Resist composition, laminate, and pattern forming method

Abstract

The present invention relates to a resist composition, a laminate, and a pattern forming method. The object of the present invention is to provide a resist composition which can achieve high sensitivity and high resolution in a pattern forming method. The means for solving the object is a resist composition comprising: a high-valent iodine compound represented by the following formula (1), a carboxyl group-containing compound, and a solvent. R 11 is a halogen atom, or a hydrocarbon group having 1 to 10 carbons which can also contain a hetero atom. R 12 is a halogen atom, or a hydrocarbon group having 1 to 40 carbons which can also contain a hetero atom. R 14 is a halogen atom, or a hydrocarbon group having 1 to 40 carbons which can also contain a hetero atom. R 13 is a carbonyl group, or a hydrocarbylene group having 1 to 10 carbons which can also contain a hetero atom. X 1 is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 1 is a nitrogen atom has R 15 .

Description

Technical Field

[0001] This invention relates to resist compositions, laminates, and methods for forming patterns. Background Technology

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

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

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

[0005] Materials used in non-chemically amplified resist compositions include polymethyl methacrylate (PMMA). PMMA is a positive resist material whose main chain is broken and its molecular weight reduced by EUV irradiation, thereby improving its solubility in organic solvent developers.

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

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

[0008] As a method to reduce the impact of shot noise from the resist aspect, introducing elements with high absorption of EUV light has attracted attention. Patent Document 1 proposes a chemically amplified resist composition containing iodine atoms with high absorption of EUV light. However, as mentioned above, chemically amplified resist compositions cannot achieve excellent resolution in EUV lithography with increasingly smaller processing dimensions in the future.

[0009] Patent document 2 claims the use of a negative resist composition of tin compounds. This is because tin, which has high absorption under EUV light, is used as the main component, thus improving randomness and achieving high sensitivity and high resolution. However, such a metal resist has many problems, such as insufficient solubility in the resist solvent, storage stability, and defects caused by residues after etching.

[0010] In contrast, Patent Document 3 proposes a positive resist composition using a high-valent iodine compound. It contains iodine, which has high absorption for EUV light, thus improving randomness similar to metal resists and achieving high sensitivity and resolution. Furthermore, since it consists only of organic molecules, it addresses the problems of metal resists, namely developer solubility and residue. However, the performance of this resist material remains unsatisfactory, and there is a need to develop resist materials useful for forming finer patterns.

[0011] Existing technical documents

[0012] Patent documents

[0013] [Patent Document 1] Japanese Patent Application Publication No. 2018-5224

[0014] [Patent Document 2] Japanese Patent Publication No. 2021-503482

[0015] [Patent Document 3] Japanese Patent Application Publication No. 2023-167368

[0016] Non-patent literature

[0017] [Non-Patent Literature 1] SPIE Vol. 5039 p1 (2003)

[0018] [Non-Patent Literature 2] SPIE Vol. 6520 p65203L-1 (2007) Summary of the Invention

[0019] [The problem that the invention aims to solve]

[0020] The present invention was made in view of the foregoing circumstances, and its object is to provide a resist composition that can achieve high sensitivity and high resolution in a pattern forming method, a laminate having a resist film obtained from the resist composition, and a pattern forming method using the resist composition.

[0021] [Methods for solving the problem]

[0022] To address the aforementioned issues, the present invention provides a resist composition characterized by containing:

[0023] The high-valent iodine compound represented by formula (1) below,

[0024] Compounds containing carboxyl groups, and

[0025] Solvent.

[0026] [Chemistry 1]

[0027]

[0028] In the formula, m1 is an integer from 0 to 2, n1 is an integer from 0 to 3 when m1 is 0, an integer from 0 to 5 when m1 is 1, and an integer from 0 to 7 when m1 is 2.

[0029] R 11 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms.

[0030] R 12 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms.

[0031] R 14 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n1 is 2 or more, each R 14 They can be the same or different. Also, multiple R's...14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0032] R 13 It is a carbonyl group, or may contain heteroatoms and carbonyl groups with 1 to 10 carbon atoms.

[0033] X 1 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 1 When it is a nitrogen atom, it has R 15 R 15 It consists of a hydrogen atom, a carbonyl group, a halogen atom, or a hydrocarbon group or ester with 1 to 20 carbon atoms that may also contain heteroatoms.

[0034] Thus, the resist composition of the present invention has iodine atoms with high absorption capacity for EUV light. Furthermore, the high-valent iodine compound represented by formula (1) is obtained by introducing a substituent R at the ortho position of the iodine atom. 12 The photodegradability is improved by the strain energy caused by the steric barrier. As a result, the resist composition of the present invention exhibits higher sensitivity than when using other high-valent iodine compounds alone. That is, due to these characteristics, the resist composition of the present invention can achieve high sensitivity, high resolution, and low LWR in patterning methods.

[0035] The aforementioned carboxyl-containing compounds are preferably polymers containing repeating units represented by formula (2) or compounds represented by formula (3).

[0036] [Chemistry 2]

[0037]

[0038] In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group.

[0039] X A For single bonds, phenylene, naphthylene or -C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. It represents the atomic bonds between carbon atoms in the main chain and the main chain.

[0040] p can be 1, 2, 3 or 4.

[0041] R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms. When p is 2, R 31It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing a heteroatom, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be replaced by a group containing a heteroatom.

[0042] R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group may be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group may also be replaced by a group containing a heteroatom. When p is 2, 3 or 4, each R 32 They can be the same or different.

[0043] If the resist composition contains such a carboxyl-containing compound, then high sensitivity, high resolution and low LWR can be achieved more reliably in the pattern forming method.

[0044] It should contain at least one of the high-valent iodine compounds represented by formula (4) or (5).

[0045] [Chemistry 3]

[0046]

[0047] In the formula, m4 and m5 are integers from 0 to 2.

[0048] When m4 is 0, n4 is an integer from 0 to 3; when m4 is 1, n4 is an integer from 0 to 5; and when m4 is 2, n4 is an integer from 0 to 7.

[0049] When m5 is 0, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 5, and satisfies 1≤(n5+n6)≤6.

[0050] When m5 is 1, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 7, and satisfies 1≤(n5+n6)≤8.

[0051] When m5 is 2, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 9, and satisfies 1≤(n5+n6)≤10.

[0052] 1 and 2 represents the atomic bond of the carbon atom in the aromatic ring in the formula. However, 1 and 2. It must be bonded to an adjacent carbon atom on the aromatic ring.

[0053] R 41 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms.

[0054] R 42It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n4 is 2 to 7, each R 42 They can be the same or different. Also, multiple R's... 42 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. However, R 42 It will not be key to and 1. Carbon atoms on adjacent aromatic rings.

[0055] R 43 It is a carbonyl group, or may contain heteroatoms and carbonyl groups with 1 to 10 carbon atoms.

[0056] X 4 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 4 When it is a nitrogen atom, it has R 44 R 44 It consists of a hydrogen atom, a carbonyl group, a halogen atom, or a hydrocarbon group or ester with 1 to 20 carbon atoms that may also contain heteroatoms.

[0057] R 51 and R 52 Each R is an independent hydrocarbon group with 1 to 10 carbon atoms, which may also contain heteroatoms. When n6 is 2 to 3, each R 51 and R 52 They can be the same or different.

[0058] R 53 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n5 is 2 to 9, each R 53 They can be the same or different. Also, multiple R's... 53 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0059] By using high-valent iodine compounds containing the above formula (4) or formula (5), the reactivity to light can be controlled, and the sensitivity can be adjusted.

[0060] Furthermore, the present invention provides a laminated body characterized by comprising:

[0061] substrate, and

[0062] The resist film on the substrate is derived from the resist composition of the present invention.

[0063] The laminate of the present invention, comprising a resist film derived from the resist composition of the present invention, exhibits high sensitivity and excellent limiting resolution, is effective in precision micro-machining, and is applicable to the formation of any pattern, both positive and negative. Therefore, the laminate of the present invention has a wide range of applications and is highly useful in resist manufacturing technology.

[0064] At this time, a lower resist film may also be provided between the aforementioned substrate and the aforementioned resist film.

[0065] When forming a pattern, if a photoresist underlayer is necessary, a photoresist underlayer can also be appropriately placed between the substrate and the photoresist film.

[0066] Furthermore, the aforementioned resist film may contain the coordination exchange reaction products of the aforementioned high-valent iodine compound and the aforementioned carboxyl-containing compound.

[0067] For example, resist films may also contain coordination exchange reaction products of high-valent iodine compounds and carboxyl-containing compounds, but are not limited to this.

[0068] Furthermore, the present invention provides a pattern forming method, characterized by comprising the following steps:

[0069] A resist film is formed on a substrate or on a substrate having a resist underlayer film stacked thereon using the resist composition of the present invention.

[0070] The aforementioned resist film was exposed to high-energy rays, and

[0071] The previously exposed resist film was developed using a developer.

[0072] If this is the pattern forming method of the present invention, then by using the resist composition of the present invention, high sensitivity, high resolution and low LWR can be achieved.

[0073] For example, the aforementioned high-energy rays can be i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet light.

[0074] High-energy rays can be various types of high-energy rays as described above.

[0075] For example, the aforementioned developer can be used to dissolve the exposed portion but not the unexposed portion.

[0076] Alternatively, the aforementioned developer can be used to dissolve the unexposed areas without dissolving the exposed areas.

[0077] Thus, the pattern forming method of the present invention can be applied to the formation of any pattern, whether positive or negative.

[0078] [The effects of the invention]

[0079] As described above, the resist composition of the present invention can achieve both high sensitivity and high resolution in patterning methods, such as optical lithography using high-energy rays, especially electron beam (EB) lithography and EUV lithography. Therefore, the resist composition of the present invention is extremely useful in forming fine patterns.

[0080] Furthermore, if it is a laminate of the present invention, it can be applied to the formation of any pattern in positive and negative molds, with a wide range of uses and high usefulness in resist manufacturing technology.

[0081] Moreover, the pattern forming method of the present invention can achieve both high sensitivity and high resolution. Attached Figure Description

[0082] [ Figure 1 This is a schematic cross-sectional view showing an example of the laminate of the present invention. Detailed Implementation

[0083] As mentioned above, there is a need to develop resist compositions that can achieve high sensitivity and high resolution in patterning methods.

[0084] After repeated and in-depth exploration of the above-mentioned issues, the inventors obtained the following insights and thus completed the present invention: a resist composition mainly composed of a predetermined high-valent iodine compound and a carboxyl-containing polymer has extremely high sensitivity and can provide a resist film exhibiting excellent resolution, which is extremely effective in precision micro-machining.

[0085] That is, the present invention is a resist composition characterized by containing:

[0086] The high-valent iodine compound represented by formula (1) below,

[0087] Compounds containing carboxyl groups, and

[0088] Solvent.

[0089] [Chemistry 4]

[0090]

[0091] In the formula, m1 is an integer from 0 to 2, n1 is an integer from 0 to 3 when m1 is 0, an integer from 0 to 5 when m1 is 1, and an integer from 0 to 7 when m1 is 2.

[0092] R 11 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms.

[0093] R 12 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms.

[0094] R 14 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n1 is 2 or more, each R 14 They can be the same or different. Also, multiple R's... 14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0095] R 13 It is a carbonyl group, or may contain heteroatoms and carbonyl groups with 1 to 10 carbon atoms.

[0096] X 1 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 1 When it is a nitrogen atom, it has R 15 R 15 It consists of a hydrogen atom, a carbonyl group, a halogen atom, or a hydrocarbon group or ester with 1 to 20 carbon atoms that may also contain heteroatoms.

[0097] The present invention will now be described in detail, but it is not limited thereto.

[0098] [Resist Composition]

[0099] The resist composition of the present invention contains a high-valent iodine compound represented by formula (1), a carboxyl-containing compound, and a solvent as the main components.

[0100] [Chemistry 5]

[0101]

[0102] In the formula, m1 is an integer from 0 to 2, n1 is an integer from 0 to 3 when m1 is 0, an integer from 0 to 5 when m1 is 1, and an integer from 0 to 7 when m1 is 2.

[0103] R 11 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms.

[0104] R 12 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms.

[0105] R 14 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n1 is 2 or more, each R 14 They can be the same or different. Also, multiple R's... 14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0106] R 13 It is a carbonyl group, or may contain heteroatoms and carbonyl groups with 1 to 10 carbon atoms.

[0107] X 1 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 1 When it is a nitrogen atom, it has R 15 R 15 It consists of a hydrogen atom, a carbonyl group, a halogen atom, or a hydrocarbon group or ester with 1 to 20 carbon atoms that may also contain heteroatoms.

[0108] As described above, the resist composition of the present invention contains a high-valent iodine compound represented by formula (1) and a carboxyl-containing compound as its main components. On the other hand, the resist composition of the present invention may not contain the base polymer containing acid-instable groups or the photoacid generator found in conventional chemically amplified resist compositions. However, the resist composition of the present invention, especially when exposed to EB or EUV, can still produce differences in solubility between the exposed and unexposed areas, forming positive or negative patterns. The mechanism is not fully elucidated, but is speculated, for example, as follows, but is not limited to theoretical explanations.

[0109] The high-valent iodine compound represented by formula (1) is a compound having a tricoordinate high-valent iodine atom with a carboxylic acid ligand. It is believed that by mixing such a tricoordinate iodine compound with a carboxylic acid compound, the exchange of carboxylic acid ligands will occur in an equilibrium reaction. At this time, if the original carboxylic acid ligand can be removed by any method, a high-valent iodine compound with a new ligand will be generated. For example, if 3-methyl-1-acetoxy-1,2-benzoiodoxapentane-3-(1H)-one, which is more easily obtained in the form of a high-valent iodine compound, and a carboxylic acid compound with a large molecular weight are mixed, and the low-boiling acetic acid generated is removed, the ligand exchange will be completed. Here, the carboxyl-containing compound becomes a polymer crosslinked with the high-valent iodine compound.

[0110] Polymers crosslinked with high-valent iodine compounds are formed during film formation. This is because even if such crosslinked polymers are synthesized beforehand, they are insoluble in most organic solvents, making solution preparation impossible. It is speculated that this is because the high-valent iodine compounds, which originally have high polarization and low solvent solubility, use carboxyl-containing compounds as ligands, further worsening their solubility. Therefore, it is advisable to remove the original low-molecular-weight carboxylic acid components during film formation and the subsequent baking step, thereby completing the ligand exchange reaction and simultaneously forming the resist film.

[0111] In the resist film of the present invention, which is formed on a substrate in this manner, the high-valent iodine compound, as its main component, decomposes under light, thereby changing its polarity and forming a pattern using a development step. Furthermore, by appropriately selecting a developer, either a positive or negative pattern can be formed.

[0112] The resist composition of this invention can be either positive or negative depending on the selection of its components. In the positive case, it contains a polymer bonded by hypervalent iodine compounds during film formation. This polymer decomposes under light, becoming a monovalent iodine compound, while the bonds between the carboxyl-containing compound and the hypervalent iodine compound break, resulting in a decrease in molecular weight. It is presumably the result of forming a positive pattern where the exposed areas are removed by organic solvents.

[0113] On the other hand, in the negative case, there is a polymer cross-linked with high-valent iodine compounds generated during film formation. This polymer decomposes under light, causing cross-linking or bond exchange, and resulting in increased molecular weight and polarity reversal. It is speculated that this will result in a negative pattern where the unexposed areas are removed by the alkaline solution.

[0114] Based on the foregoing, it can be inferred 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 a base polymer containing acid-instable groups or a photoacid generator as in known chemically amplified resist compositions, thus avoiding adverse effects caused by acid diffusion (e.g., image blurring) and enabling the resolution of fine patterns.

[0115] The resist composition of the present invention is particularly effective in EUV lithography. This is because the resist composition of the present invention has iodine atoms with high absorption capacity for EUV light, and the high-valent iodine compound represented by formula (1) has a substituent R introduced at the ortho position of the iodine atom. 12 Therefore, the photodegradability is improved due to the strain energy caused by the steric barrier, resulting in a higher sensitivity compared to using other high-valent iodine compounds alone. That is, the resist composition of the present invention, by virtue of these characteristics, can achieve high sensitivity, high resolution, and low LWR in the patterning method.

[0116] Regarding resist compositions for EUV lithography capable of forming fine patterns, there have been reports of metal resists with tin compounds as the main component, which have a similar high absorption capacity for EUV light as iodine atoms (e.g., Patent Document 2). However, as mentioned above, such metal resists suffer from many problems, including insufficient solvent solubility, poor storage stability, and defects caused by etching residues due to the presence of metal elements. On the other hand, the resist composition of the present invention does not use metal elements, thus it is more advantageous than metal resists in terms of defects and does not have the problem of solvent solubility. Furthermore, the resist composition of the present invention is applicable to both positive and negative modes, thus having a wide range of applications. For example, in the contact hole formation step, metal resists implemented with negative development require a reversal process after the pillar pattern is formed, while positive resists do not require such a step. Therefore, from the viewpoint of process simplicity, the resist composition of the present invention can be considered more useful than metal resists.

[0117] Japanese Patent Application Publication Nos. 2015-180928 and 2018-95853 disclose resist compositions containing hypervalent iodine compounds as additives, and resist compositions formed by incorporating hypervalent iodine compounds into the polymer backbone of a base polymer. However, in these patent documents, regarding the characteristics of the aforementioned resist compositions, only the ability to improve line edge roughness is described, but the possibility of photodecomposition of the hypervalent iodine compounds is not mentioned at all, nor is the possibility of functioning as a material in non-chemically amplified resist compositions mentioned. Furthermore, according to the descriptions and specific examples related to their doping amounts, the hypervalent iodine compounds are not the main component. Also, Patent Document 3 proposes a positive resist composition using hypervalent iodine compounds, but does not describe the hypervalent iodine compounds represented by formula (1) of the present invention, and does not mention at all the effect of improving photodecomposability and further improving sensitivity by introducing substituents at the ortho position of iodine atoms due to strain energy caused by steric hindrance. Therefore, these patent documents cannot conceive of a non-chemically amplified resist composition as presented in this invention, which offers extremely high sensitivity and excellent resolution, and is highly effective in precision micro-machining. In other words, this invention clearly provides a novel resist composition and a method for patterning.

[0118] The components of the resist composition of the present invention will be described below.

[0119] [High-valent iodine compounds]

[0120] The aforementioned high-valent iodine compounds are tricoordinate high-valent iodine compounds represented by the following formula (1).

[0121] [Chemistry 6]

[0122]

[0123] In the formula, m1 is an integer from 0 to 2, n1 is an integer from 0 to 3 when m1 is 0, an integer from 0 to 5 when m1 is 1, and an integer from 0 to 7 when m1 is 2.

[0124] R 11 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms.

[0125] R 12 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms.

[0126] R 14 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n1 is 2 or more, each R 14 They can be the same or different. Also, multiple R's... 14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0127] R13 It is a carbonyl group, or may contain heteroatoms and carbonyl groups with 1 to 10 carbon atoms.

[0128] X 1 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 1 When it is a nitrogen atom, it has R 15 R 15 It consists of a hydrogen atom, a carbonyl group, a halogen atom, or a hydrocarbon group or ester with 1 to 20 carbon atoms that may also contain heteroatoms.

[0129] In equation (1), m1 is an integer from 0 to 2, and n1 is an integer from 0 to 3 when m1 is 0, an integer from 0 to 5 when m1 is 1, and an integer from 0 to 7 when m1 is 2. n1 should preferably be 0 to 7, 0 to 5 is better, 0 to 3 is even better, 0 to 1 is still better, and 0 is the best.

[0130] In equation (1), R 11 A hydrocarbon group having 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms. Specific examples of the aforementioned halogen atoms include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The aforementioned hydrocarbon groups having 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups having 1 to 10 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms, such as decyl and adamantyl; alkenyl groups with 2 to 10 carbon atoms, such as vinyl and allyl; aryl groups with 6 to 10 carbon atoms, such as phenyl and naphthyl; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone, sulfonyl, or carboxylic anhydride (-C(=O)-OC(=O)-), etc.] 11 It is preferable to use a hydrocarbon group with 1 to 4 carbon atoms or a fluorinated hydrocarbon group with 1 to 4 carbon atoms, with a hydrocarbon group with 1 to 4 carbon atoms being more preferred.

[0131] In equation (1), R 12A hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. Specific examples of the aforementioned halogen atoms include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The aforementioned hydrocarbon groups with 1 to 40 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, these groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.] 12 It is particularly good for hydrocarbon groups with 1 to 40 carbon atoms that may also contain heteroatoms.

[0132] In equation (1), R 14 A hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. Specific examples of the aforementioned halogen atoms include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The aforementioned hydrocarbon groups with 1 to 40 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6[Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups can also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulfonyl ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc. When n1 is 2 or more, each R...] 14 They can be the same or different. Also, multiple R's... 14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0133] In equation (1), R 13 It is a carbonyl group, or a hydrocarbon group with 1 to 10 carbon atoms that may also contain heteroatoms. The aforementioned hydrocarbon groups with 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkylene groups with 1 to 10 carbon atoms, such as methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-2,3-diyl, butane-1,4-diyl, 2-methylpropane-1,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, and decane-1,10-diyl; cyclopentanediyl, cyclohexanediyl, norcamphenediyl, adamantanediyl, and tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms, such as decanediyl; vinylidene, propenide, etc., with 2 to 10 carbon atoms; arylene groups with 6 to 10 carbon atoms, such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, naphthylene; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, these groups may contain hydroxyl, cyano, halogenated alkyl, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulpholactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.] 13 It is preferable to use a carbonyl group, a hydrocarbon group with 1 to 4 carbon atoms, or a fluorinated hydrocarbon group with 1 to 4 carbon atoms.

[0134] In equation (1), X 1It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 1 When it is a nitrogen atom, it has R 15 That is, X 1 When the atom is nitrogen, equation (1) contains NR. 15 Base. On the other hand, X 1 When the atom is oxygen or sulfur, formula (1) does not contain R. 15 base.

[0135] In equation (1), R 15 It is a hydrocarbon group or ester with 1 to 20 carbon atoms, consisting of hydrogen atoms, carbonyl groups, halogen atoms, or heteroatoms. Specific examples of the aforementioned halogen atoms include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The aforementioned hydrocarbon groups with 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 20 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; aryl groups with 6 to 20 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, these groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.]

[0136] Specific examples of high-valent iodine compounds represented by formula (1) are shown below, but are not limited thereto. Additionally, in the following formula, Me represents methyl and Ph represents phenyl.

[0137] [Chemistry 7]

[0138]

[0139] [Chemistry 8]

[0140]

[0141] [Chemistry 9]

[0142]

[0143] [Chemistry 10]

[0144]

[0145] [Chemistry 11]

[0146]

[0147] [Chemistry 12]

[0148]

[0149] [Chemistry 13]

[0150]

[0151] [Chemistry 14]

[0152]

[0153] [Chemistry 15]

[0154]

[0155] [Chemistry 16]

[0156]

[0157] [Chemistry 17]

[0158]

[0159] [Chemistry 18]

[0160]

[0161] [Chemistry 19]

[0162]

[0163] [Chemistry 20]

[0164]

[0165] [Chemistry 21]

[0166]

[0167] [Chemistry 22]

[0168]

[0169] [Chemistry 23]

[0170]

[0171] [Chemistry 24]

[0172]

[0173] [Chemistry 25]

[0174]

[0175] [Chemistry 26]

[0176]

[0177] [Chemistry 27]

[0178]

[0179] [Chemistry 28]

[0180]

[0181] [Chemistry 29]

[0182]

[0183] [Chemistry 30]

[0184]

[0185] [Chemistry 31]

[0186]

[0187] [Chemistry 32]

[0188]

[0189] [Chemistry 33]

[0190]

[0191] [Chemistry 34]

[0192]

[0193] [Chemistry 35]

[0194]

[0195] [Chemistry 36]

[0196]

[0197] [Chemistry 37]

[0198]

[0199] [Chemistry 38]

[0200]

[0201] [Chemistry 39]

[0202]

[0203] [Chemistry 40]

[0204]

[0205] [Chemistry 41]

[0206]

[0207] [Chemistry 42]

[0208]

[0209] [Chemistry 43]

[0210]

[0211] [Chemistry 44]

[0212]

[0213] [Chemistry 45]

[0214]

[0215] [Chemistry 46]

[0216]

[0217] [Chemistry 47]

[0218]

[0219] [Chemistry 48]

[0220]

[0221] [Chemistry 49]

[0222]

[0223] [Transformation 50]

[0224]

[0225] [Chemistry 51]

[0226]

[0227] [Preparation of high-valent iodine compounds]

[0228] The high-valent iodine compound used in this invention can be obtained using known methods. For example, when the desired high-valent iodine compound is a 5-membered heterocycle containing iodine(III) and nitrogen, it can be obtained by oxidizing and clotting a 2-iodobenzoamide derivative with an oxidizing agent such as peracetic acid, and then acetylifying the OH and NH groups with acetic anhydride or the like. For compounds containing a 5-membered heterocycle in which oxygen and sulfur replace nitrogen, 2-iodobenzoic acid derivatives and 2-iodothiobenzoic acid derivatives can also be used as raw materials and obtained in the same manner. In the above formula (1), X 1 It is a nitrogen atom and R 15 When the atom is not hydrogen, it can also be used with R. 15 Using substituted 2-iodobenzamide as a starting material, R can also be introduced through appropriate substitution reactions after the formation of a 5-membered heterocycle. 15 Synthetic methods can be found in, for example, J.Am.Chem.Soc., 1997, vol.119, No.31, pp.7408-7409, and Japanese Patent Application Publication No. 2015-186792.

[0229] [Compounds containing carboxyl groups]

[0230] The aforementioned carboxyl-containing compounds are preferably polymers containing repeating units represented by formula (2) or compounds represented by formula (3).

[0231] [Chemistry 52]

[0232]

[0233] In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group.

[0234] X A For single bonds, phenylene, naphthylene or -C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. It represents the atomic bonds between carbon atoms in the main chain and the main chain.

[0235] p can be 1, 2, 3 or 4.

[0236] R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms. When p is 2, R 31It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing a heteroatom, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be replaced by a group containing a heteroatom.

[0237] R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group may be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group may also be replaced by a group containing a heteroatom. When p is 2, 3 or 4, each R 32 They can be the same or different.

[0238] In equation (2), R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A For single bonds, phenylene, naphthylene or -C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. It represents the atomic bonds between carbon atoms in the main chain and the main chain.

[0239] In equation (3), p is 1, 2, 3 or 4.

[0240] In equation (3), R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms. When p is 2, R 31 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing a heteroatom, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be replaced by a group containing a heteroatom.

[0241] In equation (3), R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group may be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group may also be replaced by a group containing a heteroatom. When p is 2, 3 or 4, each R 32 They can be the same or different.

[0242] R 31The p-valent hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned p-valent hydrocarbon group is a group obtained by removing p hydrogen atoms from a hydrocarbon. Examples of such hydrocarbons include: alkanes with 1-40 carbon atoms, alkenes with 2-40 carbon atoms, alkynes with 2-40 carbon atoms, cyclic saturated hydrocarbons with 3-40 carbon atoms, cyclic unsaturated hydrocarbons with 3-40 carbon atoms, and aromatic hydrocarbons with 6-40 carbon atoms.

[0243] Examples of alkane with 1 to 40 carbon atoms include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[0244] Examples of alkenes with 2 to 40 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and their structural isomers.

[0245] Examples of alkynes with 2 to 40 carbon atoms include: acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, and their structural isomers.

[0246] Examples of the aforementioned cyclic saturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norcamphene, etc.

[0247] Examples of cyclic unsaturated hydrocarbons with 3 to 40 carbon atoms include cyclopropylene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norcamphene.

[0248] Examples of aromatic hydrocarbons with 6 to 40 carbon atoms include benzene, naphthalene, and biphenyl.

[0249] R 31 The p-valent heterocyclic group is a group obtained by removing p hydrogen atoms from a heterocyclic compound. Examples of such heterocyclic compounds include furan, pyridine, pyrazole, and tetrahydrothiazole.

[0250] In the aforementioned p-valent hydrocarbon groups or p-valent heterocyclic groups, some or all of the hydrogen atoms can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, resulting in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, and iodine atoms. Furthermore, in the aforementioned p-valent hydrocarbon groups, a portion of the -CH2- group can be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms, resulting in the presence of carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, carbamate bonds, lactone rings, sulfonyl lactone rings, and carboxylic anhydrides (-C(=O)-OC(=O)-), etc.

[0251] R 32The derivatized hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1, Alkyl groups with 1 to 20 carbon atoms, such as 11-diyl and dodecane-1,12-diyl; cyclic saturated alkylene groups with 3 to 20 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norcamphenediyl, and adamantanediyl; unsaturated aliphatic alkylene groups with 2 to 20 carbon atoms, such as vinylene and propene-1,3-diyl; aryl groups with 6 to 20 carbon atoms, such as phenylene and naphthylene; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned alkylene group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and a portion of the -CH2- constituting the aforementioned alkylene group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, carbamate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides, etc.

[0252] Among the carboxylic acid compounds represented by formula (3), it is preferable that p is 2, 3 or 4. Such carboxylic acid compounds, when mixed with high-valent iodine compounds, easily form a high-molecular-weight, robust resist film, which is ideal considering etching resistance and developer resistance.

[0253] Specific examples of the repeating unit containing a carboxyl group represented by equation (2) are shown below, but are not limited thereto. Additionally, in the following equation, R... A Same as above.

[0254] [Chemistry 53]

[0255]

[0256] [Chemistry 54]

[0257]

[0258] Carboxylic acid compounds represented by formula (3) can be listed as follows, but are not limited thereto.

[0259] [Chemistry 55]

[0260]

[0261] [Chemistry 56]

[0262]

[0263] [Chemistry 57]

[0264]

[0265] [Chem.58]

[0266]

[0267] [Chemistry 59]

[0268]

[0269] [Transformation 60]

[0270]

[0271] Polymers containing carboxyl groups that contain repeating units represented by formula (2) may also contain repeating units other than those represented by formula (2) (hereinafter also referred to as other repeating units). There are no particular limitations on the aforementioned other repeating units, but they should be those that can improve the solubility of polymers that are poorly soluble in solvents when they only contain repeating units with carboxyl groups. The aforementioned other repeating units should preferably be repeating units with a ring structure that can be expected to have high etch resistance due to a rigid backbone, or repeating units containing a styrene backbone.

[0272] Specific examples of the aforementioned repeating units may be listed below, but are not limited to these. Additionally, in the following formula, R... A As mentioned above, X B They are either -CH2- or -O-, respectively.

[0273] [Chemistry 61]

[0274]

[0275] [Chemistry 62]

[0276]

[0277] [Chemistry 63]

[0278]

[0279] [Chemistry 64]

[0280]

[0281] [Chemistry 65]

[0282]

[0283] [Chemistry 66]

[0284]

[0285] [Chemistry 67]

[0286]

[0287] [Chemistry 68]

[0288]

[0289] [Chemistry 69]

[0290]

[0291] [Chemistry 70]

[0292]

[0293] [Chemistry 71]

[0294]

[0295] [Chemistry 72]

[0296]

[0297] [Chemistry 73]

[0298]

[0299] [Chemistry 74]

[0300]

[0301] [Chemistry 75]

[0302]

[0303] [Chemistry 76]

[0304]

[0305] [Chemistry 77]

[0306]

[0307] [Chemistry 78]

[0308]

[0309] [Chemistry 79]

[0310]

[0311] [Chemistry 80]

[0312]

[0313] [Chemistry 81]

[0314]

[0315] [Chemistry 82]

[0316]

[0317] [Chemistry 83]

[0318]

[0319] [Chemistry 84]

[0320]

[0321] [Chemistry 85]

[0322]

[0323] [Chemistry 86]

[0324]

[0325] [Chemistry 87]

[0326]

[0327] [Chemistry 88]

[0328]

[0329] [Chemistry 89]

[0330]

[0331] [Chemistry 90]

[0332]

[0333] In the resist composition of the present invention, the molar ratio of the high-valent iodine compound represented by formula (1) to the carboxyl-containing compound (when the carboxyl-containing compound is a carboxyl-containing polymer, the molar ratio of the high-valent iodine compound represented by formula (1) to the repeating unit containing carboxylic acid in the polymer) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20. The high-valent iodine compound represented by formula (1) can be used alone or in combination with two or more compounds. Similarly, the carboxyl-containing compound can be used alone or in combination with two or more compounds. When the carboxyl-containing compound is a polymer, it can be used alone or in combination with two or more compounds with different composition ratios, Mw, and / or Mw / Mn.

[0334] In the aforementioned carboxyl-containing polymers, the molar ratio of carboxyl-containing repeating units to other repeating units should preferably be 10:90~90:10, more preferably 15:85~85:15, and even more preferably 20:80~80:20.

[0335] The weight-average molecular weight (Mw) of the aforementioned carboxyl-containing polymers is preferably 1,000 to 500,000, and more preferably 3,000 to 100,000. Furthermore, in this invention, the weight-average molecular weight Mw and number-average molecular weight Mn are polystyrene conversion values ​​determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0336] The molecular weight distribution Mw / Mn can be obtained from the Mw and Mn thus derived. Furthermore, in the aforementioned carboxyl-containing polymers, a wide molecular weight distribution (Mw / Mn) may result in the presence of both low and high molecular weight polymers, raising concerns about foreign matter and pattern shape deterioration observed on the pattern after exposure. Therefore, as the pattern becomes more regular and refined, the influence of Mw and Mw / Mn tends to increase. Thus, to obtain a resist composition ideally suited for fine pattern sizes, the aforementioned carboxyl-containing polymers should preferably have a narrow dispersion of Mw / Mn between 1.00 and 2.00. Mw / Mn should preferably be greater than 1.30, with a lower limit of 1.40, 1.50, or 1.60, and an upper limit of 1.70, 1.80, or 1.90.

[0337] Examples of methods for synthesizing the aforementioned carboxyl-containing polymers include: polymerizing a monomer that provides the aforementioned repeating unit in an organic solvent by adding a free radical polymerization initiator and heating it.

[0338] Specific examples of organic solvents used in the polymerization reaction include: toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, cyclopentanone, cyclohexanone, methyl ethyl ketone (MEK), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), etc. Specific examples of polymerization initiators include: 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, lauroyl peroxide, etc. The amount of the aforementioned polymerization initiator added, relative to the total amount of monomers used to polymerize, should preferably be 0.01~25 mol%. The reaction temperature should preferably be 50~150℃, preferably 60~100℃. The reaction time should ideally be 2 to 24 hours, but from a production efficiency perspective, 2 to 12 hours is even better.

[0339] The aforementioned polymerization initiator can be added to the monomer solution and supplied to the reactor, or an initiator solution different from the monomer solution can be prepared and supplied to the reactor separately. Since there is a possibility that polymerization may proceed and generate ultrapolymers due to the generation of free radicals from the initiator during the waiting time, from a quality management perspective, the monomer solution and initiator solution should preferably be prepared separately and added dropwise. Furthermore, to adjust the molecular weight, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can also be used in combination. In this case, the amount of the aforementioned chain transfer agent added, relative to the total amount of monomers used to polymerize, should preferably be 0.01 to 20 mol%.

[0340] In addition, the amount of each monomer in the aforementioned monomer solution can be appropriately set, for example, in a manner that makes it an ideal content ratio for the aforementioned repeating units.

[0341] [Other high-valent iodine compounds]

[0342] The resist composition of the present invention may also contain other high-valent iodine compounds besides the high-valent iodine compound represented by formula (1) as any component. By adding other high-valent iodine compounds, the reactivity to light can be controlled and the sensitivity adjusted. Other high-valent iodine compounds are preferably high-valent iodine compounds represented by formula (4) or (5) below (hereinafter also referred to as other high-valent iodine compounds).

[0343] [Chemistry 91]

[0344]

[0345] In the formula, m4 and m5 are integers from 0 to 2.

[0346] When m4 is 0, n4 is an integer from 0 to 3; when m4 is 1, n4 is an integer from 0 to 5; and when m4 is 2, n4 is an integer from 0 to 7.

[0347] When m5 is 0, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 5, and satisfies 1≤(n5+n6)≤6.

[0348] When m5 is 1, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 7, and satisfies 1≤(n5+n6)≤8.

[0349] When m5 is 2, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 9, and satisfies 1≤(n5+n6)≤10.

[0350] 1 and 2 represents the atomic bond of the carbon atom in the aromatic ring in the formula. However, 1 and 2. It must be bonded to an adjacent carbon atom on the aromatic ring.

[0351] R 41 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms.

[0352] R 42 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n4 is 2 to 7, each R 42 They can be the same or different. Also, multiple R's... 42 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. However, R 42 It will not be key to and 1. Carbon atoms on adjacent aromatic rings.

[0353] R 43 It is a carbonyl group, or may contain heteroatoms and carbonyl groups with 1 to 10 carbon atoms.

[0354] X 4 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 4 When it is a nitrogen atom, it has R 44 R 44 It consists of a hydrogen atom, a carbonyl group, a halogen atom, or a hydrocarbon group or ester with 1 to 20 carbon atoms that may also contain heteroatoms.

[0355] R 51 and R 52 Each R is an independent hydrocarbon group with 1 to 10 carbon atoms, which may also contain heteroatoms. When n6 is 2 to 3, each R 51 and R 52 They can be the same or different.

[0356] R 53 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n5 is 2 to 9, each R 53 They can be the same or different. Also, multiple R's... 53 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0357] In the above general formula (4), m4 is an integer from 0 to 2. When m4 is 0, n4 is an integer from 0 to 3; when m4 is 1, n4 is an integer from 0 to 5; and when m4 is 2, n4 is an integer from 0 to 7. n4 should preferably be 0, 1, 2, 3, or 4, with 0, 1, 2, or 3 being better, 0, 1, or 2 being even better, and 0 or 1 being the best.

[0358] In the above general formula (4), R 41A hydrocarbon group having 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms. Specific examples of the aforementioned halogen atoms include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The aforementioned hydrocarbon groups having 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups having 1 to 10 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms, such as decyl and adamantyl; alkenyl groups with 2 to 10 carbon atoms, such as vinyl and allyl; aryl groups with 6 to 10 carbon atoms, such as phenyl and naphthyl; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone, sulfonyl, or carboxylic anhydride (-C(=O)-OC(=O)-), etc.] 41 It is preferable to use a hydrocarbon group with 1 to 4 carbon atoms or a fluorinated hydrocarbon group with 1 to 4 carbon atoms, with a hydrocarbon group with 1 to 4 carbon atoms being more preferred.

[0359] In the above general formula (4), R 42 A hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. Specific examples of the aforementioned halogen atoms include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The aforementioned hydrocarbon groups with 1 to 40 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6[Cyclic saturated hydrocarbon groups with 3-40 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; aryl groups with 6-40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and part of the -CH2- group in the aforementioned hydrocarbon groups can also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, these groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulfonyl ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc. When n4 is 2-7, each R...] 2 They can be the same or different. Also, multiple R's... 42 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. However, R 42 It will not be key to and 1. Carbon atoms on adjacent aromatic rings.

[0360] In the above general formula (4), R 43 It is a carbonyl group, or a hydrocarbon group with 1 to 10 carbon atoms that may also contain heteroatoms. The aforementioned hydrocarbon groups with 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkylene groups with 1 to 10 carbon atoms, such as methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-2,3-diyl, butane-1,4-diyl, 2-methylpropane-1,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, and decane-1,10-diyl; cyclopentanediyl, cyclohexanediyl, norcamphenediyl, adamantanediyl, and tricyclic [5.2.1.0] 2 ,6 [Cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms, such as decanediyl; vinylidene, propenide, etc., with 2 to 10 carbon atoms; arylene groups with 6 to 10 carbon atoms, such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, naphthylene; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, these groups may contain hydroxyl, cyano, halogenated alkyl, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulpholactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.] 43It is preferable to use a carbonyl group, a hydrocarbon group with 1 to 4 carbon atoms, or a fluorinated hydrocarbon group with 1 to 4 carbon atoms.

[0361] In the above general formula (4), X 4 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 4 When it is a nitrogen atom, it has R 44 That is, X 4 When the atom is nitrogen, equation (4) contains NR. 44 Base. On the other hand, X 4 When the atom is oxygen or sulfur, equation (4) does not contain R. 44 base.

[0362] In the above general formula (4), R 44 It is a hydrocarbon group or ester with 1 to 20 carbon atoms, consisting of hydrogen atoms, carbonyl groups, halogen atoms, or heteroatoms. Specific examples of the aforementioned halogen atoms include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The aforementioned hydrocarbon groups with 1 to 20 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 20 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; aryl groups with 6 to 20 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, these groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.]

[0363] In the above general formula (4), 1 and 2 represents the atomic bond of the carbon atom in the aromatic ring in the formula. However, 1 and Two bonds are formed between adjacent carbon atoms on the aromatic ring. Thus... 1. The combination of 2 and m4 can be considered in the following 7 states.

[0364] [Chemistry 92]

[0365]

[0366] In the formula, n4, R 42 R 43 X 4 and R 44 Same as above. The dashed line represents R. 41 -C(=O)-O- atomic bonds.

[0367] Specific examples of high-valent iodine compounds represented by the above general formula (4) are shown below, but are not limited thereto. Additionally, in the following formula, Me is a methyl group.

[0368] [Chemistry 93]

[0369]

[0370] [Chemistry 94]

[0371]

[0372] [Chemistry 95]

[0373]

[0374] [Chemistry 96]

[0375]

[0376] [Chemistry 97]

[0377]

[0378] [Chem. 98]

[0379]

[0380] [Chemistry 99]

[0381]

[0382] [Chemistry 100]

[0383]

[0384] [Chemistry 101]

[0385]

[0386] [Chemistry 102]

[0387]

[0388] [Chemistry 103]

[0389]

[0390] [Chemistry 104]

[0391]

[0392] [Chemistry 105]

[0393]

[0394] [Chemistry 106]

[0395]

[0396] [Chemistry 107]

[0397]

[0398] [Chemistry 108]

[0399]

[0400] [Chemistry 109]

[0401]

[0402] [Chemical 110]

[0403]

[0404] [Chemistry 111]

[0405]

[0406] [Chemistry 112]

[0407]

[0408] [Chemistry 113]

[0409]

[0410] [Chemistry 114]

[0411]

[0412] [Chemistry 115]

[0413]

[0414] [Chemistry 116]

[0415]

[0416] [Chemistry 117]

[0417]

[0418] [Chemistry 118]

[0419]

[0420] [Chemistry 119]

[0421]

[0422] [Chemistry 120]

[0423]

[0424] [Chemistry 121]

[0425]

[0426] [Chemistry 122]

[0427]

[0428] [Chemistry 123]

[0429]

[0430] [Chemistry 124]

[0431]

[0432] [Chemistry 125]

[0433]

[0434] [Chemistry 126]

[0435]

[0436] [Chemistry 127]

[0437]

[0438] [Chemistry 128]

[0439]

[0440] [Chemistry 129]

[0441]

[0442] [Chemistry 130]

[0443]

[0444] [Chemistry 131]

[0445]

[0446] [Chemistry 132]

[0447]

[0448] [Chemistry 133]

[0449]

[0450] [Chemistry 134]

[0451]

[0452] [Chemistry 135]

[0453]

[0454] [Chemistry 136]

[0455]

[0456] [Chemistry 137]

[0457]

[0458] [Chemistry 138]

[0459]

[0460] [Chemistry 139]

[0461]

[0462] [Chemistry 140]

[0463]

[0464] [Chemistry 141]

[0465]

[0466] [Chemistry 142]

[0467]

[0468] [Chemistry 143]

[0469]

[0470] [Chemistry 144]

[0471]

[0472] [Chemistry 145]

[0473]

[0474] [Chemistry 146]

[0475]

[0476] [Chemistry 147]

[0477]

[0478] [Chemistry 148]

[0479]

[0480] [Chemistry 149]

[0481]

[0482] [Chemistry 150]

[0483]

[0484] [Chemistry 151]

[0485]

[0486] [Chemistry 152]

[0487]

[0488] [Chemistry 153]

[0489]

[0490] [Chemistry 154]

[0491]

[0492] [Chemistry 155]

[0493]

[0494] [Chemistry 156]

[0495]

[0496] In the above general formula (5), m5 is an integer from 0 to 2.

[0497] When m5 is 0, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 5, and satisfies 1≤(n5+n6)≤6.

[0498] When m5 is 1, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 7, and satisfies 1≤(n5+n6)≤8.

[0499] When m5 is 2, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 9, and satisfies 1≤(n5+n6)≤10.

[0500] In the above general formula (5), R 51 and R 52 Each R is an independent hydrocarbon group with 1 to 10 carbon atoms, which may also contain heteroatoms. When n6 is 2 to 3, each R 51 and R 52 They can be the same or different. Also, R 51 and R 52 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms. Examples of halogen atoms include: fluorine, chlorine, bromine, iodine, etc. The aforementioned hydrocarbon groups with 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 10 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms, such as decyl and adamantyl; alkenyl groups such as vinyl and allyl; aryl groups with 6 to 10 carbon atoms, such as phenyl and naphthyl; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulfonyl ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.] 51 and R 52 It should preferably be a hydrocarbon group with 1 to 4 carbon atoms.

[0501] In the above general formula (5), R 53 A hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. The hydrocarbon group with 1 to 40 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6[Cyclic saturated hydrocarbon groups with 3-40 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; aryl groups with 6-40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups can also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulfonyl ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc. When n5 is 2-9, each R...] 53 They can be the same or different. Also, multiple R's... 53 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0502] Specific examples of high-valent iodine compounds represented by the above general formula (5) are listed below, but are not limited thereto.

[0503] [Chemistry 157]

[0504]

[0505] [Chemistry 158]

[0506]

[0507] [Chemistry 159]

[0508]

[0509] [Chemistry 160]

[0510]

[0511] When the resist composition of the present invention contains other high-valent iodine compounds, the other high-valent iodine compounds may be only the high-valent iodine compounds represented by the above general formula (4), or only the high-valent iodine compounds represented by the above general formula (5), or a combination of the high-valent iodine compounds represented by the above general formula (4) and the high-valent iodine compounds represented by the above general formula (5). Furthermore, the high-valent iodine compounds represented by the above general formula (4) and the high-valent iodine compounds represented by the above general formula (5) may each be used individually, or two or more different compounds may be used in combination.

[0512] When the resist composition of the present invention contains other high-valent iodine compounds represented by formula (4) or formula (5) above, the molar ratio of the other high-valent iodine compounds represented by formula (4) or formula (5) above to the carboxyl-containing compounds (when the carboxyl-containing compounds are carboxyl-containing polymers, it is the molar ratio of the other high-valent iodine compounds represented by formula (4) or formula (5) above to the repeating units containing carboxylic acids in the aforementioned polymers) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20. Furthermore, the molar ratio of the other high-valent iodine compounds represented by formula (4) or formula (5) above to the high-valent iodine compounds represented by formula (1) above is preferably such that the ratio of the other high-valent iodine compounds represented by formula (4) or formula (5) above to the high-valent iodine compounds represented by formula (1) is 1:99 to 99:1, and more preferably 1:99 to 50:50.

[0513] [solvent]

[0514] The resist composition of the present invention contains a solvent. There are no particular limitations on the solvent being a soluble high-valent iodine compound represented by formula (1), a carboxyl-containing compound, other high-valent iodine compounds, and other components described below, and which can form a resist film by being contained in the resist composition. Such a solvent is preferably an organic solvent, and specific examples include: ketones such as cyclohexanone, methyl-2-n-pentyl ketone, and methyl isopentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, 4-methyl-2-pentanol, and methyl 2-hydroxyisobutyrate; and propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol monoethyl ether. Ethers such as monoethyl ether of alcohol, dimethyl propylene glycol, and dimethyl ethylene glycol; esters such as propylene glycol monomethyl ether acetate, monoethyl propylene glycol acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and monotert-butyl propylene glycol acetate; carboxylic acids such as formic acid, acetic acid, and propionic acid; lactones such as γ-butyrolactone; and their mixed solvents, etc.

[0515] In the resist composition of the present invention, the content of the aforementioned solvent is preferably such that the concentration of the solid component in the resist composition is 0.1% to 20% by mass, more preferably 0.1% to 15% by mass, and even more preferably 0.1% to 10% by mass. Furthermore, in the present invention, "solid component" refers to all components of the resist composition other than the solvent. The aforementioned solvent may be used alone or in combination of two or more.

[0516] [Other ingredients]

[0517] The resist composition of the present invention may further contain a surfactant. The aforementioned surfactant is preferably a fluorinated and / or polysiloxane surfactant. Specific examples of such surfactants include the surfactant described in paragraph

[0276] of U.S. Patent Application Publication 2008 / 0248425. Alternatively, surfactants other than the fluorinated and / or polysiloxane surfactants described in paragraph

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

[0518] When the resist composition of the present invention contains the aforementioned surfactant, its content in the total solid components is preferably 0.0001 to 2% by mass. The aforementioned surfactant may be used alone or in combination of two or more.

[0519] The resist composition of the present invention may further contain at least one selected from free radical scavengers and crosslinking agents. This allows for control of the photoresist reaction in optical lithography and adjustment of sensitivity.

[0520] Specific examples of the aforementioned free radical scavengers include hindered phenols, quinones, hindered amines, and thiols. Specifically, examples of hindered phenols include butylated hydroxytoluene (BHT) and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). Examples of quinones include 4-methoxyphenol (MEHQ) and hydroquinone. Examples of hindered amines include 2,2,6,6-tetramethylpiperidine-N-oxy radical. Examples of thiols include dodecyl mercaptan and hexadecyl mercaptan.

[0521] When the resist composition of the present invention contains the aforementioned free radical scavenger, its content in the total solid components is preferably 0.01 to 10% by mass. The aforementioned free radical scavenger may be used alone or in combination of two or more.

[0522] Specific examples of the aforementioned crosslinking agents include compounds with carbon-carbon unsaturated bonds as functional groups, such as vinyl, (meth)acrylate, allyl, alkynyl, and aromatic rings. Specifically, examples of compounds with vinyl groups include: chain alkenes, branched alkenes, and cyclic alkenes, which may also have substituents. Examples of compounds with (meth)acrylate groups include: acrylic acid, methacrylic acid, acrylates, and methacrylates, which may also have substituents. Examples of compounds with allyl groups include: allyl alcohols, allyl ethers, allyl esters, allyl amides, allylamines, and isocyanurates containing allyl groups, which may also have substituents. Examples of compounds with alkynyl groups include: chain alkynes, branched alkynes, cyclic alkynes, alkynyl alcohols, alkynyl ethers, alkynyl esters, alkynyl amides, alkynylamines, and isocyanurates containing alkynyl groups, which may also have substituents. Specific examples of compounds containing aromatic rings include: aromatic hydrocarbons, heteroaromatic hydrocarbons, styrene, stilbene, phenylacetylene, acenaphthene, chalcone, etc., which may also have substituents. The crosslinking agent may have only one of the aforementioned functional groups or multiple functional groups. The number of the aforementioned functional groups in the crosslinking agent is preferably 1 to 10, and more preferably 2 to 8.

[0523] When the resist composition of the present invention contains the aforementioned crosslinking agent, its content in the total solid components is preferably 0.01 to 50% by mass. The aforementioned crosslinking agent may be used alone or in combination of two or more.

[0524] [Layered Body]

[0525] The laminate of the present invention is characterized by having:

[0526] substrate, and

[0527] A resist film derived from the resist composition of the present invention is located on the substrate.

[0528] In the laminate of the present invention, which contains a resist film derived from the resist composition of the present invention, the resist film exhibits high sensitivity and excellent limiting resolution, is effective in precision micro-machining, and is applicable to the formation of any pattern, both positive and negative. Therefore, the laminate of the present invention has a wide range of applications and is highly useful in resist manufacturing technology.

[0529] For example, it can also be as follows Figure 1 The laminate 10 shown generally has a lower resist film 2 between the substrate 3 and the resist film 1.

[0530] When pattern formation requires a photoresist underlayer, the photoresist underlayer can be appropriately positioned between the substrate and the photoresist film.

[0531] For example, the resist film 1 may contain the coordination exchange reaction products of a high-valent iodine compound and a carboxyl-containing compound.

[0532] Resist films can be formed, for example, by a coordination exchange reaction between a high-valent iodine compound contained in the resist composition and a carboxyl-containing compound. Therefore, the resist film may also contain products of such a coordination exchange reaction.

[0533] [Pattern Formation Method]

[0534] When the resist composition of the present invention is used in the manufacture of various integrated circuits, known photolithography techniques can be employed. For example, a patterning method may include the following steps:

[0535] A resist film is formed on the substrate using the aforementioned resist composition.

[0536] The aforementioned resist film was exposed to high-energy rays, and

[0537] The previously exposed resist film should be developed using a developer solution as needed.

[0538] That is, the pattern forming method of the present invention includes the following steps:

[0539] A resist film is formed on a substrate or on a substrate having a resist underlayer film stacked thereon using the resist composition of the present invention.

[0540] The aforementioned resist film was exposed to high-energy rays, and

[0541] The previously exposed resist film was developed using a developer.

[0542] First, the resist composition of the present invention is applied, for example, by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or blade coating, to a substrate for integrated circuit manufacturing, or a substrate on which a resist underlayer film (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective film, etc.) is laminated, to a substrate for mask circuit manufacturing, or a substrate on which a resist underlayer film (Cr, CrO, CrON, MoSi2, SiO2, etc.) is laminated. The resulting coating film can then be pre-baked, for example, on a hot plate at a temperature preferably 60-200°C for 10 seconds to 30 minutes, and more preferably at 80-180°C for 30 seconds to 20 minutes, to form a resist film. In addition, the underlayer of the resist refers to the film formed between the substrate and the resist film in the multilayer resist process. There are no particular limitations on the aforementioned underlayer of the resist, and known ones can be used.

[0543] Then, the aforementioned photoresist film is exposed using high-energy radiation. Specific examples of such high-energy radiation include: ultraviolet rays (gamma rays (436nm), h-rays (405nm), i-rays (365nm), etc.), far ultraviolet rays, EB, EUV, X-rays, soft X-rays, excimer lasers (KrF excimer lasers, ArF excimer lasers, etc.), gamma rays, synchrotron radiation, etc. I-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet radiation are preferred for high-energy radiation. When using ultraviolet rays, far ultraviolet rays, EUV, X-rays, soft X-rays, excimer lasers, gamma rays, synchrotron radiation, etc., the exposure dose should be approximately 1~300 mJ / cm², either directly or using a mask to form the desired pattern. 2 And preferably, it should be approximately 10~200 mJ / cm 2 Irradiation is performed in a manner that allows for direct exposure or by using a mask to form the desired pattern. When using EB (Extracorporeal Electrode) for high-energy radiation, the exposure dose is preferably approximately 0.1~2000 μC / cm. 2 And preferably, it is about 0.5~1500 μC / cm. 2 The resist composition of the present invention is particularly suitable for fine patterning under high-energy radiation, such as EB or EUV.

[0544] After exposure, PEB should be applied as needed. In this case, it is advisable to apply the PEB on a heated plate or in an oven at 30~150℃ for 10 seconds~30 minutes, or more preferably 60~120℃ for 30 seconds~20 minutes.

[0545] After exposure or PEB, development and patterning are performed using a developer solution as needed. Examples of developers used at this time include: alkaline aqueous solutions such as tetramethylammonium hydroxide; 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methyl acetophenone, isopropanol, isoamyl alcohol, n-butanol, n-pentanol, cyclohexanol, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butyl acetate, isoamyl acetate, cyclohexyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl valerate, methyl valerate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate. Organic solvents such as ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, ethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, 1-propanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, and 4-methyl-2-pentanol are used. These developers can be used alone or in combination of two or more.

[0546] After development, rinsing should be performed as needed. The rinsing solution should ideally be miscible with the developer and not dissolve the resist film. Suitable solvents include: alcohols with 3-10 carbon atoms, ether compounds with 8-12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents with 6-12 carbon atoms. Alternatively, water can be used as the rinsing solution instead of an organic solvent.

[0547] By performing rinsing, the collapse of the resist pattern and the occurrence of defects can be reduced. Furthermore, rinsing is not necessary; by not performing rinsing, the amount of solvent used can be reduced.

[0548] The resist composition of the present invention utilizes exposure to create a difference in solubility between exposed and unexposed areas, thus forming positive or negative patterns. Therefore, a developer can be used that dissolves the exposed areas but not the unexposed areas, and vice versa. Thus, the pattern forming method of the present invention, by appropriately selecting the developer, can form positive or negative patterns, and is therefore widely applicable to the formation of various fine patterns.

[0549] Example

[0550] The present invention will be specifically described below using synthetic examples, embodiments and comparative examples, but the present invention is not limited thereto.

[0551] [1] Synthesis of high-valent iodine compounds

[0552] The high-valent iodine compounds used in the comparative examples and embodiments are represented by the formulas (RI-1)~(RI-3) and (I-1)~(I-3).

[0553] [Chemistry 161]

[0554]

[0555] The high-valent iodine compounds represented by formula (RI-1) and (I-1) were synthesized according to Org. Biomol. Chem., 2015, 13, 8812. The high-valent iodine compound represented by formula (RI-2) was synthesized according to Org. Lett., 2023, 25, 2739. The high-valent iodine compound represented by formula (I-2) was synthesized using 2-iodo-3-methylbenzoic acid as a starting material, except that it was synthesized by the same method as (RI-2). The high-valent iodine compound represented by formula (RI-3) was synthesized according to Org. Biomol. Chem., 2020, 18, 1679. The high-valent iodine compound represented by formula (I-3) was synthesized using 2-(2-iodo-3-methylphenyl)propane-2-ol as a starting material, except that it was synthesized by the same method as (RI-3).

[0556] [2] Polymer synthesis

[0557] The monomers used in the synthesis of the polymer are described below.

[0558] [Chemistry 162]

[0559]

[0560] [Chemistry 163]

[0561]

[0562] [Chemistry 164]

[0563]

[0564] [Synthetic Example 1] Synthesis of Polymer P-1

[0565] Under nitrogen atmosphere, monomer a-1 (56g), monomer b-1 (105g), V-601 (manufactured by Fujifilm and Koimitsu Chemicals) (5.4g), and MEK (methyl ethyl ketone) (180g) were measured in a flask to prepare a monomer-polymerization initiator solution. In another flask conditioned under nitrogen atmosphere, 55g of MEK was measured, and the mixture was heated to 80°C with stirring. The previously prepared monomer-polymerization initiator solution was then added dropwise over 4 hours. After the addition was complete, the polymerization solution was stirred continuously at 80°C for 2 hours, and then cooled to room temperature. The resulting polymerization solution was added dropwise to 4000g of vigorously stirred hexane, and the precipitated polymer was filtered and separated. The obtained polymer was then washed twice with 1200g of hexane and dried under vacuum at 50°C for 20 hours to obtain a white powdered polymer P-1 (yield 155g, 96% yield). The Mw of polymer P-1 is 7700, and the Mw / Mn ratio is 1.82. Furthermore, Mw and Mn are polystyrene conversion values ​​determined by GPC using THF as a solvent. The determinations were performed under the following conditions (the same applies below).

[0566] • Device: HLC-8320GPC

[0567] • Column: TSK guardcolumn

[0568] +TSKgel G4000HXL

[0569] +TSKgel G2000HXL

[0570] +TSKgel superH5000

[0571] • Pump and tubing constant temperature: 40℃

[0572] • Extraction solution: THF

[0573] • Detector: RI (Differential Refraction) detector

[0574] Injection volume: 100 μl

[0575] [Chemistry 165]

[0576]

[0577] [Synthetic Examples 2-10] Synthesis of Polymers P-2-P-10

[0578] By changing the types and blending ratios of the monomers, but otherwise using the same method as in Synthesis Example 1, the polymers shown in Table 1 below were synthesized. Additionally, polymer P-10 is a polymer without carboxyl groups (-COOH) and is not among the carboxyl-containing compounds of this invention.

[0579] [Table 1]

[0580]

[0581] [3] Preparation of the resist composition

[0582] [Examples 1-1 to 1-24, Comparative Examples 1-1 to 1-8]

[0583] High-valent iodine compounds, other high-valent iodine compounds, and polymers were dissolved in a solvent containing 0.01% by mass of a surfactant (PF-636, manufactured by OMNOVA) according to the compositions shown in Table 2 below. The resulting solutions were filtered through a 0.2 μm Teflon (registered trademark) filter to prepare resist compositions (R-01 to R-24) and comparative resist compositions (CR-01 to CR-06). Furthermore, polymers, photoacid generators, and sensitivity modifiers were dissolved in a solvent containing 0.01% by mass of a surfactant (PF-636, manufactured by OMNOVA) according to the compositions shown in Table 3 below. The resulting solutions were filtered through a 0.2 μm Teflon (registered trademark) filter to prepare comparative resist compositions (CR-07 to CR-08).

[0584] [Table 2]

[0585]

[0586] [Table 3]

[0587]

[0588] In Tables 2 and 3, the other high-valent iodine compound O-1, carboxyl-containing compounds m-1 to m-6, photoacid generator PAG-1, sensitivity modifier Q-1, and solvents are described below.

[0589] [Chemistry 166]

[0590]

[0591] [Chemistry 167]

[0592]

[0593] [Chemistry 168]

[0594]

[0595] [Chemistry 169]

[0596]

[0597] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[0598] AcOH (acetic acid)

[0599] HBM (methyl 2-hydroxyisobutyrate)

[0600] PA (propionic acid)

[0601] GBL (γ-butyrolactone)

[0602] [4] Evaluation of EUV lithography (line and space pattern, positive tone development)

[0603] [Examples 2-1 to 2-24, Comparative Examples 2-1 to 2-8]

[0604] Each resist composition (R-01~R-24, CR-01~CR-08) was spin-coated onto a Si substrate containing a silicon-containing spin-coated hard mask SHB-A940 (43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., with a film thickness of 20 nm. A photoresist film with a thickness of 40 nm was obtained by photocoating followed by baking (PAB) at the temperatures listed in Table 4 for 60 seconds using a heated plate. Each resist film was then exposed to a 36 nm line-to-spacing (LS) 1:1 pattern using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9, 90-degree dipole illumination). Afterward, a PEB was performed on the heated plate at the temperatures listed in Table 4 for 60 seconds, followed by development with the developer listed in Table 4 for 30 seconds, forming an LS pattern with a spacing width of 18 nm and a pitch of 36 nm.

[0605] The obtained resist pattern was evaluated as follows. The results are shown in Table 4.

[0606] [Sensitivity Evaluation]

[0607] The aforementioned LS pattern was observed using a Hitachi Advanced Technology Co., Ltd. (GAD) CG-6300 measuring SEM, and the optimal exposure Eop (mJ / cm²) for obtaining an LS pattern with a spacing width of 18nm and a pitch of 36nm was determined. 2 And make it a sensitivity.

[0608] [LWR Evaluation]

[0609] The dimensions of 10 points on an LS pattern obtained by exposure to the optimal amount of light along the length direction of the pitch width were measured using a Hitachi Advanced Technology Co., Ltd. The LWR was defined as three times the standard deviation (σ) obtained from the results (3σ). The smaller this value, the more uniform and less rough the pitch width pattern can be obtained.

[0610] [Limited Resolution Evaluation]

[0611] Using a Hitachi Advanced Technologies (AGT) CG-6300 long-range SEM, the linewidth (nm) that can be resolved by gradually increasing the exposure amount to form the aforementioned LS pattern from the optimal exposure amount is determined, and this is set as the limiting resolution (nm). The smaller this value, the better the limiting resolution, and the finer the pattern can be formed.

[0612] [Table 4]

[0613]

[0614] Developer: nBA (Butyl acetate)

[0615] CHA (cyclohexyl acetate)

[0616] TMAH (2.38% by mass tetramethylammonium hydroxide aqueous solution)

[0617] [5] Evaluation of EUV lithography (line and spacing patterns, negative tone development)

[0618] [Examples 3-1 to 3-24, Comparative Examples 3-1 to 3-8]

[0619] Each resist composition (R-1~R-24, CR-01~CR-08) was spin-coated onto a Si substrate with a silicon-containing spin-coating hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., having been formed to a thickness of 20 nm. The substrate was then coated and baked (PAB) for 60 seconds at the temperatures listed in Table 5 using a heated plate to obtain a resist film with a thickness of 40 nm. Each resist film was then exposed to a 36 nm line-to-spacing (LS) 1:1 pattern using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9, 90-degree dipole illumination). After exposure, the film was baked (PEB) for 60 seconds at the temperatures listed in Table 5 using a heated plate, followed by development for 30 seconds using the developer listed in Table 5, forming an LS pattern with a spacing of 18 nm and a pitch of 36 nm.

[0620] The obtained resist patterns were evaluated as follows. The results are shown in Table 5.

[0621] [Sensitivity Evaluation]

[0622] The aforementioned LS pattern was observed using a Hitachi Advanced Technology Co., Ltd. (GAD) CG-6300 measuring SEM, and the optimal exposure Eop (mJ / cm²) for obtaining an LS pattern with a spacing width of 18nm and a pitch of 36nm was determined. 2 And make it a sensitivity.

[0623] [LWR Evaluation]

[0624] The dimensions of 10 points on an LS pattern obtained by exposure to the optimal amount of light along the length direction of the pitch width were measured using a Hitachi Advanced Technology Co., Ltd. The LWR was defined as three times the standard deviation (σ) obtained from the results (3σ). The smaller this value, the more uniform and less rough the pitch width pattern can be obtained.

[0625] [Limited Resolution Evaluation]

[0626] Using a Hitachi Advanced Technologies (AGT) CG-6300 long-range SEM, the linewidth (nm) that can be resolved by gradually increasing the exposure amount to form the aforementioned LS pattern from the optimal exposure amount is determined, and this is set as the limiting resolution (nm). The smaller this value, the better the limiting resolution, and the finer the pattern can be formed.

[0627] [Table 5]

[0628]

[0629] As shown in Table 4 and Table 5, the resist composition of the present invention exhibits excellent sensitivity, LWR, and resolution during line and spacing pattern formation under EUV exposure, regardless of whether it is positive or negative tone development.

[0630] [6] Evaluation of EUV lithography (contact hole pattern)

[0631] [Examples 4-1 to 4-24, Comparative Examples 4-1 to 4-8]

[0632] Each resist composition (R-01~R-24, CR-01~CR-08) was spin-coated onto a Si substrate with a silicon-containing spin-coated hard mask SHB-A940 (43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., having a film thickness of 20 nm. The substrate was then coated and baked (PAB) for 60 seconds at the temperatures listed in Table 6 using a heated plate to obtain a resist film with a thickness of 50 nm. The resist film was then exposed using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, 64 nm pitch, +20% offset aperture pattern mask on wafer). The mask was then baked (PEB) for 60 seconds at the temperatures listed in Table 6 using a heated plate, followed by 30 seconds of development with the developer listed in Table 6 to obtain an aperture pattern with a size of 32 nm.

[0633] The obtained resist patterns were evaluated as follows. The results are shown in Table 6.

[0634] [Sensitivity Evaluation]

[0635] The aforementioned contact hole pattern was observed using a Hitachi Advanced Technology Co., Ltd. (HIT) CG-6300 SEM, and the optimal exposure value Eop (mJ / cm²) for obtaining a hole pattern with a size of 32nm was determined. 2 ).

[0636] [CD Uniformity (CDU) Evaluation]

[0637] The dimensions of 50 hole patterns obtained by irradiation with the optimal exposure were measured, and the standard deviation (σ) of the results was defined as three times the value of 3σ (CDU). The smaller this value, the more uniform the hole diameter of the pattern can be obtained.

[0638] [Limited Resolution Evaluation]

[0639] Using a Hitachi Advanced Technologies (AGT) CG-6300 long-range SEM, the limiting aperture diameter (nm) was determined by gradually decreasing the exposure amount to form the aforementioned aperture pattern from the optimal exposure amount. This value was then designated as the limiting resolution (nm). The smaller the value, the better the limiting resolution, and the more fine the aperture pattern can be formed.

[0640] [Table 6]

[0641]

[0642] As shown in Table 6, the resist composition of the present invention exhibits excellent sensitivity, CDU, and resolution during contact hole pattern formation under EUV exposure.

[0643] In other words, as can be seen from the above embodiments, if it is the resist composition of the present invention, it can take into account both high sensitivity and high resolution in the pattern forming method, which is extremely useful when forming fine patterns.

[0644] The present invention includes the following states.

[0645] [1] A resist composition characterized by containing:

[0646] The high-valent iodine compound represented by formula (1) below,

[0647] Compounds containing carboxyl groups, and

[0648] Solvent.

[0649] [Chemistry 170]

[0650]

[0651] In the formula, m1 is an integer from 0 to 2, n1 is an integer from 0 to 3 when m1 is 0, an integer from 0 to 5 when m1 is 1, and an integer from 0 to 7 when m1 is 2.

[0652] R 11 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms.

[0653] R 12 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms.

[0654] R 14 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n1 is 2 or more, each R 14 They can be the same or different. Also, multiple R's... 14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0655] R 13 It is a carbonyl group, or may contain heteroatoms and carbonyl groups with 1 to 10 carbon atoms.

[0656] X 1 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 1 When it is a nitrogen atom, it has R 15 R 15 It consists of a hydrogen atom, a carbonyl group, a halogen atom, or a hydrocarbon group or ester with 1 to 20 carbon atoms that may also contain heteroatoms.

[0657] [2] As described in [1], the aforementioned carboxyl-containing compound is a polymer containing a repeating unit represented by the following formula (2) or a compound represented by the following formula (3).

[0658] [Chemistry 171]

[0659]

[0660] In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group.

[0661] X A For single bonds, phenylene, naphthylene or -C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. It represents the atomic bonds between carbon atoms in the main chain and the main chain.

[0662] p can be 1, 2, 3 or 4.

[0663] R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms. When p is 2, R 31It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing a heteroatom, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be replaced by a group containing a heteroatom.

[0664] R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group may be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group may also be replaced by a group containing a heteroatom. When p is 2, 3 or 4, each R 32 They can be the same or different.

[0665] [3] The resist composition as described in [1] or [2] also contains at least one of the high-valent iodine compounds represented by formula (4) or (5).

[0666] [Chemistry 172]

[0667]

[0668] In the formula, m4 and m5 are integers from 0 to 2.

[0669] When m4 is 0, n4 is an integer from 0 to 3; when m4 is 1, n4 is an integer from 0 to 5; and when m4 is 2, n4 is an integer from 0 to 7.

[0670] When m5 is 0, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 5, and satisfies 1≤(n5+n6)≤6.

[0671] When m5 is 1, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 7, and satisfies 1≤(n5+n6)≤8.

[0672] When m5 is 2, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 9, and satisfies 1≤(n5+n6)≤10.

[0673] 1 and 2 represents the atomic bond of the carbon atom in the aromatic ring in the formula. However, 1 and 2. It must be bonded to an adjacent carbon atom on the aromatic ring.

[0674] R 41 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms.

[0675] R 42 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n4 is 2 to 7, each R 42They can be the same or different. Also, multiple R's... 42 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. However, R 42 It will not be key to and 1. Carbon atoms on adjacent aromatic rings.

[0676] R 43 It is a carbonyl group, or may contain heteroatoms and carbonyl groups with 1 to 10 carbon atoms.

[0677] X 4 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 4 When it is a nitrogen atom, it has R 44 R 44 It consists of a hydrogen atom, a carbonyl group, a halogen atom, or a hydrocarbon group or ester with 1 to 20 carbon atoms that may also contain heteroatoms.

[0678] R 51 and R 52 Each R is an independent hydrocarbon group with 1 to 10 carbon atoms, which may also contain heteroatoms. When n6 is 2 to 3, each R 51 and R 52 They can be the same or different.

[0679] R 53 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms. When n5 is 2 to 9, each R 53 They can be the same or different. Also, multiple R's... 53 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0680] [4] A laminated body, characterized by having:

[0681] substrate, and

[0682] The substrate has a resist film derived from any of the resist compositions described in [1] to [3].

[0683] [5] As in [4], a laminated body is provided, wherein a lower resist film is provided between the aforementioned substrate and the aforementioned resist film.

[0684] [6] As described in [4] or [5], wherein the aforementioned resist film contains the coordination exchange reaction product of the aforementioned high-valent iodine compound and the aforementioned carboxyl-containing compound.

[0685] [7] A method for forming a pattern, characterized by comprising the following steps:

[0686] A resist film is formed on a substrate or on the resist underlayer film of a substrate having a resist underlayer film laminated with any of the resist compositions described in [1] to [3].

[0687] The aforementioned resist film was exposed to high-energy rays, and

[0688] The previously exposed resist film was developed using a developer.

[0689] [8] The pattern forming method described in [7] wherein the aforementioned high-energy rays are i-rays, KrF excimer lasers, ArF excimer lasers, electron beams or extreme ultraviolet rays.

[0690] [9] The pattern forming method described in [7] or [8], wherein the aforementioned developing solution is used to dissolve the exposed portion but not the unexposed portion.

[0691]

[10] The pattern forming method described in [7] or [8], wherein the aforementioned developer is used to dissolve the unexposed portion and not the exposed portion.

[0692] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative examples, and those having substantially the same structure and performing the same effects as the technical concept described in the claims of the present invention are intended to be included within the technical scope of the present invention.

[0693] Explanation of reference numerals in the attached figures

[0694] 1: Resist film

[0695] 2: Underlayer film of resist

[0696] 3:Substrate

[0697] 10: Layered bodies

Claims

1. A resist composition, characterized in that: contain: The high-valent iodine compound represented by formula (1) below, Compounds containing carboxyl groups, and Solvent; In the formula, m1 is an integer from 0 to 2, n1 is an integer from 0 to 3 when m1 is 0, an integer from 0 to 5 when m1 is 1, and an integer from 0 to 7 when m1 is 2; R 11 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms; R 12 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain halogen atoms or heteroatoms; R 14 It is a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms; when n1 is 2 or more, each R 14 They can be the same or different; also, multiple Rs 14 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; R 13 It is a carbonyl group, or may contain heteroatoms and carbonyl groups with 1 to 10 carbon atoms; X 1 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 1 When it is a nitrogen atom, it has R 15 ;R 15 It consists of a hydrogen atom, a carbonyl group, a halogen atom, or a hydrocarbon group or ester with 1 to 20 carbon atoms that may also contain heteroatoms.

2. The resist composition according to claim 1, wherein, The carboxyl-containing compound is a polymer containing a repeating unit represented by formula (2) or a compound represented by formula (3); In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group; X A For single bonds, phenylene, naphthylene or -C(=O)-OX A1 -;X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring; This represents the atomic bonds between carbon atoms in the main chain; p is 1, 2, 3 or 4; R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms. When p is 2, R 31 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group or sulfonyl group; furthermore, part or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing heteroatoms, and part of the -CH2- of the p-valent hydrocarbon group can also be replaced by a group containing heteroatoms. R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group can be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group can also be replaced by a group containing a heteroatom; when p is 2, 3 or 4, each R 32 They can be the same or different.

3. The resist composition according to claim 1 further comprises at least one of the high-valent iodine compounds represented by formula (4) or (5); In the formula, m4 and m5 are integers from 0 to 2. When m4 is 0, n4 is an integer from 0 to 3; when m4 is 1, n4 is an integer from 0 to 5; and when m4 is 2, n4 is an integer from 0 to 7. When m5 is 0, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 5, and satisfies 1≤(n5+n6)≤6; When m5 is 1, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 7, and satisfies 1≤(n5+n6)≤8; When m5 is 2, n6 is an integer from 1 to 3, and n5 is an integer from 0 to 9, and satisfies 1≤(n5+n6)≤10; 1 and 2 represents the atomic bond of the carbon atom in the aromatic ring in the formula; however, 1 and 2. It must be bonded to an adjacent carbon atom on the aromatic ring; R 41 It is a hydrocarbon group with 1 to 10 carbon atoms, which may contain halogen atoms or heteroatoms; R 42 The group consists of a halogen atom, or may contain heteroatoms, a hydrocarbon group with 1 to 40 carbon atoms; when n4 is 2 to 7, each R 42 They can be the same or different; also, multiple Rs 42 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; however, R 42 It will not be key to and 1. Carbon atoms on adjacent aromatic rings; R 43 It is a carbonyl group, or may contain heteroatoms and carbonyl groups with 1 to 10 carbon atoms; X 4 It is an oxygen atom, a nitrogen atom, or a sulfur atom, and X 4 When it is a nitrogen atom, it has R 44 ;R 44 It consists of hydrogen atoms, carbonyl groups, halogen atoms, or hydrocarbon groups or esters with 1 to 20 carbon atoms that may also contain heteroatoms; R 51 and R 52 Each R is an independent hydrocarbon group with 1 to 10 carbon atoms, or may contain heteroatoms; when n6 is 2 to 3, each R 51 and R 52 They can be the same or different; R 53 The group consists of a halogen atom, or may contain heteroatoms, a hydrocarbon group with 1 to 40 carbon atoms; when n5 is 2 to 9, each R 53 They can be the same or different; also, multiple Rs 53 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

4. A laminated body, characterized by having: substrate, and The resist film on the substrate is derived from the resist composition according to any one of claims 1 to 3.

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

6. The laminate according to claim 4, wherein, The resist film contains the coordination exchange reaction product of the high-valent iodine compound and the carboxyl-containing compound.

7. A method for forming a pattern, characterized by comprising the following steps: A resist film is formed on a substrate or on the resist underlayer film of a substrate having a resist underlayer film laminated using the resist composition according to any one of claims 1 to 3. The resist film was exposed to high-energy rays, and The exposed resist film was developed using a developer.

8. The pattern forming method according to claim 7, wherein, This high-energy radiation uses i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet light.

9. The pattern forming method according to claim 7, wherein, This developer is used to dissolve the exposed areas but not the unexposed areas.

10. The pattern forming method according to claim 7, wherein, This developer is used to dissolve the unexposed areas but not the exposed areas.

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