same or different from each other, and there may be multiple R 46 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n18 is 2 or more, each R 49 These may be the same or different from each other, and there may be multiple R 49 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n19 is 2 or more, each R 50 These may be the same or different from each other, and there may be multiple R 50 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded.

[0037] R 31 ~R 34 , R 37 , R 39 ~R 46 , R 49 , R 50 Examples of halogen atoms represented by R include fluorine, chlorine, bromine, and iodine atoms. 31 ~R 34 , R 37 , R 39 ~R 46 , R 49 , R 50The C1-C40 hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include C1-C40 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.0 2,6 Examples include cyclic saturated hydrocarbyl groups having 3 to 40 carbon atoms, such as decyl groups, adamantyl groups, and adamantylmethyl groups; and aryl groups having 6 to 40 carbon atoms, such as phenyl groups, naphthyl groups, and anthracenyl groups. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- groups of the hydrocarbyl group may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, which may result in the presence of hydroxyl groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, carbamate bonds, lactone rings, sultone rings, carboxylic acid anhydrides (-C(=O)-OC(=O)-), etc.

[0038] In formula (4), R 35 R is a (n8) valent hydrocarbon group having 1 to 40 carbon atoms or a (n8) valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, 35 This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. Furthermore, some or all of the hydrogen atoms of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the (n8) valent hydrocarbon group may be substituted with a group containing a heteroatom, R 34 and R35 However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms.

[0039] R 35 The (n8) valent hydrocarbon group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. The (n8) valent hydrocarbon group is obtained by removing (n8) hydrogen atoms from a hydrocarbon. Examples of the 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.

[0040] Specific examples of the aforementioned alkanes having 1 to 40 carbon atoms include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[0041] Specific examples of alkenes having 2 to 40 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and their structural isomers.

[0042] Specific examples of alkynes having 2 to 40 carbon atoms include acetylene, propyne, butyne, pentine, hexine, heptine, octin, nonine, decine, and their structural isomers.

[0043] Specific examples of the cyclic saturated hydrocarbons having 3 to 40 carbon atoms include cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, and the like.

[0044] Specific examples of the cyclic unsaturated hydrocarbons having 3 to 40 carbon atoms include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norbornene.

[0045] Specific examples of aromatic hydrocarbons having 6 to 40 carbon atoms include benzene, naphthalene, and biphenyl.

[0046] R 35 The (n8)-valent heterocyclic group represented by is a group obtained by the elimination of (n8) hydrogen atoms from a heterocyclic compound. Examples of such heterocyclic compounds include furan, pyridine, pyrazole, and thiazolidine.

[0047] R 35 The (n8) valent hydrocarbon group or (n8) valent heterocyclic group represented by may have some or all of its hydrogen atoms substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or halogen atom, and as a result may contain a hydroxyl group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Furthermore, the n7 valent hydrocarbon group may have some of its constituent -CH2- substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result may contain a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), etc.

[0048] In formula (5), R 36 R is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 36 Specific examples of halogen atoms and hydrocarbyl groups represented by R are, respectively. 1 ~R 22 Examples of halogen atoms and hydrocarbyl groups represented by the same symbols as those exemplified are also included.

[0049] In formula (5), R 38This is a carbonyl group or a C1-C10 hydrocarbylene group which may contain a heteroatom. The C1-C10 hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include alkylene groups with 1 to 10 carbon atoms, such as methanediyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-2,3-diyl group, butane-1,4-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, etc.; cyclopentanediyl group, cyclohexanediyl group, norbornanediyl group, adamantanediyl group, tricyclo[5.2.1.0 2,6 Examples include cyclic saturated hydrocarbylene groups having 3 to 10 carbon atoms, such as decanediyl groups; alkenylene groups having 2 to 10 carbon atoms, such as vinylene groups and propynylene groups; arylene groups having 6 to 10 carbon atoms, such as phenylene groups, methylphenylene groups, ethylphenylene groups, n-propylphenylene groups, isopropylphenylene groups, n-butylphenylene groups, and naphthylene groups; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- of the hydrocarbylene group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, it may contain a hydroxyl group, a cyano group, an alkyl halide, a halogen atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), etc. 38 Preferred members include carbonyl groups, C1-C4 hydrocarbylene groups, or C1-C4 fluorinated hydrocarbylene groups.

[0050] In equation (5), *1 and *2 represent the bonds with the carbon atoms of the aromatic ring in the equation. However, *1 and *2 are bonded to adjacent carbon atoms of the aromatic ring. There are seven possible combinations of *1, *2 and m2, as shown below. [ka] (In the formula, n9, R 37 and R 38 The same as above. The dashed line is R 36 (This represents a bond between -C(=O)-O-.)

[0051] L1 is bondless (in this case, the carbon atoms of the aromatic ring are replaced by hydrogen atoms), has a single bond, is -O-, -S-, -NH-, or -CH2-.

[0052] In formula (10), R 47 R is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 47 Specific examples of halogen atoms and hydrocarbyl groups represented by R are, respectively. 1 ~R 22 Examples of halogen atoms and hydrocarbyl groups represented by the same symbols as those exemplified are also included.

[0053] In equation (10), X is nitrogen or sulfur, and if it is nitrogen, R 48 It may have R 48 R is a hydrocarbyl group having 1 to 20 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom. 48 Specific examples of halogen atoms and hydrocarbyl groups represented by R are, respectively. 1 ~R 22 Examples of halogen atoms and hydrocarbyl groups represented by the same symbols as those exemplified are also included. Note, R 31 ~R 34 , R 37 ~R 46 , R 49 , R 50 The above formula allows for the substitution of any position in the aromatic ring.

[0054] Specific examples of hypervalent iodine compounds represented by formula (2) are listed below, but are not limited to these. [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] Specific examples of hypervalent iodine compounds represented by formula (3) are listed below, but are not limited to these. [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] Specific examples of hypervalent iodine compounds represented by formula (4) are listed below, but are not limited to these. [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] Specific examples of hypervalent iodine compounds represented by formula (5) are listed below, but are not limited to these. In the following formula, Me represents a methyl group. [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083]

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[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] Specific examples of hypervalent iodine compounds represented by formula (6) are listed below, but are not limited to these. [ka]

[0133] [ka]

[0134] [ka]

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[0146] [ka]

[0147] [ka]

[0148] Specific examples of hypervalent iodine compounds represented by formula (7) are listed below, but are not limited to these. In the following formulas, L1 is the same as described above. [ka]

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] [ka]

[0153] [ka]

[0154] [ka]

[0155] [ka]

[0156] [ka]

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] [ka]

[0163] [ka]

[0164] Specific examples of hypervalent iodine compounds represented by formula (8) are listed below, but are not limited to these. [ka]

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] Specific examples of hypervalent iodine compounds represented by formula (9) are listed below, but are not limited to these. [ka]

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] Specific examples of hypervalent iodine compounds represented by formula (10) are listed below, but are not limited to these. [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185]

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[0196] [ka]

[0197] Specific examples of hypervalent iodine compounds represented by formula (11) are listed below, but are not limited to these. [ka]

[0198] [ka]

[0199] [ka]

[0200] [ka]

[0201] [ka]

[0202] [ka]

[0203] [ka]

[0204] [ka]

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[0250] [ka]

[0251] [Carboxylate group-containing polymer] The carboxyl group-containing polymer of the present invention is a polymer containing repeating carboxylic acid derivative units represented by the following formula (1), wherein the degree of dispersion Mw / Mn, determined from the weight-average molecular weight Mw and number-average molecular weight Mn measured by GPC of the polymer, is 1.30 or less. The theoretical lower limit of the degree of dispersion is 1, and the closer it is to 1, the more monodisperse it becomes. In the present invention, in order to obtain a non-chemically amplified resist composition with excellent sensitivity and critical resolution, it is important that the dispersion degree Mw / Mn is narrowly dispersed to 1.30 or less. If the dispersion degree exceeds 1.30, the molecular weight distribution of the polymer broadens, and when used as a resist, the roughness increases and the solubility becomes non-uniform due to the broad molecular weight. As a result, the polymer is prone to swelling, which may cause pattern collapse in line-and-space patterns or blockage between patterns in contact hole patterns. A dispersion degree Mw / Mn of 1.0 to 1.30 is preferred, and 1.0 to 1.1 is more preferred. [ka] R A X is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. A This refers to a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 - is X A1This is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. * represents a bond with a carbon atom of the polymer backbone.

[0252] In this invention, Mw and Mn are measured values ​​converted to standard polystyrene using gel permeation chromatography (GPC) with tetrahydrofuran (THF) as the solvent. A typical technician knows that GPC (also known as size exclusion chromatography (SEC)) can be used to measure the molecular weight distribution (dispersion) of polymers, and knows how to calibrate GPC and what columns, detectors, and temperature settings should be applied to reliably measure Mw and Mn depending on the carboxyl group-containing polymer in this invention. Thus, the dispersion of the above polymer can be determined reproducibly within the range of normal error.

[0253] Specific examples of carboxyl group-containing repeating units represented by formula (1) are, but are not limited to, those listed below. Note that in the following formula, R A This is the same as described above. [ka]

[0254] [ka]

[0255] A carboxyl group-containing polymer containing repeating units represented by formula (1) may further contain repeating units other than those represented by formula (1) (hereinafter also referred to as other repeating units). The other repeating units are not particularly limited, but those that can improve the solubility in solvents of polymers that are poorly soluble with only carboxyl group-containing repeating units are preferred. The other repeating units are preferably repeating units having a rigid skeleton and a cyclic structure that is expected to have high etching resistance, or repeating units containing a styrene skeleton.

[0256] Specific examples of the aforementioned other repeating units include, but are not limited to, those listed below. Note that in the following formula, R A This is the same as above, X B These are, independently, -CH2- or -O-. [ka]

[0257] [ka]

[0258] [ka]

[0259] [ka]

[0260] [ka]

[0261] [ka]

[0262] [ka]

[0263]

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[0264]

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[0270]

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[0284] [ka]

[0285] [ka]

[0286] The method for synthesizing the above-mentioned carboxyl group-containing polymer is not particularly limited as long as it satisfies the above-mentioned degree of dispersion, but it is preferable that it be synthesized by living radical polymerization using a radical initiator and a reversible addition-cleavage chain transfer agent (RAFT agent). That is, the present invention also provides a method for producing the above-mentioned resist composition, characterized by comprising the steps of synthesizing the carboxyl group-containing polymer by living radical polymerization using a radical initiator and a reversible addition-cleavage chain transfer agent (RAFT agent) represented by the following formula (R-1) or (R-2), and mixing the obtained carboxyl group-containing polymer with the hypervalent iodine compound and the solvent. Hereinafter, living radical polymerization using a RAFT agent will also be referred to as "RAFT polymerization".

[0287] Living polymerization is an effective polymerization method for synthesizing polymers with precisely controlled structures. It is known as a method for obtaining polymers with a narrow degree of dispersion, and living polymerization with different reaction mechanisms, such as anionic, cationic, radical, coordination, and ring-opening (metathesis), has been utilized. The carboxyl group-containing polymer in the present invention is obtained by (co)polymerizing monomers corresponding to the carboxyl group-containing repeating unit represented by formula (1) above, and optionally monomers corresponding to other repeating units above. As a polymerization method to obtain the carboxyl group-containing polymer of the present invention having a dispersion degree Mw / Mn of 1.30 or less as measured by GPC, living radical polymerization is preferred, and RAFT polymerization is more preferred.

[0288] RAFT polymerization itself is a known technique, as disclosed in Japanese Patent Publication No. 2007-520587, Japanese Patent Application Publication No. 2006-002096, Japanese Patent Application Publication No. 2007-246588, etc. However, in conventional living radical polymerization systems, RAFT reagent residues having unsaturated bonds in their structure have a strong absorption band in the ultraviolet region. Therefore, while RAFT reagents are effective in controlling polymerization, they are often insufficient for improving the performance of the resist resin (see paragraph

[0007] of Japanese Patent Application Publication No. 2006-002096). It was considered extremely difficult to obtain a resist composition that exceeds the conventional sensitivity and limiting resolution in photolithography using high-energy rays such as EUV. Despite these circumstances, surprisingly, the present invention provides a non-chemically amplified resist composition with excellent sensitivity and limiting resolution in EUV lithography, etc., without causing the above-mentioned problems, using a resist composition containing a hypervalent iodine compound, a specific carboxyl group-containing polymer, and a solvent. The RAFT polymerization method used in this invention will be described below.

[0289] [RAFT agent] The RAFT agent is preferably a reversible addition-cleavage chain transfer agent (RAFT agent) represented by the following formula (R-1) or (R-2). [ka]

[0290] In the formula, R X1 and R X3 These are, independently, a saturated hydrocarboxylthio group with 3 to 20 carbon atoms, an aralkylthio group with 7 to 20 carbon atoms, a heterocyclyl group with 5 to 20 carbon atoms, and -N(Z A )(Z B ), -COOZ A ,-OCOZ A , -CON(Z A )(Z B ), -P(=O)(OZ A )2 or -OP(=O)(Z A )(Z B ) is Z A and ZB Each of these is independently a saturated hydrocarbyl 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 case, some or all of the hydrogen atoms bonded to the carbon atom may be substituted with cyano groups, carboxyl groups, etc. R X2 and R X4 These are, independently, a saturated hydrocarbyl group having 2 to 20 carbon atoms, which may contain heteroatoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0291] The RAFT agents are, respectively, a trithiocarbonate compound and a dithioester compound. Specific examples of the trithiocarbonate compound include 2-cyano-2-propyldodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, cyanomethyldodecyltrithiocarbonate, and 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid. Specific examples of the dithioester compound include 1-ethoxycarbonyl-1-phenylmethylbenzodithioate, 2-phenyl-2-propylbenzodithioate, 4-cyano-4-(phenylthiocarbonylthio)pentanoic acid, and 2-cyano-2-propylbenzodithioate.

[0292] Among the RAFT agents mentioned above, from the viewpoint of availability, it is preferable to use 2-cyano-2-propyldodecyltrithiocarbonate as the trithiocarbonate compound and 1-ethoxycarbonyl-1-phenylmethylbenzodithioate as the dithioester compound.

[0293] The amount of RAFT agent used is preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the total monomers. The upper limit of the amount used is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the total monomers. The RAFT agent may be used alone or in combination of two or more types.

[0294] In the resist composition, the content ratio of the hypervalent iodine compound to the carboxyl group-containing compound (or, if the carboxyl group-containing compound is a carboxyl group-containing polymer, the content ratio of the hypervalent iodine compound to the carboxylic acid-containing repeating units in the polymer) is preferably, in molar ratio, hypervalent iodine compound:carboxyl group-containing compound = 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30. The hypervalent iodine compound may be used alone, or two or more types with different composition ratios, Mw, and / or Mw / Mn may be used in combination. The carboxyl group-containing polymer may be used alone, or two or more types with different composition ratios, Mw, and / or Mw / Mn may be used in combination.

[0295] In the carboxyl group-containing polymer, the content ratio (molar ratio) of carboxyl group-containing repeating units and other repeating units is preferably carboxyl group-containing repeating units:other repeating units = 10:90 to 90:10, more preferably 15:85 to 85:15, and even more preferably 20:80 to 80:20.

[0296] The weight-average molecular weight (Mw) of the carboxyl group-containing polymer is preferably 1,000 to 500,000, and more preferably 3,000 to 100,000. In this invention, Mw is a standard polystyrene equivalent value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0297] Living radical polymerization reactions are (1) A method in which all monomers, polymerization initiators, and RAFT agents are added to the solvent at once in a reactor and dissolved, and then the reactor is heated to start the reaction. (2) A method of starting a reaction by supplying a solution in which each monomer, polymerization initiator and RAFT agent are dissolved in the solvent to a reactor that has been preheated by charging a portion of the solvent into the reactor, and (3) A method in which the reaction is started by supplying a solution in which each monomer and polymerization initiator are dissolved in the solvent to a reactor that has been preheated by charging it with the RAFT agent and some of the solvent. The process can be carried out by selecting any of the following methods as appropriate. In the case of methods (2) and (3), the monomer, initiator solution and RAFT agent solutions may be prepared separately and supplied to the reactor. During the waiting time, the polymerization reaction may proceed due to radicals generated from the initiator, potentially producing a superpolymer. From the viewpoint of quality control, it is preferable to prepare at least the monomer solution and initiator solution separately and add them dropwise.

[0298] In the living radical polymerization reaction described above, the reaction temperature is preferably 50 to 150°C, and more preferably 60 to 100°C. The reaction time is preferably 2 to 24 hours, and more preferably 2 to 12 hours from the viewpoint of production efficiency.

[0299] After the living radical polymerization reaction step, a purification step may be included in which the reaction solution is added to a poor solvent and reprecipitation is performed as needed. The poor solvent used at this time can be appropriately selected depending on the type of polymer, but typical 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 ether and butyl acetate; and water, but are not limited to these. These solvents may be used individually or as a mixture of two or more.

[0300] By adding a radical generator and a thiol compound to the polymer solution obtained after polymerization and heating the mixture, the terminal structures can be removed from the polymer's main chain. This operation replaces the terminal structures of the polymer with hydrogen atoms. Although some undegraded radical generators may remain from the radical polymerization step, it is preferable to add the radical generator simultaneously with the thiol compound to efficiently replace the terminal structures with hydrogen atoms in a short time.

[0301] The radical generator added after polymerization can be appropriately selected from the same ones exemplified during polymerization. The amount of radical initiator used is preferably 0.5 to 10 moles, and more preferably 0.5 to 2 moles, per mole of RAFT agent used during polymerization.

[0302] In the present invention, the thiol compound used after polymerization is preferably a compound represented by the following formula (SH-1) or (SH-2). [ka]

[0303] In formula (SH-1), R SH1 This is a hydrocarbylene group having 1 to 3 carbon atoms. Specific examples of the hydrocarbylene group include methanediyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, and the like.

[0304] In formula (SH-1), R SH2 This is an aliphatic hydrocarbyl group having 4 to 8 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, which may contain heteroatoms. Examples of the heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, etc.

[0305] R SH2The aliphatic hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include linear or branched aliphatic hydrocarbyl groups such as n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 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, and octadecyl. Examples of locarbyl groups include cyclopentyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-vinylcyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-vinylcyclohexyl group, norbornyl group, 1-methylnorbornyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, 1-methyladamantyl group, 1-ethyladamantyl group, and other cyclic aliphatic hydrocarbyl groups.

[0306] R SH2 Specific examples of aralkyl groups with 7 to 18 carbon atoms represented by include the benzyl group, phenethyl group, 4-methoxybenzyl group, and 9-anthracenylmethyl group. SH2 Specific examples of aryl groups with 6 to 18 carbon atoms represented by include phenyl group, naphthyl group, 4-methoxyphenyl group, 2-anthracenyl group, and 9-anthracenyl group.

[0307] In formula (SH-2), R SH3 This is a saturated hydrocarbyl group having 6 to 20 carbon atoms, which may contain heteroatoms, an aralkyl group having 7 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

[0308] R SH3The saturated hydrocarbyl group represented by can be linear, branched, or cyclic, and specific examples include n-hexyl group, 3-methylpentyl group, n-heptyl group, n-octyl group, 1-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, 2,2,4,6,6-pentamethylheptan-4-yl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosanyl group, 2,3,3,4,4,5-pexamethylhexane-2-yl group, etc.

[0309] R SH3 Specific examples of aralkyl groups with 7 to 18 carbon atoms represented by include the benzyl group, phenethyl group, 4-methoxybenzyl group, and 9-anthracenylmethyl group. SH2 Specific examples of aryl groups with 6 to 18 carbon atoms represented by include phenyl group, naphthyl group, 4-methoxyphenyl group, 2-anthracenyl group, and 9-anthracenyl group.

[0310] The following compounds are preferred as the compound represented by formula (SH-1). [ka]

[0311] [ka]

[0312] The following compounds are preferred as the compound represented by formula (SH-2). [ka]

[0313] The amount of thiol compound used after polymerization is preferably 1 to 20 moles, and more preferably 1 to 4 moles, per mole of RAFT agent used during polymerization. The radical initiator and thiol compound added after polymerization may be added independently to the solution containing the polymer, or they may be mixed and added to the solution containing the polymer simultaneously. From the viewpoint of operational efficiency, it is preferable to add a mixture of the initiator and thiol compound dissolved simultaneously in the solvent to the solution containing the polymer, and it is more preferable to add the mixed solution of the initiator and thiol to the reaction solution in which living radical polymerization was carried out in the solvent.

[0314] The reaction temperature after polymerization is preferably 50 to 150°C, and more preferably 60 to 100°C. The reaction time after polymerization is preferably 2 to 24 hours, and more preferably 2 to 5 hours from the viewpoint of production efficiency.

[0315] 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), and γ-butyrolactone (GBL). Specific examples of polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The amount of polymerization initiator added is preferably 0.01 to 25 mol% of the total amount of monomers to be polymerized.

[0316] Polymers synthesized by living radical polymerization have a narrow dispersion, resulting in reduced roughness when used as a resist. Their uniform solubility also minimizes polymer swelling, effectively preventing pattern collapse in line-and-space patterns and blockage between contact hole patterns.

[0317] The amount of each monomer in the monomer solution can be appropriately set, for example, to achieve a preferred content ratio of the repeating units described above.

[0318] [solvent] The resist composition of the present invention contains a solvent. The solvent is not particularly limited as long as it can dissolve the hypervalent iodine compound, the carboxyl group-containing compound and other components described later, and form a film. Such solvents are preferably organic solvents, and specific examples include ketones such as cyclohexanone, methyl-2-n-pentyl ketone, and methyl isoamyl 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; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, Examples include ethers such as 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 mixed solvents thereof.

[0319] In the resist composition of the present invention, the amount of solvent is preferably such that the solid content concentration 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. In the present invention, "solid content" refers to all components of the resist composition other than the solvent. The solvent may be used alone or as a mixture of two or more types.

[0320] [Other ingredients] The resist composition may further contain a surfactant. A fluorine-based and / or silicone-based surfactant is preferred. Examples of such surfactants include those described in paragraph

[0276] of U.S. Patent Application Publication 2008 / 0248425. Furthermore, surfactants other than the fluorine-based and / or silicone-based surfactants described in paragraph

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

[0321] If the resist composition contains the surfactant, its content is preferably 0.0001 to 2% by mass of the total solids. The surfactant may be used alone or in combination of two or more types.

[0322] The resist composition may further contain a radical scavenger. By adding a radical scavenger, the photoreaction during photolithography can be controlled and the sensitivity adjusted.

[0323] Examples of the radical scavengers include hindered phenols, quinones, hindered amines, and thiol compounds. Specifically, examples of hindered phenols include dibutylhydroxytoluene (BHT) and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). Examples of quinones include 4-methoxyphenol (methoquinone) and hydroquinone. Examples of hindered amines include 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethylpiperidine-N-oxy radical. Examples of thiols include dodecanethiol and hexadecanethiol.

[0324] If the resist composition contains the radical scavenger, its content is preferably 0.01 to 10% by mass of the total solids. The radical scavenger may be used alone or in combination of two or more types.

[0325] The resist composition may further contain a crosslinking agent. Adding a crosslinking agent promotes the crosslinking reaction during photolithography, improving the glass transition temperature of the pattern and resulting in a pattern with excellent resolution at fine lines.

[0326] Examples of crosslinking agents include compounds having carbon-carbon unsaturated bonds as functional groups, such as vinyl groups, (meth)acrylate groups, allyl groups, alkynyl groups, and aromatic rings. Specifically, examples of compounds having vinyl groups include linear alkenes, branched alkenes, and cyclic alkenes, which may have substituents. Examples of compounds having (meth)acrylate groups include acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, which may have substituents. Examples of compounds having allyl groups include allyl alcohol, allyl ether, allyl ester, allyl amide, allylamine, and allyl group-containing isocyanurates, which may have substituents. Examples of compounds having alkynyl groups include linear alkynes, branched alkynes, cyclic alkynes, alkynyl alcohol, alkynyl ether, alkynyl ester, alkynyl amide, alkynylamine, and alkynyl group-containing isocyanurates, which may have substituents. Compounds having an aromatic ring include arenes, heteroarenes, styrene, stilbene, phenylacetylene, acenaphthylene, and chalcone, which may have substituents. The crosslinking agent may have only one of the above functional groups or may have multiple of them. The number of above functional groups contained in the crosslinking agent is preferably 1 to 10, and more preferably 2 to 8.

[0327] If the resist composition contains the crosslinking agent, its content is preferably 0.01 to 50% by mass of the total solids. The crosslinking agent may be used alone or in combination of two or more types.

[0328] If the resist composition contains the crosslinking agent, it may further contain a photopolymerization initiator. The photopolymerization initiator can generate radicals by irradiation with high-energy rays, thereby promoting the crosslinking of the crosslinking agent.

[0329] Specific examples of the aforementioned photopolymerization initiators include benzophenone, benzophenone derivatives such as methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morphol Acetophenone derivatives such as nopropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methylpropan-1-one, and methyl phenylglyoxylate; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, and diethylthioxanthone; benzyl, benzyldimethylketal, benzyl Benzyl derivatives such as benzoin-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether, and 2-hydroxy-2-methyl-1-phenylpropan-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, Oxime compounds such as 2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)]ethanone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime);α-hydroxyketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropane; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl) Examples include α-aminoalkylphenone compounds such as butan-1-one; phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium.

[0330] If the resist composition contains the photopolymerization initiator, its content is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and most preferably 0.1 to 1% by mass, based on the total solid content. A content of 0.1% by mass or more is sufficient to obtain the desired blending effect.

[0331] As described above, the resist composition mainly contains hypervalent iodine compounds and carboxyl group-containing compounds, but does not require acid-unstable group-containing polymers or photoacid generators, as is common in conventional chemically amplified resist compositions. However, the resist composition of the present invention can form a positive-type pattern in which the exposed areas are soluble in the developer, or a negative-type pattern in which the exposed areas are insoluble in the developer, particularly by EB or EUV exposure. The mechanism is not fully clear, but it can be inferred, for example, as follows.

[0332] In the present invention, preferred hypervalent iodine compounds are compounds containing a three-coordinate hypervalent iodine having an aryl group and a carboxylate ligand. It is believed that when such a three-coordinate iodine compound is mixed with a carboxyl group-containing compound, an equilibrium reaction occurs in which the carboxylate ligand is exchanged. In this case, if the original carboxylate ligand can be removed by some method, a hypervalent iodine compound with a new ligand is produced. For example, if 1-iodonaphthylenediacetate is mixed with a carboxyl group-containing compound as the hypervalent iodine compound and the resulting low-boiling point acetic acid is removed, the ligand exchange is completed. Here, the carboxyl group-containing compound becomes a polymer crosslinked by the hypervalent iodine compound.

[0333] Polymers crosslinked with hypervalent 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 it impossible to prepare a solution. This is presumed to be because hypervalent iodine compounds, which inherently have low solvent solubility due to their high polarization, become even less soluble when carboxyl group-containing compounds are used as ligands. Therefore, it is desirable to remove the original low-molecular-weight carboxylic acid component during film formation and the subsequent baking process to complete the ligand exchange reaction and form a resist film.

[0334] The resist film obtained from the resist composition of the present invention undergoes a change in polarity when its main component, a hypervalent iodine compound, is decomposed by light, and a pattern is formed during the development process. Although the mechanism is not fully understood, it can be speculated as follows.

[0335] The resist composition of the present invention can be either positive or negative depending on the selection of its components. In the case of the positive type, it contains a polymer to which a hypervalent iodine compound is bonded during film formation. When this is decomposed by light, it becomes a monovalent iodine compound, and at the same time, the bond between the carboxyl group-containing compound and the hypervalent iodine compound is released, and the molecular weight decreases. As a result, it is presumed that a positive type pattern is formed in which the exposed areas are removed by an organic solvent.

[0336] On the other hand, in the case of the negative type, the polymer contains a hypervalent iodine compound crosslinked with a hypervalent iodine compound generated during film formation. When this is decomposed by light, crosslinking or re-bonding occurs, leading to an increase in molecular weight and a change in polarity. As a result, it is presumed that a negative type pattern is formed in which the unexposed areas are removed by an alkaline aqueous solution.

[0337] From the above inference, it can be said that the resist composition of the present invention is a non-chemically amplified resist composition. The resist composition of the present invention does not require acid-unstable group-containing polymers or photoacid generators like conventional chemically amplified resist compositions. Therefore, adverse effects due to acid diffusion (e.g., image blurring) do not occur, and fine patterns can be resolved.

[0338] The resist composition of the present invention is particularly effective in EUV lithography. This is due to the presence of iodine atoms with high absorption capacity for EUV light. That is, shot noise is reduced, and higher resolution and lower LWR can be achieved.

[0339] As an EUV resist composition capable of forming fine patterns, metal resists mainly composed of metallic tin compounds, which have high absorption capacity to EUV light similar to iodine atoms, have been reported (for example, Patent Document 2). However, as mentioned above, such metal resists have many problems, such as insufficient solubility in solvents, storage stability, and defects due to etching residues caused by the presence of metallic elements. On the other hand, the resist composition of the present invention does not use metallic elements, making it more advantageous than metal resists in terms of defects, and there are no problems with solubility in solvents. Furthermore, the resist composition of the present invention can be applied to both positive and negative type processes, thus offering a wide range of applications. For example, in the contact hole formation process, a metal resist developed using negative type development requires an inversion process after pillar pattern formation, but such a process is unnecessary with positive type resists. Therefore, from the viewpoint of process simplicity, the resist composition of the present invention is more useful than metal resists.

[0340] The resist film preferably has a thickness of 10 to 70 nm, and more preferably 20 to 50 nm.

[0341] The resist composition may also contain a photoacid generator. The presence of a photoacid generator in the resist composition of the present invention allows for the formation of positive patterns with higher sensitivity compared to a resist composition without a photoacid generator. While the mechanism is not entirely clear, it can be inferred, for example, as follows.

[0342] In the resist composition of the present invention, the addition of a photoacid generator causes the acid generated by the photoacid generator during the resist exposure process to exchange with the ligand of the hypervalent iodine compound, becoming a new ligand and thereby releasing the bond between the carboxyl group-containing polymer and the hypervalent iodine compound. Therefore, in addition to the cleavage of the IO bond by light, a change in polarity or a decrease in molecular weight occurs due to the exchange of new ligands by the acid generated by the photoacid generator, and it is presumed that a positive pattern can be formed with high sensitivity by organic solvent development.

[0343] Based on the above inference, the resist composition of the present invention is a non-chemically amplified resist composition containing a photoacid generator and does not require an acid-unstable group-containing polymer like conventional chemically amplified resist compositions. Therefore, the acid generated from the photoacid generator reacts with the ligand of the hypervalent iodine compound in the exposed area to form a new hypervalent iodine ligand. In other words, since it does not have an amplification mechanism that regenerates acid by reacting with acid-unstable groups like chemically amplified resist compositions, adverse effects due to acid diffusion (e.g., image blurring) do not occur, and fine patterns can be resolved.

[0344] Specific examples of the aforementioned photoacid generator include the following onium salt compounds.

[0345] [Onium salt compounds] The onium salt compound contains, as a cation, a sulfonium cation represented by the following formula (5-1) or an iodonium cation represented by the following formula (5-2). [ka]

[0346] In equations (5-1) and (5-2), R 61 ~R 65 Each of these is independently a hydrocarbyl group having 1 to 30 carbon atoms, which may contain a halogen atom or a heteroatom.

[0347] R 61 ~R 65 Specific examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms.

[0348] R 61 ~R 65The hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include C1-C30 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups; C3-C30 cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups; C2-C30 alkenyl groups such as vinyl, allyl, propenyl, butenyl, and hexenyl groups; C3-C30 cyclic unsaturated hydrocarbyl groups such as cyclohexenyl groups; C6-C30 aryl groups such as phenyl, naphthyl, and thienyl groups; C7-C30 aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl groups; and groups obtained by combining these, but aryl groups are preferred. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, it may contain a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc.

[0349] Also, R 61 and R 62 However, they may bond with each other to form a ring with the sulfur atom to which they are bonded. In this case, specific examples of the structure of the ring include those represented by the following formula. [ka] (In the formula, the dashed line represents R 63 (This is a combination of the two.)

[0350] Specific examples of sulfonium cations represented by formula (5-1) are listed below, but are not limited to these. [ka]

[0351] [ka]

[0352] [ka]

[0353] [ka]

[0354] [ka]

[0355] [ka]

[0356] [ka]

[0357] [ka]

[0358] [ka]

[0359] [ka]

[0360]

change

[0361]

change

[0362]

change

[0363]

change

[0364]

change

[0365]

change

[0366]

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[0367]

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[0368]

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[0369]

change

[0370]

change

[0371] [ka]

[0372] [ka]

[0373] [ka]

[0374] [ka]

[0375] [ka]

[0376] [ka]

[0377] Specific examples of iodonium cations represented by formula (5-2) are listed below, but are not limited to these. [ka]

[0378] [ka]

[0379] The onium salt compound includes, as an anion, a halide ion, a nitrate ion, a bisulfate ion, a bicarbonate ion, a tetraphenylborate ion, or any of the following formulas (5-3) to (5-9). [ka]

[0380] In equations (5-3) and (5-5), k1 and k2 are independently 1, 2, 3, or 4. Rf 1 and Rf 2 Each of these is independently a hydrogen atom, a fluorine atom, or a fluorine-containing alkyl group having 1 to 6 carbon atoms, but all Rf 1 and Rf 2 They cannot simultaneously become hydrogen atoms.

[0381] In formula (5-3), R 71 This is a hydrocarbyl group having 1 to 50 carbon atoms, which may contain a hydrogen atom, a halogen atom, a hydroxyl group, or a heteroatom.

[0382] In formula (5-4), R 72 This refers to a C1-C50 hydrocarbyl group which may contain a hydrogen atom, a halogen atom, a hydroxyl group, or a heteroatom. However, this excludes cases where the hydrogen atoms on the α and β carbon atoms of the sulfo group are substituted with a fluorine atom or a fluoroalkyl group.

[0383] In formula (5-5), R 81 This is a hydrocarbyl group having 1 to 50 carbon atoms, which may contain a hydrogen atom, a halogen atom, a hydroxyl group, or a heteroatom.

[0384] In formula (5-6), R 82 This refers to a C1-C50 hydrocarbyl group which may contain a hydrogen atom, a halogen atom, a hydroxyl group, or a heteroatom. However, this excludes cases where the hydrogen atoms on the α and β carbon atoms of the carboxyl group are substituted with a fluorine atom or a fluoroalkyl group.

[0385] In formula (5-7), R 91 and R 92 Each of these is independently a hydrocarbyl group having 1 to 50 carbon atoms, which may contain heteroatoms.

[0386] In formula (5-8), R101 ~R 103 Each of these is independently a hydrocarbyl group having 1 to 50 carbon atoms, which may contain heteroatoms.

[0387] In formula (5-9), R 111 This is a fluorine atom or a fluorinated hydrocarbyl group having 1 to 10 carbon atoms, and the fluorinated hydrocarbyl group may contain a hydroxyl group, an ether bond, or an ester bond. 112 R is a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and the hydrocarbyl group may contain a hydroxyl group, an ether bond, or an ester bond. 111 and R 112 However, they may bond with each other to form a ring with the atom they bond to.

[0388] The anion of the 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 more preferably a halide ion, a nitrate ion, or an anion represented by formulas (5-4), (5-6), or (5-8).

[0389] R 71 , R 72 , R 81 , R 82 , R 91 , R 92 , R 101 , R 102 and R 103 The C1-C50 hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include C1-C50 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.02,6 Examples include cyclic saturated hydrocarbyl groups with 3 to 50 carbon atoms, such as decyl groups, adamantyl groups, and adamantylmethyl groups; alkenyl groups with 2 to 30 carbon atoms, such as vinyl groups, 1-propenyl groups, 2-propenyl groups, butenyl groups, and hexenyl groups; cyclic unsaturated hydrocarbyl groups with 3 to 30 carbon atoms, such as cyclohexenyl groups; aryl groups with 6 to 50 carbon atoms, such as phenyl groups, naphthyl groups, and anthracenyl groups; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- constituting the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, it may contain a hydroxyl group, a cyano group, a halogen atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), etc.

[0390] R 111 A fluorinated hydrocarbyl group having 1 to 10 carbon atoms, represented by R, is a group in which some or all of the hydrogen atoms of a hydrocarbyl group having 1 to 10 carbon atoms are replaced with fluorine atoms. The hydrocarbyl group having 1 to 10 carbon atoms may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R 71 , R 72 , R 81 , R 82 , R 91 , R 92 , R 101 , R 102 and R 103 Among the examples of hydrocarbyl groups with 1 to 50 carbon atoms represented by , those with 1 to 10 carbon atoms are cited.

[0391] R 112 The hydrocarbyl group, represented by , having 1 to 20 carbon atoms, can be saturated or unsaturated, and can be linear, branched, or cyclic. A specific example is R 71 , R 72 , R 81, R 82 , R 91 , R 92 , R 101 , R 102 and R 103 Among the examples of hydrocarbyl groups with 1 to 50 carbon atoms represented by , those with 1 to 20 carbon atoms are particularly noteworthy.

[0392] Anions represented by any of formulas (5-3) to (5-9) may contain polymerizable functional groups in their structure and may have a hydrocarbyl group having 2 to 50 carbon atoms, which may also contain heteroatoms. Specific examples are listed below, but are not limited to these. [ka]

[0393] [ka]

[0394] [ka]

[0395] [ka]

[0396] Specific examples of anions represented by formula (5-3) are listed below, but are not limited to these. In the formula below, Ac is an acetyl group, and Rf 1 This is the same as above. [ka]

[0397] [ka]

[0398]

change

[0399]

change

[0400]

change

[0401]

change

[0402]

change

[0403]

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[0404]

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[0405]

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[0406]

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[0407]

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[0408]

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[0409] Specific examples of anions represented by formula (5-4) are listed below, but are not limited to these. [ka]

[0410] [ka]

[0411] [ka]

[0412] [ka]

[0413] [ka]

[0414] [ka]

[0415] Specific examples of anions represented by formula (5-5) are listed below, but are not limited to these. [ka]

[0416] [ka]

[0417] Specific examples of anions represented by formula (5-6) are listed below, but are not limited to these. [ka]

[0418] [ka]

[0419] [ka]

[0420] [ka]

[0421] Specific examples of anions represented by formula (5-7) are listed below, but are not limited to these. [ka]

[0422] [ka]

[0423] Specific examples of anions represented by formula (5-8) are listed below, but are not limited to these. [ka]

[0424] [ka]

[0425] [ka]

[0426] Specific examples of anions represented by formula (5-9) are listed below, but are not limited to these. [ka]

[0427] [ka]

[0428] Specific examples of onium salts include any combination of anion and cation as mentioned above.

[0429] Onium salts may be used individually or in combination of two or more. When using two or more onium salts in combination, it is preferable to use photoacid generators with different acidity levels. The lower acidity of the photoacid generator quenches the acid generated in the resist-exposed area, preventing it from diffusing into the unexposed area and thus suppressing diffusion and allowing for the formation of a high-resolution pattern.

[0430] In the resist composition of the present invention, the molar ratio of the hypervalent iodine compound to the photoacid generator is preferably hypervalent iodine compound:photoacid generator = 1:1000 to 1000:1, and more preferably 1:500 to 500:1.

[0431] When the onium salt has a large molecular weight and bulky substituents introduced, it has a large excluded volume and highly suppresses the diffusion of generated acids, making it suitable for forming fine patterns.

[0432] When the onium salt contains elements with high EUV light absorption effects, such as fluorine atoms and iodine atoms, the amount of secondary electrons generated increases, promoting cation decomposition, making it suitable for highly sensitive fine pattern formation.

[0433] [Laminated structure] The present invention provides a laminate characterized by comprising a substrate and a resist film formed on the substrate, which is a film formed from the resist composition described above. Such a laminate comprising a resist film obtained from the non-chemically amplified resist composition of the present invention is extremely effective for precise microfabrication because the resist film, which is a film formed from the resist composition described above, is extremely sensitive and exhibits excellent limiting resolution. Furthermore, it can be applied to the formation of both positive and negative patterns, thus having a wide range of applications and being extremely useful in resist process technology. In this case, a resist underlayer film may be provided between the substrate and the resist film as needed. Furthermore, it is preferable that the laminate of the present invention contains a resist film which includes a ligand exchange reaction product between the hypervalent iodine compound and the carboxyl group-containing compound. In other words, the laminate is obtained by forming a resist film obtained from the resist composition of the present invention on a substrate, and it is preferable that the resist film is formed by ligand exchange between the hypervalent iodine compound and the carboxyl group-containing compound. As described above, by removing the low molecular weight carboxylic acid produced as a by-product during film formation and the subsequent baking process, the hypervalent iodine compound undergoes a ligand exchange reaction with the carboxyl group-containing compound, forming a resist film containing the ligand exchange reaction product (i.e., giving a film-forming material). Upon completion of the ligand exchange, the carboxyl group-containing compound becomes a polymer crosslinked by the hypervalent iodine compound. Thus, it is preferable to complete the ligand exchange reaction and form a resist film.

[0434] [Pattern formation method] When the resist composition of the present invention is used in the manufacture of various integrated circuits, known lithography techniques can be applied. For example, a pattern formation method may include the steps of forming a resist film on a substrate using the resist composition described above, or on the resist underlayer of a substrate on which a resist underlayer film is laminated; exposing the resist film with high-energy rays; and developing the exposed resist film using a developer. Hereinafter, the resist underlayer film will also be simply referred to as the "underlayer film".

[0435] First, the resist composition of the present invention is applied to a substrate for integrated circuit manufacturing, or onto the underlying layer of a substrate with a laminated underlying layer (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.), or to a substrate for mask circuit manufacturing, or onto the underlying layer of a substrate with a laminated underlying layer (Cr, CrO, CrON, MoSi2, SiO2, etc.) using an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, so that the coating thickness is 0.01 to 2 μm. This is then pre-baked on a hot plate, preferably at 60 to 200°C for 10 seconds to 30 minutes, more preferably at 80 to 180°C for 30 seconds to 20 minutes, to form a resist film. The underlying layer refers to the film formed between the substrate and the resist film in a multilayer resist process, and the underlying layer is not particularly limited; conventionally known films can be used.

[0436] Next, the resist film is exposed using high-energy rays. Examples of high-energy rays include ultraviolet rays (g-rays (436 nm), h-rays (405 nm), i-rays (365 nm), etc.), far ultraviolet rays, EB, EUV, X-rays, soft X-rays, excimer laser light (KrF excimer laser light, ArF excimer laser light, etc.), gamma rays, and synchrotron radiation. Preferably, i-rays, KrF excimer laser light, ArF excimer laser light, electron beams, or extreme ultraviolet rays are used as the high-energy rays. When ultraviolet rays, far ultraviolet rays, EUV, X-rays, soft X-rays, excimer laser light, gamma rays, synchrotron radiation, etc. are used as the high-energy rays, the exposure amount is preferably 1 to 300 mJ / cm², either directly or using a mask to form the desired pattern. 2 To the extent, more preferably 10-200 mJ / cm² 2 Irradiate to a degree that results in the desired exposure. When using electroluminescence (EB) as the high-energy beam, the exposure amount is preferably 0.1 to 8000 μC / cm², either directly or using a mask to form the desired pattern. 2 To a degree, more preferably 0.5 to 5000 μC / cm² 2 The pattern is drawn to a certain extent. Furthermore, the resist composition of the present invention is particularly suitable for fine patterning using EB or EUV, among other high-energy rays.

[0437] After exposure, PEB (Photopolymerization) is performed as needed. In this case, it is preferable to perform the PEB on a hot plate or in an oven at 30 to 200°C for 10 seconds to 30 minutes, more preferably at 60 to 120°C for 30 seconds to 20 minutes.

[0438] After exposure or PEB, develop the image using a developer and then perform patterning. The developing solution used at this time is an alkaline aqueous solution such as tetramethylammonium hydroxide aqueous solution or tetrabutylammonium hydroxide aqueous solution; 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutylketone, 5-methyl-2-hexanone, methylcyclohexanone, acetophenone, methylacetophenone, isopropyl alcohol, isoamyl alcohol, n-butanol, tert-butyl alcohol, tert-pentyl alcohol, n-pentanol, cyclohexanol, formic acid, acetic acid, propionic acid, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, cyclohexyl acetate, 4-tert-butylcyclohexyl acetate, octyl acetate, isobornyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotate, chloro Ethyl tonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenyl acetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate Examples of organic solvents include zyl, 2-phenylethyl acetate, 1-propanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methyl-1-butanol, diacetone alcohol, 4-methyl-2-pentanol, 3-methylcyclohexanol, 3,5,5-trimethylhexyl alcohol, 2,6-dimethyl-4-heptanol, toluene, anisole, and ε-caprolactone. These developers may be used individually or in mixtures of two or more.

[0439] After development, rinsing is performed as needed. A solvent that mixes with the developer but does not dissolve the resist film is preferred as the rinsing solution. Preferred solvents include C3-C10 alcohols, C8-C12 ether compounds, C6-C12 alkanes, alkenes, alkynes, and aromatic solvents.

[0440] Rinsing can reduce the occurrence of deformation and defects in the resist pattern. However, rinsing is not always necessary, and omitting it can reduce the amount of solvent used.

[0441] As described above, the resist composition of the present invention, upon exposure, creates a difference in solubility between the exposed and unexposed areas, allowing for the formation of positive or negative patterns. Therefore, it is possible to use a developer that dissolves the exposed areas but not the unexposed areas, or vice versa. Thus, the pattern formation method of the present invention can be widely applied to the formation of various fine patterns, as it can form positive or negative patterns by appropriately selecting the developer. [Examples]

[0442] The present invention will be specifically described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0443] [1] Synthesis of carboxyl group-containing polymers The monomers used in the synthesis of the carboxyl group-containing polymer are as follows: [ka]

[0444] [ka]

[0445] [ka]

[0446] [Synthesis Example 1-1] Preparation of Polymer P-1 Under a nitrogen atmosphere, monomer a-1 (56g) and monomer b-1 (36g) were dissolved in 100g of MEK, and solution A was prepared by repeating vacuum degassing and nitrogen purging for 20 minutes three times. Separately, solution B was prepared by dissolving 2.90g of 2,2'-dimethyl(I-1) 2,2'-azobisisobutyrate in 10.0g of MEK, and repeating vacuum degassing and nitrogen purging for 20 minutes three times. Furthermore, solution C was prepared by dissolving 8.79g of 2-cyano-2-propylbenzodithioate in 20.0g of MEK, and repeating vacuum degassing and nitrogen purging for 20 minutes three times. The reactor for solution C was then heated to a temperature of 80°C. Solutions A and B were then added dropwise, independently using syringe pumps, over a period of 2 hours. After the addition was complete, the polymerization solution was stirred at 80°C for 6 hours and then cooled to room temperature (this is referred to as step RM-1). Next, 8.60 g of dimethyl 2,2'-azobisisobutyrate and 15.0 g of thioglycolic acid were dissolved in 33.3 g of MEK, and solution D was prepared by repeating vacuum degassing and nitrogen purging for 20 minutes three times. Solution D was added dropwise to the reaction solution of step RM-1 over 5 minutes using a syringe pump. After the addition was complete, the reactor was heated again to a temperature of 80°C, stirred for 2 hours while maintaining 80°C, and then cooled to room temperature. Next, the obtained polymerization solution was added dropwise to 4000 g of hexane that had been vigorously stirred, and the precipitated polymer was filtered off. The obtained polymer was washed twice with hexane (1200 g) and then vacuum-dried at 50°C for 20 hours to obtain polymer P-1, a white powder (yield 90 g, yield 98%). The Mw of polymer P-1 was 8000, and the Mw / Mn ratio was 1.11. Note that Mw is a standard polystyrene equivalent measurement obtained by GPC using THF as the solvent. Specifically, the details are as follows (the same applies below). ·Equipment: HLC-8320GPC • Column: TSK guardcolumn +TSKgel G4000HXL +TSKgel G2000HXL +TSKgel Super H5000 Pump and column constant temperature: 40°C ·Eluent:THF • Detector: RI (Differential Refraction) detector ·Injection volume: 100 μl

[0447] [Synthesis Examples 1-2 to 1-12] Synthesis of Polymers P-2 to P-12 The polymers shown in Table 1 below were synthesized using the same method as in Synthesis Example 1-1, except that the types and mixing ratios of each monomer were changed.

[0448] [Synthesis Example 1-13] Synthesis of Polymer P-13 Under a nitrogen atmosphere, monomer a-1 (56g), monomer b-1 (36g), 5.4g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 180g of MEK were placed in a flask to prepare a monomer-polymerization initiator solution. In another flask under a nitrogen atmosphere, 55g of MEK was placed and heated to 80°C with stirring, and then the monomer-polymerization initiator solution was added dropwise over 4 hours. After the addition was complete, the polymerization solution was kept at 80°C and stirred for 2 hours, then cooled to room temperature. The obtained polymerization solution was added dropwise to 4000g of hexane that had been vigorously stirred, and the precipitated polymer was filtered off. The obtained polymer was washed twice with hexane (1200g) and then vacuum-dried at 50°C for 20 hours to obtain a white powdery polymer P-13 (yield 90g, yield 98%). The Mw of polymer P-13 was 8000, and the Mw / Mn ratio was 1.42. Note that Mw is a polystyrene-converted measurement value obtained by GPC using THF as the solvent.

[0449] [Synthesis Examples 1-14, 1-15] Synthesis of polymers P-14 and P-15 The polymers shown in Table 1 below were synthesized using the same method as in Synthesis Example 1-13, except that the types and mixing ratios of each monomer were changed.

[0450] [Table 1]

[0451] As shown in Table 1, living radical polymerization using a RAFT agent yielded a narrowly dispersed polymer with low dispersion (Mw / Mn).

[0452] [2] Preparation of resist composition [Examples 2-1 to 2-20, Comparative Examples 2-1 to 2-4] Resist compositions (R-01 to R-20, CR-01 to CR-02) were prepared by dissolving hypervalent iodine compounds and carboxyl group-containing compounds in a solvent containing 0.01% by mass of surfactant (PF-636, manufactured by Omnova) in the compositions shown in Table 2 below, and filtering the resulting solution through a 0.2 μm Teflon® filter. Furthermore, resist compositions (CR-03 to CR-04) were prepared by dissolving polymers, photoacid generators, and sensitivity modifiers in a solvent containing 0.01% by mass of surfactant (PF-636, manufactured by Omnova) in the compositions shown in Table 3 below, and filtering the resulting solution through a 0.2 μm Teflon® filter.

[0453] [Table 2]

[0454] [Table 3]

[0455] In Tables 2 and 3, the hypervalent iodine compounds I-1 to I-9, the photoacid generator PAG-1, the sensitivity modifier Q-1, and the solvent are as follows: [ka]

[0456] [ka]

[0457] [ka]

[0458] • Solvent: PGMEA (Propylene glycol monomethyl ether acetate) AcOH (acetic acid) GBL (γ-butyrolactone)

[0459] [3] EUV lithography evaluation (line and space pattern) [Examples 3-1 to 3-20, Comparative Examples 3-1 to 3-4] Each resist composition (R-01 to R-20, CR-01 to CR-04) was spin-coated onto a Si substrate formed with a silicon-containing spin-on hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. to a thickness of 20 nm. The resist film was then pre-baked (PAB) for 60 seconds at the temperature listed in Table 4 using a hot plate to produce a resist film with a thickness of 40 nm. A 36 nm line-and-space (LS) 1:1 pattern was exposed onto the resist film using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9, 90-degree dipole illumination). PEB was then performed on a hot plate for 60 seconds at the temperature listed in Table 4, followed by development for 30 seconds using the developer listed in Table 4 to form an LS pattern with a space width of 18 nm and a pitch of 36 nm.

[0460] The obtained resist patterns were evaluated as follows. The results are shown in Table 4.

[0461] [Sensitivity evaluation] The aforementioned LS pattern was observed using a Hitachi High-Tech SEM (CG-6300) to determine the optimal exposure dose Eop(mJ / cm²) for obtaining an LS pattern with a space width of 18 nm and a pitch of 36 nm. 2 We calculated this value and defined it as the sensitivity.

[0462] [LWR rating] The LS pattern obtained by irradiating with the optimal exposure was measured at 10 points along the longitudinal direction of the space width using a Hitachi High-Tech SEM (CG-6300), and the LWR was calculated as three times the standard deviation (σ) (3σ) from the results. The smaller this value, the less roughness and the more uniform the space width pattern obtained.

[0463] [Evaluation of Limit Resolution] The minimum line width (nm) at which the pattern can be resolved by gradually increasing the exposure from the optimal exposure for forming the aforementioned LS pattern was determined using a Hitachi High-Tech SEM (CG-6300), and this was defined as the limiting resolution (nm). A smaller value indicates superior limiting resolution and the ability to form finer patterns.

[0464] [Table 4]

[0465] Developer: nBA (butyl acetate) TMAH (2.38% by mass tetramethylammonium hydroxide aqueous solution)

[0466] The results shown in Table 4 indicate that both positive and negative patterns can be formed depending on the developer used. Furthermore, comparing the resist compositions of Comparative Examples 3-1 and 3-2 with the resist composition of the present invention, it was found that Examples 3-1 to 3-20 exhibited excellent sensitivity, resolution, and LWR. This was also evident when compared to Comparative Examples 3-3 and 3-4, which are chemically amplified resist compositions using an acid catalyst reaction. Therefore, the resist composition of the present invention was found to exhibit excellent sensitivity, resolution, and LWR in LS pattern formation by EUV exposure.

[0467] [4] EUV lithography evaluation (contact hole pattern) [Examples 4-1 to 4-20, Comparative Examples 4-1 to 4-4] Each resist composition (R-01 to R-20, CR-01 to CR-04) was spin-coated onto a Si substrate formed with a silicon-containing spin-on hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. to a thickness of 20 nm. The resist film was then processed using a hot plate at the temperature listed in Table 5 for 60 seconds to produce a resist film with a thickness of 50 nm. Next, the resist film was exposed using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9 / 0.6, quadruple pole illumination, wafer-mounted dimensions of 64 nm pitch, +20% bias hole pattern mask). The resist film was then processed using a hot plate at the temperature listed in Table 5 for 60 seconds, followed by development using the developer listed in Table 5 for 30 seconds to obtain a hole pattern with dimensions of 32 nm.

[0468] The obtained resist patterns were evaluated as follows. The results are shown in Table 5.

[0469] [Sensitivity evaluation] The aforementioned contact hole pattern was observed using a Hitachi High-Tech SEM (CG-6300) to determine the optimal exposure dose Eop(mJ / cm²) for obtaining a hole pattern with dimensions of 22 nm. 2 We calculated this value and defined it as the sensitivity.

[0470] [CDU Rating] The dimensions of 50 hole patterns obtained by irradiating with the optimal exposure were measured, and the standard deviation (σ) calculated from these results was multiplied by three (3σ) to determine the CDU. A smaller CDU value indicates a more uniform hole diameter pattern.

[0471] [Evaluation of Limit Resolution] The minimum hole diameter (nm) that can be resolved by gradually decreasing the exposure amount from the optimal exposure amount for forming the aforementioned hole pattern was determined using a Hitachi High-Technologies Corporation length-measuring SEM (CG-6300), and this was defined as the limiting resolution (nm). A smaller value indicates superior limiting resolution and the ability to form patterns with finer hole diameters.

[0472] [Table 5]

[0473] The results shown in Table 5 indicate that both positive and negative patterns can be formed depending on the developer used. Furthermore, comparing the resist compositions of Comparative Examples 4-1 and 4-2 with the resist composition of the present invention, it was found that Examples 4-1 to 4-20 exhibited excellent sensitivity, resolution, and CDU. This was also evident when compared to Comparative Examples 4-3 and 4-4, which are chemically amplified resist compositions using an acid catalyst reaction. Therefore, the resist composition of the present invention was found to exhibit excellent sensitivity, resolution, and CDU in CH pattern formation by EUV exposure.

[0474] This specification includes the following embodiments: [1]: A resist composition comprising a hypervalent iodine compound, a carboxyl group-containing polymer, and a solvent, A resist composition characterized in that the carboxyl group-containing polymer is a polymer containing repeating units of a carboxylic acid derivative represented by the following formula (1), and the degree of dispersion Mw / Mn, determined from the weight-average molecular weight Mw and number-average molecular weight Mn measured by gel permeation chromatography of the polymer, is 1.30 or less. [ka] (In the formula, R A X is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. A This refers to a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 - is X A1 This is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. (* represents a bond with a carbon atom of the polymer backbone.) [2]: The resist composition of [1], characterized in that the hypervalent iodine compound is at least one selected from the group consisting of hypervalent iodine compounds represented by the following formulas (2) to (11). [ka] (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, and when m3 is 1 When n10 is 0, 1, 2, 3, 4, 5, or 6, and 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, and 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, and when m5 is 1, n12 is 0, 1, 2, 3, 4, 5, or 6, and n13, n14 are 0, 1, 2, 3, 4, 5, or 6, and n15, n16 are 0 n17 is 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; 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, and R. 1 ~R 22 Each of these is independently a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 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 However, they may bond to each other and form a ring together with the carbonyloxy groups to which they are bonded and the atoms between the carbonyloxy groups, R 21 and R 22 These atoms may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between the carbon atoms. 31 ~R 34 , R 37 , R 39 ~R 46 , R 49 , R 50 Each of these is a hydrocarbyl group having 1 to 40 carbon atoms, which may each contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 31 These may be the same or different from each other, and there may be multiple R 31 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 32 These may be the same or different from each other, and there may be multiple R 32However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 33 These may be the same or different from each other, and there may be multiple R 33 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 34 These may be the same or different from each other, and there may be multiple R 34 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n9 is 2 or more, each R 37 These may be the same or different from each other, and there may be multiple R 37 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n10 is 2 or more, each R 39 These may be the same or different from each other, and there may be multiple R 39 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n11 is 2 or more, each R 40 These may be the same or different from each other, and there may be multiple R 40 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n12 is 2 or more, each R 41 These may be the same or different from each other, and there may be multiple R 41 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n13 is 2 or more, each R 42 These may be the same or different from each other, and there may be multiple R 42 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n14 is 2 or more, each R 43 These may be the same or different from each other, and there may be multiple R 43 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n15 is 2 or more, each R 44 These may be the same or different from each other, and there may be multiple R 44 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n16 is 2 or more, each R 45These may be the same or different from each other, and there may be multiple R 45 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n17 is 2 or more, each R 46 These may be the same or different from each other, and there may be multiple R 46 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n18 is 2 or more, each R 49 These may be the same or different from each other, and there may be multiple R 49 However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n19 is 2 or more, each R 50 These may be the same or different from each other, and there may be multiple R 50 However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 35 R is a (n8) valent hydrocarbon group having 1 to 40 carbon atoms or a (n8) valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, 35 This may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. Furthermore, some or all of the hydrogen atoms of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- of the (n8) valent hydrocarbon group may be substituted with a group containing a heteroatom, R 34 and R 35 However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms. 36 R is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 38 is a carbonyl group or a C1-C10 hydrocarbylene group which may contain a heteroatom. *1 and *2 represent the bonds with the carbon atoms of the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms of the aromatic ring. L1 is bondless, a single bond, -O-, -S-, -NH- or -CH2-, and R 47is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. X is nitrogen or sulfur, and in the case of nitrogen, R 48 It may have R 48 This is a hydrocarbyl group having 1 to 20 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom. [3]: A laminate characterized by comprising a substrate and a resist film which is a film formed of the resist composition of [1] or [2] on the substrate. [4]: The laminate of [3], further comprising a resist underlayer film between the substrate and the resist film. [5]: A laminate of [3] or [4] characterized in that the resist film contains ligand exchange reaction products of the hypervalent iodine compound and the carboxyl group-containing polymer. [6]: A pattern forming method characterized by comprising the steps of: forming a resist film on a substrate or on a resist underlayer of a substrate having a resist underlayer laminated thereon using the resist composition of [1] or [2]; exposing the resist film with a high-energy beam; and developing the exposed resist film using a developer. [7]: The pattern formation method of [6], characterized in that the high-energy ray is an i-ray, a KrF excimer laser beam, an ArF excimer laser beam, an electron beam, or an extreme ultraviolet beam. [8]: A method for producing a resist composition of [1] or [2], A method for producing a resist composition, comprising the steps of synthesizing the carboxyl group-containing polymer by living radical polymerization using a radical initiator and a reversible addition-cleavage chain transfer agent (RAFT agent) represented by the following formula (R-1) or (R-2), and mixing the obtained carboxyl group-containing polymer with the hypervalent iodine compound and the solvent. [ka] (In the formula, R X1 and R X3These are, independently, a saturated hydrocarboxylthio group with 3 to 20 carbon atoms, an aralkylthio group with 7 to 20 carbon atoms, a heterocyclyl group with 5 to 20 carbon atoms, and -N(Z A )(Z B ), -COOZ A ,-OCOZ A , -CON(Z A )(Z B ), -P(=O)(OZ A )2 or -OP(=O)(Z A )(Z B ) is Z A and Z B Each of these is independently a saturated hydrocarbyl 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 case, some or all of the hydrogen atoms bonded to the carbon atom may be substituted with cyano groups, carboxyl groups, etc. X2 and R X4 These are, independently, a saturated hydrocarbyl group having 2 to 20 carbon atoms, which may contain heteroatoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0475] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that has substantially the same technical idea as described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. A resist composition comprising a hypervalent iodine compound, a carboxyl group-containing polymer, and a solvent, A resist composition characterized in that the carboxyl group-containing polymer is a polymer containing repeating units of a carboxylic acid derivative represented by the following formula (1), and the degree of dispersion Mw / Mn, determined from the weight-average molecular weight Mw and number-average molecular weight Mn measured by gel permeation chromatography of the polymer, is 1.30 or less. 【Chemistry 1】 (In the formula, R Ａ X is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. Ａ This refers to a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-X Ａ１ - is true. X Ａ１ This is a saturated hydrocarbylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. (* indicates a bond with a carbon atom of the polymer backbone.)

2. The resist composition according to claim 1, characterized in that the hypervalent iodine compound is at least one selected from the group consisting of hypervalent iodine compounds represented by the following formulas (2) to (11). 【Chemistry 2】 (In the formula, m1 is 0, 1, or 2. When m1 is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1 ≤ n1 + n2 ≤ 6.) When m1 is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1 ≤ n1 + n2 ≤ 8. When m1 is 2, n1 is 1, 2, or 3, 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, 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; when m6 is 2, n17 is 0, 1, 2, 3, 4, 5, 6, 7 or 8, where 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 of these is independently a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. 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 may combine with each other to form a ring together with the carbonyl oxy group to which they are attached and the atoms between the carbonyl oxy groups. R ２１ and R ２２ may combine with each other to form a ring together with the carbon atoms to which they are attached and the atoms between the carbon atoms. R ３１ to R ３４ , R ３７ , R ３９ to R ４６ , R ４９ , R ５０ is, independently of each other, a halogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a hetero atom. When n2 is 2 or more, each R ３１ may be the same as or different from each other, and a plurality of R ３１ may combine with each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. When n4 is 2 or more, each R ３２ may be the same as or different from each other, and a plurality of R ３２ may combine with each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. When n6 is 2 or more, each R ３３ may be the same as or different from each other, and a plurality of R ３３ may combine with each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. When n7 is 2 or more, each R ３４ may be the same as or different from each other, and a plurality of R ３４ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n9 is 2 or more, each R ３７ These may be the same or different from each other, and there may be multiple R ３７ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n10 is 2 or more, each R ３９ These may be the same or different from each other, and there may be multiple R ３９ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n11 is 2 or more, each R ４０ These may be the same or different from each other, and there may be multiple R ４０ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n12 is 2 or more, each R ４１ These may be the same or different from each other, and there may be multiple R ４１ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n13 is 2 or more, each R ４２ These may be the same or different from each other, and there may be multiple R ４２ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n14 is 2 or more, each R ４３ These may be the same or different from each other, and there may be multiple R ４３ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n15 is 2 or more, each R ４４ These may be the same or different from each other, and there may be multiple R ４４ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n16 is 2 or more, each R ４５ These may be the same or different from each other, and there may be multiple R ４５ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n17 is 2 or more, each R ４６ These may be the same or different from each other, and there may be multiple R ４６ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n18 is 2 or more, each R ４９ These may be the same or different from each other, and there may be multiple R ４９ However, they may bond with each other and form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n19 is 2 or more, each R ５０ These may be the same or different from each other, and there may be multiple R ５０ However, they may bond with each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. ３５ is a (n8) valent hydrocarbon group having 1 to 40 carbon atoms or a (n8) valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R ３５ The (n8) valent hydrocarbon group or (n8) valent heterocyclic group may 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 of the (n8) valent hydrocarbon group or (n8) valent heterocyclic group may be substituted with a group containing a heteroatom, and the (n8) valent hydrocarbon group may be -CH ２ - may be partially substituted with a group containing a heteroatom, R ３４ and R ３５ However, they may bond with each other to form a ring together with the carbon atoms to which they are bonded and the atoms between those carbon atoms. ３６ This is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. ３８ This is a carbonyl group or a C1-C10 hydrocarbylene group which may contain a heteroatom. *1 and *2 represent the bonds with the carbon atoms of the aromatic ring in the formula. However, *1 and *2 are bonded to adjacent carbon atoms of the aromatic ring. L １ This can be any bondless, single bonded, -O-, -S-, -NH-, or -CH ２ - and R ４７ This is a C1-C10 hydrocarbyl group which may contain a halogen atom or a heteroatom. X is nitrogen or sulfur, and in the case of nitrogen, R ４８ It may have R. ４８ This is a hydrocarbyl group having 1 to 20 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom.

3. A laminate characterized by comprising a substrate and a resist film on the substrate which is a film formed from the resist composition described in claim 1 or claim 2.

4. The laminate according to claim 3, further comprising a resist underlayer film between the substrate and the resist film.

5. The laminate according to claim 3, characterized in that the resist film contains a ligand exchange reaction product between the hypervalent iodine compound and the carboxyl group-containing polymer.

6. A pattern forming method characterized by comprising the steps of: forming a resist film on a substrate or on a resist underlayer of a substrate having a resist underlayer laminated thereon using the resist composition according to claim 1 or claim 2; exposing the resist film with a high-energy beam; and developing the exposed resist film using a developer.

7. The pattern formation method according to claim 6, characterized in that i-rays, KrF excimer laser light, ArF excimer laser light, electron beams, or extreme ultraviolet light are used as the high-energy rays.

8. A method for producing the resist composition according to claim 1, A method for producing a resist composition, comprising the steps of synthesizing the carboxyl group-containing polymer by living radical polymerization using a radical initiator and a reversible addition-cleavage chain transfer agent (RAFT agent) represented by the following formula (R-1) or (R-2), and mixing the obtained carboxyl group-containing polymer with the hypervalent iodine compound and the solvent. 【Transformation 3】 (wherein, R Ｘ１ and R Ｘ３ are each independently a saturated hydrocarbylthio group having 3 to 20 carbon atoms, an aralkylthio group having 7 to 20 carbon atoms, a heterocyclyl group having 5 to 20 carbon atoms, -N(Z Ａ )(Z Ｂ ), -COOZ Ａ , -OCOZ Ａ , -CON(Z Ａ )(Z Ｂ ), -P(=O)(OZ Ａ )<00,00087> or -O-P(=O)(Z Ａ )(Z Ｂ ). Z Ａ and Z Ｂ are each independently a saturated hydrocarbyl 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 may have a part or all of the hydrogen atoms bonded to the carbon atoms thereof substituted with a cyano group, a carboxy group or the like. R Ｘ２ and R Ｘ４ are each independently a saturated hydrocarbyl group having 2 to 20 carbon atoms which may contain a heteroatom, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.).

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