Laminate, process for manufacturing laminate, and patterning process

Abstract

The present invention addresses the problem of providing a multilayer material that achieves both high sensitivity and high resolution and can form fine patterns in photolithography using high-energy rays, as well as a method for manufacturing such a multilayer material and a method for forming such a pattern. The solution to this problem is a multilayer material characterized by comprising, in sequence: a substrate, a silicon-containing resist lower layer film derived from a silicon-containing resist lower layer film composition containing a thermally crosslinked polysiloxane, the thermally crosslinked polysiloxane containing any one or more repeating units represented by general formulas (1) to (3) and any one or more repeating units represented by general formulas (4) to (6), and a resist film derived from a resist composition containing at least one superatomic iodine compound selected from superatomic iodine compounds represented by formula (7), superatomic iodine compounds represented by formula (8), and superatomic iodine compounds represented by formula (9), a carboxyl-containing compound, and a solvent.

Description

Technical Field

[0001] This invention relates to a laminate, a method for manufacturing a laminate, and a method for forming a pattern. Prior Technology

[0002] With the expansion of the IoT market, there is a growing demand for highly integrated, high-speed, and low-power LSIs, and the miniaturization of patterning is also progressing rapidly. In particular, logic devices are leading the way in miniaturization. As for the most advanced miniaturization technologies, mass production of 10nm node devices using ArF immersion lithography with dual, triple, and quadruple patterning is already underway. In addition, research is progressing on the next generation of 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, chemical amplification inhibitors 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 amplifying inhibitor compositions include polymethyl methacrylate (PMMA). PMMA is a positive inhibitor material that improves the solubility in organic solvent developers by breaking down the main chain and reducing the molecular weight through EUV irradiation.

[0006] Hydrosilsesquioxane (HSQ) is a negative resist material that is insoluble in alkaline developers, resulting from the cross-linking reaction of silanol produced by EUV irradiation. Additionally, chlorinated calixarnes also function as negative resist materials. Because these negative resist materials have small molecular sizes before cross-linking and are free from blurring caused by acid diffusion, they can be used as pattern transfer materials with low edge roughness and very high resolution, showcasing the resolving limits of exposure equipment. However, these materials have insufficient sensitivity and require further improvement.

[0007] One of the main reasons for the difficulty in developing materials for EUV lithography applications is the low photon count in EUV exposure. EUV energy is much higher than ArF excimer laser light, 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 easily affected by variations in the photon count. These variations in the photon count in extremely short wavelength emission regions constitute shot noise, a physical phenomenon that cannot be eliminated. Therefore, 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 the overall performance of the device. When considering practical sensitivity, resistive compositions with PMMA and HSQ as the main components are significantly affected by stochastics and cannot achieve the desired resolution performance.

[0008] As a method to reduce the impact of shot noise from the perspective of resistors, the introduction of elements with high absorption of EUV light has attracted attention. Patent Document 1 proposes a chemical amplification resist composition containing iodine atoms with high absorption of EUV light. However, as mentioned above, chemical amplification resist compositions cannot achieve excellent resolution performance in EUV lithography with increasingly smaller processing dimensions in the future. Especially in line and space patterns, as the pattern size decreases, pattern collapse and line breaks increase significantly, so reducing these issues is closely related to improving the limiting resolution.

[0009] Patent document 2 proposes a negative resist composition using tin compounds. It uses tin, which has high absorption under EUV light, as the main component, thus improving stochastics and achieving high sensitivity and high resolution. However, such metal resists suffer from several issues, including insufficient solubility in resist solvents, storage stability, and defects caused by etching residues. Furthermore, since the exposed portion of the metal resist becomes a metal oxide and is therefore insoluble in the developer, an additional inversion process is required when using it for contact hole patterning, raising concerns about cost. [Previous Technical Documents] [Patent Literature]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2018-5224 [Patent Document 2] Japanese Patent Publication No. 2021-503482

[0011] [Non-Patent Literature 1] SPIE Vol. 5039 p1 (2003) [Non-Patent Literature 2] SPIE Vol. 6520 p65203L-1 (2007) Summary of the Invention

[0012] [The problem that the invention aims to solve] The present invention is made in view of the foregoing circumstances, and aims to provide a multilayer comprising a resist film and a silicon-containing resist underlayer film located below the resist film, wherein the resist film is derived from a non-chemically amplified resist composition with excellent sensitivity and limiting resolution suitable for photolithography using high-energy rays, especially electron beam (EB) lithography and EUV lithography; and to provide a method for patterning the upper layer of the multilayer. [Methods for solving problems]

[0013] To address the aforementioned issues, the present invention provides a laminated body, characterized by comprising, in sequence: substrate, The silicon-containing inhibitor lower layer film is obtained from a silicon-containing inhibitor lower layer film composition containing a thermally crosslinked polysiloxane, wherein the thermally crosslinked polysiloxane contains any one or more repeating units represented by general formulas (1) to (3) below, and any one or more repeating units represented by general formulas (4) to (6) below, and The inhibitor film is derived from an inhibitor composition containing at least one superatomic iodine compound selected from the following formula (7), the following formula (8), the following formula (9), a carboxyl-containing compound, and a solvent. [Chemistry 1] In the formula, R1 is an organic group with a carboxyl group or an organic group with a carboxyl group that is replaced by an acid-instable group, and R2, R3 and R4 are monovalent organic groups with 1 to 30 carbon atoms that may be the same or different. [Chemistry 2] In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, or 5, and 1 ≤ n1 + n2 ≤ 6. When m is 1, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1 ≤ n1 + n2 ≤ 8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1 ≤ n1 + n2 ≤ 10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4. However, 1 ≤ n3 + n4 ≤ 5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4. However, 1 ≤ n5 + n6 ≤ 5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R11 to R18 are halogen atoms, or may contain hydrocarbon groups with 1 to 10 carbon atoms. Furthermore, R11 and R12, R13 and R14, R15 and R16, or R17 and R18 may also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between those carbon atoms. R21 to R24 are each independently a halogen atom, or may contain heteroatoms and be hydrocarbon groups with 1 to 40 carbon atoms. When n2 is 2 or more, each R21 can be the same or different, and multiple R21s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R22 can be the same or different, and multiple R22s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R23 can be the same or different, and multiple R23s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R24 can be the same or different, and multiple R24s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. R25 is an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R25 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned (n8) valent hydrocarbon group or (n8) valent heterocyclic group can be substituted by a group containing heteroatoms, and part of the -CH2- of the aforementioned (n8) valent hydrocarbon group can also be substituted by a group containing heteroatoms. R24 and R25 can also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between the carbon atoms.

[0014] Such a multilayer structure would be suitable for photolithography using high-energy rays, especially for electron beam (EB) lithography and EUV lithography, offering excellent sensitivity and limiting resolution. The resist composition of this invention, due to the presence of iodine atoms with high absorption capacity for EUV light, can reduce shot noise and achieve higher resolution and lower LWR, particularly in EUV lithography.

[0015] At this time, it is advisable to have a resist lower layer film between the aforementioned substrate and the silicon-containing resist lower layer film.

[0016] Such a stacked structure can precisely transfer the pattern of the resist film with excellent resolution to the substrate, which is extremely effective for micro-processing.

[0017] The aforementioned silicon-containing inhibitor lower layer film composition should preferably contain a crosslinking catalyst (Xc) for siloxane polymerization, an alcohol-based organic solvent, and water.

[0018] If such a silicon-containing resistive underlayer film composition is used, it will become a stable and well-operated silicon-containing resistive underlayer film composition. Furthermore, the patterning ability and film strength of the resistive film as the prepared silicon-containing resistive underlayer film are ideal.

[0019] The aforementioned carboxyl-containing compound in the aforementioned inhibitor composition is preferably a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11). [Chemistry 3] In the formula, RA is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. XA represents a single bond, an enylphenyl group, an enylnaphthyl group, or *-C(=O)-O-XA1-. XA1 represents a saturated enylalkyl group, an enylphenyl group, or an enylnaphthyl group with 1 to 10 carbon atoms, and this saturated enylalkyl group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. * indicates an atomic bond with a carbon atom in the main chain. p can be 1, 2, 3 or 4. R31 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, R31 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, aminocarbamate 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 substituted by a group containing heteroatoms, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be substituted by a group containing heteroatoms. R32 is a single bond or an elongated hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the elongated hydrocarbon group may be replaced by a group containing heteroatoms, and part of the -CH2- of the elongated hydrocarbon group may also be replaced by a group containing heteroatoms. When p is 2 to 4, each R32 may be the same or different.

[0020] If a carboxyl-containing compound has such a structure, it will have high solubility in solvents, be easy to form into a composition, and achieve high etch resistance due to its rigid framework.

[0021] Furthermore, the present invention provides a method for manufacturing a laminate, characterized by comprising the following steps: A resist lower layer film is formed on the substrate. On the resist lower layer film, a silicon-containing resist lower layer film is formed from a silicon-containing resist lower layer film composition containing any one or more repeating units represented by general formulas (1) to (3) and any one or more repeating units represented by general formulas (4) to (6) below, and A resistive composition containing at least one superatomic iodine compound selected from the following formula (7), superatomic iodine compound represented by the following formula (8) and superatomic iodine compound represented by the following formula (9), a carboxyl-containing compound, and a solvent is coated onto the silicon-containing resistive lower layer film, and then subjected to heat treatment to form a resistive film. [Chemistry 4] In the formula, R1 is an organic group with a carboxyl group or an organic group with a carboxyl group that is replaced by an acid-instable group, and R2, R3 and R4 are monovalent organic groups with 1 to 30 carbon atoms that may be the same or different. [Chemistry 5] In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, or 5, and 1 ≤ n1 + n2 ≤ 6. When m is 1, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1 ≤ n1 + n2 ≤ 8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1 ≤ n1 + n2 ≤ 10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4. However, 1 ≤ n3 + n4 ≤ 5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4. However, 1 ≤ n5 + n6 ≤ 5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R11 to R18 are halogen atoms, or may contain hydrocarbon groups with 1 to 10 carbon atoms. Furthermore, R11 and R12, R13 and R14, R15 and R16, or R17 and R18 may also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between those carbon atoms. R21 to R24 are each independently a halogen atom, or may contain heteroatoms and be hydrocarbon groups with 1 to 40 carbon atoms. When n2 is 2 or more, each R21 can be the same or different, and multiple R21s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R22 can be the same or different, and multiple R22s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R23 can be the same or different, and multiple R23s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R24 can be the same or different, and multiple R24s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. R25 is an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R25 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned (n8) valent hydrocarbon group or (n8) valent heterocyclic group can be substituted by a group containing heteroatoms, and part of the -CH2- of the aforementioned (n8) valent hydrocarbon group can also be substituted by a group containing heteroatoms. R24 and R25 can also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between the carbon atoms.

[0022] By forming a silicon-containing resist lower layer film and then forming a resist film on top of it, which is composed of a resist composition with superatomic iodine compounds and carboxyl-containing compounds as the main components, a resist film with excellent resolution can be formed, and a stacked structure that is extremely effective for precision micro-machining can be manufactured.

[0023] At this point, the lower film forming material can be coated onto the substrate and subjected to heat treatment to form the aforementioned resist lower film.

[0024] Alternatively, the aforementioned resist lower layer film can also be formed using CVD or ALD methods.

[0025] In addition, the aforementioned carboxyl-containing compounds may also be defined as polymers containing repeating units represented by the following formula (10) or compounds represented by the following formula (11). [Chemistry 6] In the formula, RA is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. XA represents a single bond, an enylphenyl group, an enylnaphthyl group, or *-C(=O)-O-XA1-. XA1 represents a saturated enylalkyl group, an enylphenyl group, or an enylnaphthyl group with 1 to 10 carbon atoms, and this saturated enylalkyl group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. * indicates an atomic bond with a carbon atom in the main chain. p can be 1, 2, 3 or 4. R31 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, R31 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, aminocarbamate 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 substituted by a group containing heteroatoms, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be substituted by a group containing heteroatoms. R32 is a single bond or an elongated hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the elongated hydrocarbon group may be replaced by a group containing heteroatoms, and part of the -CH2- of the elongated hydrocarbon group may also be replaced by a group containing heteroatoms. When p is 2 to 4, each R32 may be the same or different.

[0026] If a manufacturing method is used to produce a composition containing a carboxyl-containing compound with such a specific structure, then it is ideal to produce a laminate with stable composition and high etch resistance.

[0027] This invention provides a pattern forming method, comprising the following steps: The resist film of the above-described multilayer structure was exposed to i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet light. The previously exposed resist film was developed using a developer.

[0028] This invention utilizes high-energy rays to expose the resist film and a developing solution to develop it, which can form high-sensitivity and high-resolution micro-patterns.

[0029] The aforementioned developing solution can be an organic solvent.

[0030] Due to the effects of the superatomic iodine compound and carboxylic acid compound, the resist film of the present invention has a strong film system and excellent etching resistance and developer resistance to solvent developer. Therefore, it can be ideally used in pattern forming methods that use organic solvent developer. [Effects of the Invention]

[0031] The stacked structure of the present invention is particularly useful in i-ray, KrF excimer laser, ArF excimer laser, EB lithography and EUV lithography, in order to achieve both high sensitivity and high resolution and form fine patterns. Implementation

[0032] As mentioned above, there is a need to develop high-sensitivity and high-resolution lithography materials suitable for forming fine patterns, which have excellent dimensional uniformity (CDU), low linewidth roughness (LWR), and are not prone to causing micropore blockage.

[0033] After repeated and in-depth explorations to achieve the aforementioned objectives, the following insights were obtained, leading to the completion of this invention: By coating a desired silicon-containing resist film under a resist film derived from a resist composition consisting mainly of a predetermined superatomic iodine compound and a carboxyl-containing compound, it is highly effective for providing a resist film exhibiting excellent resolution and for precise microfabrication.

[0034] The stack of the present invention is extremely useful as a stack for multilayer resistive processes such as three-layer resistive processes that use a resistive underlayer film and a silicon-containing resistive underlayer film.

[0035] The present invention will now be described in detail, but it is not limited thereto.

[0036] That is, the present invention comprises a stack having a substrate, a silicon-containing resist lower layer film, and a resist film in sequence.

[0037] [Laminated structure] The stacked body of the present invention is characterized by comprising, in sequence: substrate, The silicon-containing inhibitor lower layer film is obtained from a silicon-containing inhibitor lower layer film composition containing a thermally crosslinked polysiloxane, wherein the thermally crosslinked polysiloxane contains any one or more repeating units represented by general formulas (1) to (3) below, and any one or more repeating units represented by general formulas (4) to (6) below, and The inhibitor film is derived from an inhibitor composition containing at least one superatomic iodine compound selected from the following formula (7), the following formula (8), the following formula (9), a carboxyl-containing compound, and a solvent. [Chemistry 7] In the formula, R1 is an organic group with a carboxyl group or an organic group with a carboxyl group that is replaced by an acid-instable group, and R2, R3 and R4 are monovalent organic groups with 1 to 30 carbon atoms that may be the same or different. [Chemistry 8] In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, or 5, and 1 ≤ n1 + n2 ≤ 6. When m is 1, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1 ≤ n1 + n2 ≤ 8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1 ≤ n1 + n2 ≤ 10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4. However, 1 ≤ n3 + n4 ≤ 5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4. However, 1 ≤ n5 + n6 ≤ 5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R11 to R18 are halogen atoms, or may contain hydrocarbon groups with 1 to 10 carbon atoms. Furthermore, R11 and R12, R13 and R14, R15 and R16, or R17 and R18 may also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between those carbon atoms. R21 to R24 are each independently a halogen atom, or may contain heteroatoms and be hydrocarbon groups with 1 to 40 carbon atoms. When n2 is 2 or more, each R21 can be the same or different, and multiple R21s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R22 can be the same or different, and multiple R22s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R23 can be the same or different, and multiple R23s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R24 can be the same or different, and multiple R24s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. R25 is an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R25 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned (n8) valent hydrocarbon group or (n8) valent heterocyclic group can be substituted by a group containing heteroatoms, and part of the -CH2- of the aforementioned (n8) valent hydrocarbon group can also be substituted by a group containing heteroatoms. R24 and R25 can also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between the carbon atoms.

[0038] The following sections will describe the substrate, the silicon-containing resist lower layer film, and the resist film in that order. [Substrate] The aforementioned substrates are preferably substrates used for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, etc.) or substrates used for masking circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.).

[0039] [Silicone-containing resistive lower layer film] The aforementioned silicon-containing inhibitor underlayer film is derived from a silicon-containing inhibitor underlayer film composition containing a thermally crosslinked polysiloxane with the specific structure described below.

[0040] [Thermocrosslinked polysiloxane] The thermally crosslinked polysiloxane of the present invention will be described below. The thermally crosslinked polysiloxane of the present invention is a thermally crosslinked polysiloxane containing any one or more repeating units represented by the following general formulas (1) to (3) and any one or more repeating units represented by the following general formulas (4) to (6). [Chemistry 9] In the formula, R1 is an organic group with a carboxyl group or an organic group with a carboxyl group that is replaced by an acid-instable group, and R2, R3 and R4 are monovalent organic groups with 1 to 30 carbon atoms that may be the same or different.

[0041] R1 in the above general formulas (1) to (3) can be listed as follows, but is not limited to these. In addition, in the following formula, (Si) is recorded to indicate the position of the bond with Si. [Chemistry 10]

[0042] [Chemistry 11]

[0043] In the formula, R2, R3, and R4 are monovalent organogroups with 1 to 30 carbon atoms, which may be the same or different. R2 and R3 are preferably saturated or unsaturated organogroups with 1 to 20 carbon atoms, which may also have substituents. Examples of organogroups include: alkyl groups with 1 to 20 carbon atoms that are substituted or unsubstituted, such as chain, branched, or cyclic; alkenyl groups with 2 to 20 carbon atoms that are substituted or unsubstituted; and aryl groups with 6 to 20 carbon atoms that are substituted or unsubstituted. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, n-hexyl; vinyl, allyl, propenyl; phenyl, tolyl, etc.

[0044] Other examples of organic groups represented by R2, R3, and R4 include organic groups having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, these are organic groups having one or more groups selected from the group consisting of ether bonds, ester bonds, alkoxy groups, hydroxyl groups, etc., other than carboxyl groups. Examples can be represented by the following general formula (Sm-R).

[0045] (P-Q1-(S1)v1-Q2-)u-(T)v2-Q3-(S2)v3-Q4- (Sm-R) In the general formula (Sm-R), P is a hydrogen atom, a cyclic ether group, a hydroxyl group, an alkoxy group with 1 to 4 carbon atoms, an alkyl carbonyloxy group with 2 to 6 carbon atoms, or an alkyl carbonyl group with 2 to 6 carbon atoms. Q1, Q2, Q3, and Q4 are each independently -CqH(2q-p)Pp- (where P is the same as above, p is an integer from 0 to 3, and q is an integer from 0 to 10; however, q=0 indicates a single bond). u is an integer from 0 to 3. S1 and S2 independently represent -O-, -CO-, -OCO-, -COO-, or -OCOO-. v1, v2, and v3 each independently represent 0 or 1. T is a divalent group composed of divalent atoms other than carbon, alicyclic rings, aromatic rings, or heterocyclic rings.

[0046] Examples of alicyclic, aromatic, or heterocyclic rings that may also contain heteroatoms such as oxygen atoms are shown below as T. In T, the bond positions of Q2 and Q3 are not particularly restricted, and can be appropriately selected considering factors such as reactivity due to steric factors and the availability of commercially available reagents used in the reaction.

[0047] [Chemistry 12]

[0048] Ideal examples of organogroups having one or more carbon-oxygen single or double bonds in the general formula (Sm-R) are listed below. Additionally, in the following formula, (Si) is used to indicate the bonding position with Si.

[0049] [Chemistry 13]

[0050] [Chemistry 14]

[0051] Furthermore, examples of the organic groups R2, R3, and R4 can also use organic groups containing silicon-silicon bonds. Specific examples are listed below. [Chemistry 15]

[0052] Furthermore, examples of the organogroups R2, R3, and R4 can also be organogroups having fluorine atoms. Specific examples include the organogroups of silicon compounds shown in paragraphs (0059) to (0065) of Japanese Patent Application Publication No. 2012-53253.

[0053] The aforementioned hydrolyzable monomer (Sm) has one, two, or three chlorine, bromine, iodine, acetoxy, methoxy, ethoxy, propoxy, or butoxy groups bonded to silicon (represented by Si) in the above substructure as hydrolyzable groups.

[0054] [Synthesis Method of Thermocrosslinkable Polysiloxanes (Raw Materials)] The thermally crosslinked polysiloxanes in formulas (4) to (6) can be manufactured, for example, by hydrolyzing and condensing the following hydrolyzable monomer (Sm).

[0055] Hydrolyzable monomers (Sm) can be specifically exemplified as: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane Silane, ethyltripropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltripropoxysilane Oxysilane, isopropyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltriisopropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, isobutyltriisopropoxysilane, secondary butyltrimethoxysilane, secondary butyltriethoxysilane, secondary butyltripropoxysilane Alkane, secondary butyltriisopropoxysilane, tertiary butyltrimethoxysilane, tertiary butyltriethoxysilane, tertiary butyltripropoxysilane, tertiary butyltriisopropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, allyltriisopropoxysilane, cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane, cyclopropyltripropoxysilane cyclooxysilanes, cyclopropyltriisopropoxysilanes, cyclobutyltrimethoxysilanes, cyclobutyltriethoxysilanes, cyclobutyltripropoxysilanes, cyclobutyltriisopropoxysilanes, cyclopentyltrimethoxysilanes, cyclopentyltriethoxysilanes, cyclopentyltripropoxysilanes, cyclopentyltriisopropoxysilanes, cyclohexyltrimethoxysilanes, cyclohexyltriethoxysilanes, cyclohexyltripropoxysilanes Silane, cyclohexyltriisopropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane, cyclooctyl Triethoxysilane, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, dicycloheptenyltrimethoxysilane, dicycloheptenyltriethoxysilane, dicycloheptenyltripropoxysilane, dicycloheptenyl... Bicycloheptanyltriisopropoxysilane, bicycloheptanyltrimethoxysilane, bicycloheptanyltriethoxysilane, bicycloheptanyltripropoxysilane, bicycloheptanyltriisopropoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyltripropoxysilane, adamantyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilanePhenyltriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltripropoxysilane, benzyltriisopropoxysilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltripropoxysilane, methoxybenzyltriisopropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltripropoxysilane Alkane, tolyltriisopropoxysilane, phenylethyltrimethoxysilane, phenylethyltriethoxysilane, phenylethyltripropoxysilane, phenylethyltriisopropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltripropoxysilane, naphthyltriisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyl Dimethyl diethoxysilane, dimethyl dipropoxysilane, dimethyl diisopropoxysilane, diethyl dimethoxysilane, diethyl diethoxysilane, diethyl dipropoxysilane, diethyl diisopropoxysilane, dipropyl dimethoxysilane, dipropyl diethoxysilane, dipropyl dipropoxysilane, dipropyl diisopropoxysilane, diisopropyl dimethoxysilane, diisopropyl dimethoxysilane, diisopropyl dimethoxysilane Propyl diethoxysilane, diisopropyl dipropoxysilane, diisopropyl diisopropoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxysilane, dibutyldiisopropoxysilane, di(secondary butyl)dimethoxysilane, di(secondary butyl)diethoxysilane, di(secondary butyl)dipropoxysilane, di(secondary butyl)diisopropoxysilane Oxysilanes, bis(tert-butyl)dimethoxysilanes, bis(tert-butyl)diethoxysilanes, bis(tert-butyl)dipropoxysilanes, bis(tert-butyl)diisopropoxysilanes, dicyclopropyldimethoxysilanes, dicyclopropyldiethoxysilanes, dicyclopropyldipropoxysilanes, dicyclopropyldiisopropoxysilanes, dicyclobutyldimethoxysilanes, dicyclobutyldiethyl... Oxysilanes, dicyclobutyldipropoxysilanes, dicyclobutyldiisopropoxysilanes, dicyclopentyldimethoxysilanes, dicyclopentyldiethoxysilanes, dicyclopentyldipropoxysilanes, dicyclopentyldiisopropoxysilanes, dicyclohexyldimethoxysilanes, dicyclohexyldiethoxysilanes, dicyclohexyldipropoxysilanes, dicyclohexyldiisopropoxysilanes, dicyclohexenyldimethoxysilanes Oxysilane, dicyclohexenyldiethoxysilane, dicyclohexenyldiepropoxysilane, dicyclohexenyldieisopropoxysilane, dicyclohexenylethyldimethoxysilane, dicyclohexenylethyldiethoxysilane, dicyclohexenylethyldipropoxysilane, dicyclohexenylethyldiisopropoxysilane, dicyclooctyldimethoxysilane, dicyclooctyldiethoxysilane, dicyclooctyl Dipropoxysilane, Dicyclooctyldiisopropoxysilane, Dicyclopentadienylpropyldimethoxysilane, Dicyclopentadienylpropyldiethoxysilane, Dicyclopentadienylpropyldipropoxysilane, Dicyclopentadienylpropyldiisopropoxysilane, Bis(bicycloheptenyl)dimethoxysilane, Bis(bicycloheptenyl)diethoxysilane, Bis(bicycloheptenyl)dipropoxysilane,bis(bicycloheptenyl)diisopropoxysilane, bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis(bicycloheptenyl)dipropoxysilane, bis(bicycloheptenyl)diisopropoxysilane, diadamantyldimethoxysilane, diadamantyldiethoxysilane, diadamantyldipropoxysilane, diadamantyldiisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane Methoxysilane, methylphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethylbenzylmethoxysilane, dimethylbenzylethoxysilane, dimethylphenethylmethoxysilane, dimethylphenethylethoxysilane, etc.

[0056] The above compounds can ideally be exemplified as: tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane Alkane, cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenylethyltrimethoxysilane, phenylethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenylethylmethoxysilane, etc.

[0057] [Synthesis method (reaction) of thermocrosslinked polysiloxanes] (Synthesis Method 1: Acid Catalyst) The thermally crosslinked polysiloxane used in this invention can be manufactured by hydrolyzing and condensing one or more of hydrolyzable monomers (Sm) in the presence of an acid catalyst.

[0058] The acid catalysts that can be used at this time include: formic acid, acetic acid, oxalic acid, maleic acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid and other organic acids, hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, etc. The amount of catalyst used relative to 1 mol of monomer should preferably be 1×10⁻⁶ to 10 mol, 1×10⁻⁵ to 5 mol is better, and 1×10⁻⁴ to 1 mol is even better.

[0059] When obtaining thermally crosslinked polysiloxanes from these monomers via hydrolysis-condensation, the amount of water depends on the hydrolytic substituents of the monomers. For every 1 mole, it is preferable to add 0.01 to 100 moles, with 0.05 to 50 moles being more preferred, and 0.1 to 30 moles being even better. If the amount is below 100 moles, the equipment used for the reaction is smaller and more economical. If the amount is above 0.01 moles, the reaction will proceed fully.

[0060] The procedure involves adding the monomer to the catalyst aqueous solution and initiating the hydrolysis-condensation reaction. Alternatively, an organic solvent can be added to the catalyst aqueous solution, or the monomer can be diluted with an organic solvent; either method is acceptable. The reaction temperature should ideally be 0–100°C, with 5–80°C being more preferred. A suitable method is to maintain the temperature at 5–80°C during the dropwise addition of the monomer, followed by maturation at 20–80°C.

[0061] Organic solvents that can be added to the aqueous solution of the catalyst, or organic solvents that can dilute the monomer, are preferably: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, ethylene glycol, propylene glycol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl pentyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, and mixtures thereof.

[0062] Among these organic solvents, water-soluble solvents are ideal. Examples include: alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; polyols such as ethylene glycol and propylene glycol; polyol condensate derivatives such as butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, and ethylene glycol monopropyl ether; acetone, acetonitrile, and tetrahydrofuran. Solvents with a boiling point below 100°C are particularly ideal.

[0063] Furthermore, the optimal amount of organic solvent used relative to 1 mol of monomer is 0-1,000 ml, or 0-500 ml. Using less organic solvent results in a smaller reaction vessel, which is more economical.

[0064] Subsequently, if necessary, a neutralization reaction of the catalyst is carried out, and an aqueous solution of the reaction mixture is obtained. At this point, the amount of the alkaline substance used for neutralization should preferably be 0.1 to 2 equivalents relative to the acid used in the catalyst. This alkaline substance can be any substance that is alkaline in water.

[0065] Then, it is advisable to remove byproducts such as alcohols generated during the hydrolysis and condensation reaction from the aqueous solution of the reaction mixture using methods such as vacuum removal. The heating temperature of the aqueous reaction mixture at this time depends on the type of organic solvent added and the type of alcohols produced in the reaction; preferably 0–100°C, more preferably 10–90°C, and even more preferably 15–80°C. Furthermore, the vacuum level at this time varies depending on the type of organic solvent and alcohols to be removed, the exhaust device, the condensation and concentration device, and the heating temperature; preferably below atmospheric pressure, more preferably below 80 kPa, and even more preferably below 50 kPa. Accurately determining the amount of alcohol to be removed at this time is not easy, but removing approximately 80% or more of the generated alcohols is ideal.

[0066] The acid catalyst used in the hydrolysis and condensation can then be removed from the aqueous solution of the reaction mixture. The method for removing the acid catalyst involves mixing water with a solution of the thermally crosslinked polysiloxane and extracting the thermally crosslinked polysiloxane using an organic solvent. The organic solvent used should preferably be capable of dissolving the thermally crosslinked polysiloxane and should separate into two layers when mixed with water. Examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methylpentyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0067] Alternatively, a mixture of water-soluble organic solvents and water-insoluble organic solvents can be used. For example, suitable mixtures include methanol-ethyl acetate mixtures, ethanol-ethyl acetate mixtures, 1-propanol-ethyl acetate mixtures, 2-propanol-ethyl acetate mixtures, butanediol monomethyl ether-ethyl acetate mixtures, propylene glycol monomethyl ether-ethyl acetate mixtures, ethylene glycol monomethyl ether-ethyl acetate mixtures, butanediol monoethyl ether-ethyl acetate mixtures, propylene glycol monoethyl ether-ethyl acetate mixtures, ethylene glycol monoethyl ether-ethyl acetate mixtures, butanediol monopropyl ether-ethyl acetate mixtures, propylene glycol monopropyl ether-ethyl acetate mixtures, ethylene glycol monopropyl ether-ethyl acetate mixtures, methanol-methyl isobutyl ketone mixtures, ethanol-methyl isobutyl ketone mixtures, 1-propanol-methyl isobutyl ketone mixtures, 2-propanol-methyl isobutyl ketone mixtures, propylene glycol monomethyl ether-methyl isobutyl ketone mixtures, ethylene glycol monomethyl ether-methyl isobutyl ketone mixtures, propylene glycol monoethyl ether-methyl isobutyl ketone mixtures, propylene glycol monopropyl ether-methyl isobutyl ketone mixtures, ethylene glycol monopropyl ether-methyl isobutyl ketone mixtures, ethylene glycol monopropyl ether-methyl isobutyl ketone mixtures, propylene ...propylene glycol monopropyl ether-methyl isobutyl ketone mixture Mixtures of ketones, methanol-cyclopentyl methyl ether, ethanol-cyclopentyl methyl ether, 1-propanol-cyclopentyl methyl ether, 2-propanol-cyclopentyl methyl ether, propylene glycol monomethyl ether-cyclopentyl methyl ether, ethylene glycol monomethyl ether-cyclopentyl methyl ether, propylene glycol monoethyl ether-cyclopentyl methyl ether, ethylene glycol monoethyl ether-cyclopentyl methyl ether, propylene glycol monopropyl ether-cyclopentyl methyl ether, ethylene glycol monopropyl ether-cyclopentyl methyl ether, methanol-propylene glycol methyl ether acetate mixture, ethanol Mixtures of propylene glycol methyl ether acetate, 1-propanol-propylene glycol methyl ether acetate, 2-propanol-propylene glycol methyl ether acetate, propylene glycol monomethyl ether-propylene glycol methyl ether acetate, ethylene glycol monomethyl ether-propylene glycol methyl ether acetate, propylene glycol monoethyl ether-propylene glycol methyl ether acetate, ethylene glycol monoethyl ether-propylene glycol methyl ether acetate, propylene glycol monopropyl ether-propylene glycol methyl ether acetate, ethylene glycol monopropyl ether-propylene glycol methyl ether acetate, etc., but combinations are not limited to these.

[0068] In addition, the mixing ratio of water-soluble organic solvent and water-insoluble organic solvent can be appropriately selected. The ratio of water-soluble organic solvent to water-insoluble organic solvent should preferably be 0.1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass per 100 parts by mass.

[0069] Then, neutral water can be used for rinsing. Deionized water or ultrapure water is suitable. The amount of water relative to 1L of the thermally crosslinked polysiloxane solution should be 0.01~100L, preferably 0.05~50L, and even better, 0.1~5L. The rinsing method involves placing both solutions in the same container, stirring, and then allowing them to stand to separate the water layers. One or more rinses are sufficient; even 10 or more rinses will not achieve the desired cleaning effect, so approximately 1~5 rinses are recommended.

[0070] Other methods for removing acid catalysts include methods using ion exchange resins and methods involving neutralization with epoxy compounds such as ethylene oxide and propylene oxide. These methods can be appropriately selected based on the acid catalyst used in the reaction.

[0071] During the water washing operation, some of the thermally crosslinked polysiloxane will escape into the water layer, sometimes achieving an effect essentially equivalent to that of the grading operation. Therefore, the number of water washes and the amount of washing water can be appropriately selected based on the catalyst removal effect and the grading effect.

[0072] By adding the final solvent to either a thermally crosslinked polysiloxane solution containing residual acid catalyst or a thermally crosslinked polysiloxane solution where the acid catalyst has been removed, and then performing solvent exchange under reduced pressure, the desired thermally crosslinked polysiloxane solution can be obtained. The solvent exchange temperature depends on the type of reaction solvent and extraction solvent to be removed, and is preferably 0–100°C, more preferably 10–90°C, and even more preferably 15–80°C. Furthermore, the reduced pressure varies depending on the type of extraction solvent to be removed, the exhaust device, the condensation and concentration device, and the heating temperature, and is preferably below atmospheric pressure, more preferably below 80 kPa, and even more preferably below 50 kPa.

[0073] At this time, the thermally crosslinked polysiloxane may become unstable due to the change of solvent. This depends on the compatibility between the final solvent and the thermally crosslinked polysiloxane. To prevent this, a mono- or di-ortho-ol having a cyclic ether as a substituent, as described in paragraphs (0181) to (0182) of Japanese Patent Application Publication No. 2009-126940, can be added as a stabilizer. The amount added is preferably 0 to 25 parts by mass, more preferably 0 to 15 parts by mass, and even more preferably 0 to 5 parts by mass, relative to 100 parts by mass of the thermally crosslinked polysiloxane in the solution before solvent exchange, but preferably 0.5 parts by mass or more. If necessary, the solution before solvent exchange can be treated by adding a mono- or di-ortho-ol having a cyclic ether as a substituent before performing the solvent exchange operation.

[0074] Thermally crosslinked polysiloxanes should preferably be prepared as solutions of appropriate concentrations beforehand. The concentration should ideally be 0.1–20% by mass. At such concentrations, further condensation reactions will not occur, thus preventing the polysiloxane from becoming insoluble in organic solvents. Furthermore, the amount of solvent required is reduced, making it more economical and desirable.

[0075] The final solvent added to the thermally crosslinked polysiloxane solution should preferably be an alcohol-based solvent, preferably a monoalkyl ether derivative of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, or butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol, etc., are preferred.

[0076] If these solvents are the main components, non-alcoholic solvents can also be added as auxiliary solvents. Examples of auxiliary solvents include acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl pentyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0077] Another reaction procedure using an acid catalyst involves adding water or an aqueous organic solvent to the monomer or its organic solution to initiate the hydrolysis reaction. The catalyst can be added to the monomer or its organic solution, or to water or an aqueous organic solvent. The reaction temperature is preferably 0–100°C, with 10–80°C being more ideal. A suitable method is to heat the mixture to 10–50°C during the dropwise addition of water, followed by raising the temperature to 20–80°C to allow it to mature.

[0078] When using organic solvents, water-soluble solvents are preferred. Examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and other polyol condensate derivatives and mixtures thereof.

[0079] The optimal amount of organic solvent used relative to 1 mole of monomer is 0-1,000 ml, or 0-500 ml. Lower amounts of organic solvent result in smaller reaction vessels, making it more economical. The resulting aqueous reaction mixture can be post-treated using the same method described above to obtain thermally crosslinked polysiloxanes.

[0080] (Synthesis Method 2: Alkali Catalyst) Furthermore, thermally crosslinked polysiloxanes can be manufactured by hydrolyzing and condensing one or more hydrolyzable monomers (Sm) in the presence of an alkaline catalyst. The alkaline catalysts used at this time can include: methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperidine, pyrrolidine, piperidine, methylpyridine, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. The amount of catalyst used relative to 1 mol of monomer should preferably be 1×10⁻⁶ mol to 10 mol, preferably 1×10⁻⁵ mol to 5 mol, and even better if it is 1×10⁻⁴ mol to 1 mol.

[0081] When obtaining thermally crosslinked polysiloxanes from the above monomers via hydrolysis-condensation, the amount of water added should be 0.1 to 50 mol per mol of the hydrolyzable substituents bonded to the monomers. If the amount is less than 50 mol, the equipment used for the reaction is smaller and more economical. If the amount is 0.1 mol or more, the reaction will proceed fully.

[0082] The procedure involves adding the monomer to the catalyst aqueous solution and initiating the hydrolysis-condensation reaction. Alternatively, an organic solvent can be added to the catalyst aqueous solution, or the monomer can be diluted with an organic solvent; either method is acceptable. The reaction temperature should ideally be 0–100°C, with 5–80°C being more preferred. A suitable method is to maintain the temperature at 5–80°C during the dropwise addition of the monomer, followed by maturation at 20–80°C.

[0083] Organic solvents that can be added to aqueous solutions of alkaline catalysts, or organic solvents that can dilute the monomer, should preferably be the same as those that can be added to aqueous solutions of acidic catalysts. Furthermore, for economical reaction implementation, the amount of organic solvent used should preferably be 0 to 1,000 ml relative to 1 mol of monomer.

[0084] Subsequently, if necessary, a neutralization reaction of the catalyst is carried out, and an aqueous solution of the reaction mixture is obtained. At this point, the amount of acidic substance used for neutralization should preferably be 0.1 to 2 equivalents relative to the basic substance used in the catalyst. This acidic substance can be any substance that is acidic in water.

[0085] Then, it is advisable to remove byproducts such as alcohols generated during the hydrolysis and condensation reaction from the aqueous solution of the reaction mixture using methods such as vacuum removal. The heating temperature of the aqueous reaction mixture depends on the type of organic solvent added and the type of alcohol produced, but is preferably 0–100°C, more preferably 10–90°C, and even more preferably 15–80°C. Furthermore, the vacuum level at this point varies depending on the type of organic solvent and alcohol to be removed, the exhaust system, the condensation and concentration system, and the heating temperature; it is preferably below atmospheric pressure, more preferably below 80 kPa, and even more preferably below 50 kPa. Determining the exact amount of alcohol to be removed at this point is not easy, but removing approximately 80% or more of the generated alcohol is ideal.

[0086] Then, in order to remove the catalyst used in the hydrolysis condensation, the thermally crosslinked polysiloxane is extracted using an organic solvent. The organic solvent used at this time should preferably be able to dissolve the thermally crosslinked polysiloxane and should separate into two layers when mixed with water. Examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methylpentyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0087] Alternatively, a mixture of water-soluble organic solvents and water-insoluble organic solvents can be used.

[0088] Specific examples of organic solvents used in removing alkaline catalysts include: the organic solvents specifically exemplified above as used in removing acid catalysts, or mixtures of water-soluble organic solvents and water-insoluble organic solvents.

[0089] In addition, the mixing ratio of water-soluble organic solvent and water-poorly soluble organic solvent can be appropriately selected. Relative to 100 parts by mass of water-poorly soluble organic solvent, it is preferable to use 0.1 to 1,000 parts by mass of water-soluble organic solvent, preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0090] Then, rinse with neutral water. Deionized water or ultrapure water can be used. The amount of water relative to 1L of the thermally crosslinked polysiloxane solution should be 0.01~100L, preferably 0.05~50L, and even better, 0.1~5L. The rinsing method involves placing both solutions in the same container, stirring, and then allowing them to stand to separate the water layers. One or more rinses are sufficient; even 10 or more rinses will not achieve the desired cleaning effect, so approximately 1~5 rinses are recommended.

[0091] The final solvent is added to the cleaned thermally crosslinked polysiloxane solution, and solvent exchange is performed under reduced pressure to obtain the desired thermally crosslinked polysiloxane solution. The solvent exchange temperature depends on the type of extraction solvent to be removed, and is preferably 0–100°C, more preferably 10–90°C, and even more preferably 15–80°C. Furthermore, the reduced pressure varies depending on the type of extraction solvent to be removed, the exhaust system, the condensation and concentration system, and the heating temperature; it is preferably below atmospheric pressure, more preferably below 80 kPa, and even more preferably below 50 kPa.

[0092] The final solvent added to the thermally crosslinked polysiloxane solution should preferably be an alcohol-based solvent, preferably a monoalkyl ether derivative of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc. Specifically, it is preferable to use propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol, etc.

[0093] Furthermore, another reaction procedure using an alkaline catalyst is preferably as follows: Water or an aqueous organic solvent is added to the monomer or its organic solution to initiate the hydrolysis reaction. The catalyst can be added to the monomer or its organic solution, or to water or an aqueous organic solvent. The reaction temperature is preferably 0–100°C, with 10–80°C being more ideal. When adding water dropwise, the temperature should be raised to 10–50°C, and then further increased to 20–80°C to allow for maturation.

[0094] Organic solvents that can be used as monomers, such as organic solutions or aqueous organic solvents, should preferably be water-soluble. Examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and other polyol condensate derivatives and mixtures thereof.

[0095] The molecular weight of the thermally crosslinked polysiloxanes obtained using the above synthesis methods 1 or 2 can be adjusted not only by selecting the monomers but also by controlling the reaction conditions during polymerization. If the weight-average molecular weight is below 100,000, no foreign matter is generated and uneven coating occurs; therefore, a weight of below 100,000 is preferable, 200-50,000 is better, and 300-30,000 is even better. Furthermore, the above-mentioned weight-average molecular weight data were obtained using gel permeation chromatography (GPC) with RI as the detector and tetrahydrofuran as the dissolution solvent, using polystyrene as the standard substance, and the molecular weight was expressed in polystyrene form.

[0096] The physical properties of the thermally crosslinked polysiloxane used in this invention vary depending on the type of acid or alkali catalyst used during hydrolysis and condensation, as well as the reaction conditions. Therefore, it can be appropriately selected to match the performance of the underlying membrane used as the desired inhibitor.

[0097] In addition, a polysiloxane derivative manufactured under the aforementioned conditions using an acid or alkali catalyst can be used as a component of the composition for forming the lower layer film of the inhibitor. This can be a mixture of one or more hydrolyzable monomers (Sm) and a hydrolyzable metal compound represented by the following general formula (Mm). U(OR7)m7(OR8)m8 (Mm) In the general formula (Mm), R7 and R8 are organic groups with carbon numbers from 1 to 30, m7+m8 and the valence number determined by the type of U are the same, m7 and m8 are integers above 0, and U is an element of group III, IV or V of the periodic table excluding carbon and silicon.

[0098] Examples of hydrolyzable metal compounds represented by the general formula (Mm) used here are as follows. When U is boron, examples of hydrolyzable metal compounds represented by the general formula (Mm) include methoxy boron, ethoxy boron, propoxy boron, butoxy boron, pentoxy boron, hexoxy boron, cyclopentoxy boron, cyclohexoxy boron, allyloxy boron, phenoxy boron, methoxyethoxy boron, boric acid, boron oxide, etc.

[0099] When U is aluminum, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxyaluminum, ethoxyaluminum, propoxyaluminum, butoxyaluminum, pentoxyaluminum, hexoxyaluminum, cyclopentoxyaluminum, cyclohexyloxyaluminum, allyloxyaluminum, phenoxyaluminum, methoxyethoxyaluminum, ethoxyethoxyaluminum, dipropoxyethylacetate aluminum, dibutoxyethylacetate aluminum, propoxydiethylacetate aluminum, butoxydiethylacetate aluminum, 2,4-pentanedione aluminum, 2,2,6,6-tetramethyl-3,5-heptadecanedione aluminum, etc.

[0100] When U is gallium, the hydrolyzable metal compounds represented by the general formula (Mm) can include methoxy gallium, ethoxy gallium, propoxy gallium, butoxy gallium, pentoxy gallium, hexoxy gallium, cyclopentoxy gallium, cyclohexoxy gallium, allyloxy gallium, phenoxy gallium, methoxyethoxy gallium, ethoxyethoxy gallium, dipropoxyethylacetate gallium, dibutoxyethylacetate gallium, propoxydiethylacetate gallium, butoxydiethylacetate gallium, 2,4-pentanedione gallium, 2,2,6,6-tetramethyl-3,5-heptanedione gallium, etc.

[0101] When U is yttrium, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxyyttrium, ethoxyyttrium, propoxyyttrium, butoxyyttrium, pentooxyyttrium, hexoxyyttrium, cyclopentoxyyttrium, cyclohexoxyyttrium, allyloxyyttrium, phenoxyyttrium, methoxyethoxyyttrium, ethoxyethoxyyttrium, dipropoxyethyl acetate yttrium, dibutoxyethyl acetate yttrium, propoxydiethyl acetate yttrium, butoxydiethyl acetate yttrium, 2,4-pentanedione acid yttrium, 2,2,6,6-tetramethyl-3,5-heptadecanedione acid yttrium, etc.

[0102] When U is germanium, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxy germanium, ethoxy germanium, propoxy germanium, butoxy germanium, pentooxy germanium, hexoxy germanium, cyclopentoxy germanium, cyclohexoxy germanium, allyloxy germanium, phenoxy germanium, methoxyethoxy germanium, ethoxyethoxy germanium, etc.

[0103] When U is titanium, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxy titanium, ethoxy titanium, propoxy titanium, butoxy titanium, pentoxy titanium, hexoxy titanium, cyclopentoxy titanium, cyclohexyloxy titanium, allyloxy titanium, phenoxy titanium, methoxyethoxy titanium, ethoxyethoxy titanium, dipropoxybis(ethyl)acetate titanium, dibutoxybis(ethyl)acetate titanium, dipropoxybis(2,4-pentanedione) titanium, dibutoxybis(2,4-pentanedione) titanium, etc.

[0104] When U is hafnium, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxyhafnium, ethoxyhafnium, propoxyhafnium, butoxyhafnium, pentooxyhafnium, hexoxyhafnium, cyclopentoxyhafnium, cyclohexoxyhafnium, allyloxyhafnium, phenoxyhafnium, methoxyethoxyhafnium, ethoxyethoxyhafnium, dipropoxybis(ethyl)acetic acid hafnium, dibutoxybis(ethyl)acetic acid hafnium, dipropoxybis(2,4-pentanedione) hafnium, and dibutoxybis(2,4-pentanedione) hafnium, etc.

[0105] When U is tin, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxytin, ethoxytin, propoxytin, butoxytin, phenoxytin, methoxyethoxytin, ethoxyethoxytin, tin 2,4-pentanedione, tin 2,2,6,6-tetramethyl-3,5-heptadecanedione, etc.

[0106] When U is arsenic, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxyarsenic, ethoxyarsenic, propoxyarsenic, butoxyarsenic, phenoxyarsenic, etc.

[0107] When U is antimony, the hydrolyzable metal compounds represented by the general formula (Mm) can include methoxyantimony, ethoxyantimony, propoxyantimony, butoxyantimony, phenoxyantimony, antimony acetate, antimony propionate, etc.

[0108] When U is niobium, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxyniobium, ethoxyniobium, propoxyniobium, butoxyniobium, phenoxyniobium, etc.

[0109] When U is tantalum, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxy tantalum, ethoxy tantalum, propoxy tantalum, butoxy tantalum, phenoxy tantalum, etc.

[0110] When U is bismuth, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxybismuth, ethoxybismuth, propoxybismuth, butoxybismuth, phenoxybismuth, etc.

[0111] When U is phosphorus, hydrolyzable metal compounds represented by the general formula (Mm) can include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, phosphorus pentoxide, etc.

[0112] When U is vanadium, hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified by vanadium bis(2,4-pentanedione) oxide, vanadium 2,4-pentanedione, vanadium tributoxy, vanadium tripropoxy, etc.

[0113] When U is zirconium, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxyzirconium, ethoxyzirconium, propoxyzirconium, butoxyzirconium, phenoxyzirconium, bis(2,4-pentanedione acid) dibutoxyzirconium, bis(2,2,6,6-tetramethyl-3,5-heptadecanedione acid) dipropoxyzirconium, etc.

[0114] [Amount of thermally crosslinked polysiloxane added] In the silicon-containing inhibitor lower film composition of the present invention, the amount of thermally crosslinked polysiloxane incorporated, for example, relative to the solvent, is preferably set to 0.1 to 10 by mass.

[0115] [Crosslinking catalyst for silicate polymerization] The silicon-containing inhibitor lower film composition of the present invention contains the aforementioned thermally crosslinked polysiloxane, and in addition, contains a compound represented by the following general formula (Xc). Furthermore, this compound will sometimes be referred to as a crosslinking catalyst for siliconoxane polymerization or simply as a crosslinking catalyst.

[0116] In this invention, the crosslinking catalyst for the aforementioned silicon oxide polymerization can be a strontium salt, ferric salt, phosphonium salt, ammonium salt, or a polysiloxane having them as part of its structure, or an alkali metal salt.

[0117] Crosslinking catalysts (Xc) for siloxane polymerization can be listed as compounds represented by the following general formula (Xc0). LaHbA (Xc0) In the formula, L is lithium, sodium, potassium, rubidium, cesium, strontium, zinc, phosphorus or ammonium, A is a non-nucleophilic relative ion, a is an integer greater than or equal to 1, b is an integer greater than or equal to 0 or 1, and a+b is the valence of the non-nucleophilic relative ion.

[0118] Specific examples of (Xc0) include strontium salts of the general formula (Xc-1), monium salts of the general formula (Xc-2), phosphonium salts of the general formula (Xc-3), ammonium salts of the general formula (Xc-4), and alkali metal salts.

[0119] Luster salt (Xc-1), zirconia salt (Xc-2), and phosphorus salt (Xc-3) are exemplified below. [Chemistry 16]

[0120] Furthermore, ammonium salts (Xc-4) are exemplified as follows. [Chemistry 17] In the formula, R204, R205, R206, and R207 represent linear, branched, or cyclic alkyl, alkenyl, alkyl-oxyalkenyl, or alkenyl-oxyalkenyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, or aralkyl or aryl-oxyalkyl groups having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy groups, etc. Furthermore, R205 and R206 can also form a ring, and when a ring is formed, R205 and R206 represent alkenyl groups having 1 to 6 carbon atoms, respectively. A- represents a non-nucleophilic relative ion. R208, R209, R210, and R211 are similar to R204, R205, R206, and R207, but may also contain hydrogen atoms. R208 and R209, R208 and R209 and R210 can also form rings, and when rings are formed, R208 and R209 and R208 and R209 and R210 represent alkyl groups with 3 to 10 carbon atoms.

[0121] The aforementioned R204, R205, R206, R207, R208, R209, R210, and R211 can be the same as or different from each other. Specifically, alkyl groups can include: methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, adamantyl, etc. Alkenyl groups can include: vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl, etc. Side-oxyalkyl groups can include: 2-side-oxycyclopentyl, 2-side-oxycyclohexyl, etc., or 2-side-oxypropyl, 2-cyclopentyl-2-side-oxyethyl, 2-cyclohexyl-2-side-oxyethyl, 2-(4-methylcyclohexyl)-2-side-oxyethyl, etc. Aryl groups can be listed as: phenyl, naphthyl, etc.; or alkoxyphenyls such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, m-tert-butoxyphenyl, etc.; alkylphenyls such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, etc.; alkylnaphthyl such as methylnaphthyl, ethylnaphthyl, etc.; alkoxynaphthyl such as methoxynaphthyl, ethoxynaphthyl, etc.; dialkylnaphthyl such as dimethylnaphthyl, diethylnaphthyl, etc.; dialkoxynaphthyl such as dimethoxynaphthyl, diethoxynaphthyl, etc. Arylalkyl groups can be listed as: benzyl, phenylethyl, phenethyl, etc. Aryl alkyl groups can be listed as: 2-phenyl-2-oxyethyl, 2-(1-naphthyl)-2-oxyethyl, 2-(2-naphthyl)-2-oxyethyl, etc., 2-aryl-2-oxyethyl, etc.

[0122] Non-nucleophilic ions of the A- group include: hydroxide ions, formate ions, acetate ions, propionate ions, butyrate ions, valerate ions, hexanoate ions, heptanoate ions, octanoate ions, nonanoate ions, decanoate ions, oleic acid ions, stearate ions, linoleic acid ions, and linolenic acid ions. Monovalent ions include: phthalic acid ions, benzoic acid ions, phthalic acid ions, isophthalic acid ions, terephthalic acid ions, salicylic acid ions, trifluoroacetic acid ions, monochloroacetic acid ions, dichloroacetic acid ions, trichloroacetic acid ions, fluoride ions, chloride ions, bromide ions, iodide ions, nitrate ions, nitrite ions, chloric acid ions, bromate ions, methanesulfonic acid ions, p-toluenesulfonic acid ions, monomethyl sulfate ions, etc.; and monovalent or divalent ions such as oxalate ions, malonic acid ions, methylmalonic acid ions, ethylmalonic acid ions, propylmalonic acid ions, butylmalonic acid ions, dimethylmalonic acid ions, diethylmalonic acid ions, succinic acid ions, methylsuccinic acid ions, glutaric acid ions, adipic acid ions, itconic acid ions, maleic acid ions, fumaric acid ions, citrate ions, citric acid ions, carbonate ions, sulfate ions, etc.

[0123] Alkali metal salts include: hydroxides of lithium, sodium, potassium, and cesium; formates; acetates; propionates; butyrates; valerates; hexanoates; heptanoates; octanoates; nonanoates; decanoates; oleates; stearates; linoleic acid; linolenic acid; benzoates; phthalates; isophthalates; terephthalates; salicylates; trifluoroacetates; monochloroacetates; dichloroacetates; and divalent salts such as oxalates, malonates, methylmalonates, ethylmalonates, propylmalonates, butylmalonates, dimethylmalonates, diethylmalonates, succinates, methylsuccinates, glutarates, adipates, iconates, maleates, fumarates, citrates, and carbonates.

[0124] (Sulphur salt (Xc-1)) Specifically, strontium salts (Xc-1) can be listed as follows: triphenylstrontium formate, triphenylstrontium acetate, triphenylstrontium propionate, triphenylstrontium butyrate, triphenylstrontium benzoate, triphenylstrontium phthalate, triphenylstrontium isophthalate, triphenylstrontium terephthalate, triphenylstrontium salicylate, triphenylstrontium trifluoromethanesulfonate, triphenylstrontium trifluoroacetate, triphenylstrontium monochloroacetate, triphenylstrontium dichloroacetate, triphenylstrontium trichloroacetate, triphenylstrontium hydroxide, triphenylstrontium nitrate, triphenylstrontium chloride, triphenylstrontium bromide, triphenylstrontium oxalate, triphenylstrontium malonate, and triphenylstrontium methylmalonate. Triphenylspar, including triphenylspar ethylmalonic acid, triphenylspar propylmalonic acid, triphenylspar butylmalonic acid, triphenylspar dimethylmalonic acid, triphenylspar diethylmalonic acid, triphenylspar succinate, triphenylspar methylsuccinate, triphenylspar glutaric acid, triphenylspar adipic acid, triphenylspar iconic acid, triphenylspar maleate, triphenylspar fumarate, triphenylspar citrate, triphenylspar citrate, triphenylspar carbonate, bis(triphenylspar oxalate), bis(triphenylspar maleate), bis(triphenylspar fumarate), bis(triphenylspar citrate), bis(triphenylspar citrate), and bis(triphenylspar carbonate), etc.

[0125] (Fossilized Salt (Xc-2)) Furthermore, specific examples of ferric salts (Xc-2) include: diphenylferric formate, diphenylferric acetate, diphenylferric propionate, diphenylferric butyrate, diphenylferric benzoate, diphenylferric phthalate, diphenylferric isophthalate, diphenylferric terephthalate, diphenylferric salicylate, diphenylferric trifluoromethanesulfonate, diphenylferric trifluoroacetate, diphenylferric monochloroacetate, diphenylferric dichloroacetate, and diphenylferric trichloroacetate. Diphenyl oxalate, diphenyl nitrate, diphenyl oxalate, diphenyl oxalate, diphenyl maleate, diphenyl fumarate, diphenyl citrate, diphenyl citrate, diphenyl citrate, diphenyl citrate, diphenyl citrate, diphenyl citrate, diphenyl oxalate, diphenyl maleate, diphenyl fumarate, diphenyl citrate, diphenyl citrate, diphenyl citrate, diphenyl citrate, diphenyl citrate, etc.

[0126] (phosphonium salt (Xc-3)) Furthermore, specific examples of phosphonium salts (Xc-3) include: tetraethylphosphonium formate, tetraethylphosphonium acetate, tetraethylphosphonium propionate, tetraethylphosphonium butyrate, tetraethylphosphonium benzoate, tetraethylphosphonium phthalate, tetraethylphosphonium isophthalate, tetraethylphosphonium terephthalate, tetraethylphosphonium salicylate, tetraethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoroacetate, tetraethylphosphonium monochloroacetate, tetraethylphosphonium dichloroacetate, and trichloroacetic acid. Tetraethylphosphonium, tetraethylphosphonium hydroxide, tetraethylphosphonium nitrate, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetraethylphosphonium oxalate, tetraethylphosphonium maleate, tetraethylphosphonium fumarate, tetraethylphosphonium citrate, tetraethylphosphonium citrate, tetraethylphosphonium carbonate, bis(tetraethylphosphonium) oxalate, bis(tetraethylphosphonium) maleate, bis(tetraethylphosphonium) fumarate, bis(tetraethylphosphonium) citrate, bis(tetraethylphosphonium) citrate Tetraethylphosphonium carbonate, tetraphenylphosphonium formate, tetraphenylphosphonium acetate, tetraphenylphosphonium propionate, tetraphenylphosphonium butyrate, tetraphenylphosphonium benzoate, tetraphenylphosphonium phthalate, tetraphenylphosphonium isophthalate, tetraphenylphosphonium terephthalate, tetraphenylphosphonium salicylate, tetraphenylphosphonium trifluoromethanesulfonate, tetraphenylphosphonium trifluoroacetate, tetraphenylphosphonium monochloroacetate, tetraphenylphosphonium dichloroacetate, tetraphenylphosphonium trichloroacetate, and hydroxide. Tetraphenylphosphonium, tetraphenylphosphonium nitrate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium oxalate, tetraphenylphosphonium maleate, tetraphenylphosphonium fumarate, tetraphenylphosphonium citrate, tetraphenylphosphonium citrate, tetraphenylphosphonium carbonate, bis(tetraphenylphosphonium) oxalate, bis(tetraphenylphosphonium) maleate, bis(tetraphenylphosphonium) fumarate, bis(tetraphenylphosphonium) citrate, bis(tetraphenylphosphonium) citrate, bis(tetraphenylphosphonium) carbonate, etc.

[0127] (Ammonium salt (Xc-4)) On the other hand, specific examples of ammonium salts (Xc-4) include: tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetramethylammonium phthalate, tetramethylammonium isophthalate, tetramethylammonium terephthalate, tetramethylammonium salicylate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium monochloroacetate, tetramethylammonium dichloroacetate, tetramethylammonium trichloroacetate, tetramethylammonium hydroxide, tetramethylammonium nitrate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium monomethylsulfate, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium maleate, tetramethylammonium fumarate, tetramethylammonium citrate, tetramethylammonium citrate, tetramethylammonium carbonate, bis(tetramethylammonium oxalate) bis(tetramethylammonium malonate) bis(tetramethylammonium maleate) bis(tetramethylammonium fumarate), and bis(tetramethylammonium citrate). Ammonium, Tetramethylammonium citrate, Tetramethylammonium carbonate, Tetraethylammonium formate, Tetraethylammonium acetate, Tetraethylammonium propionate, Tetraethylammonium butyrate, Tetraethylammonium benzoate, Tetraethylammonium phthalate, Tetraethylammonium isophthalate, Tetraethylammonium terephthalate, Tetraethylammonium salicylate, Tetraethylammonium trifluoromethanesulfonate, Tetraethylammonium trifluoroacetate, Tetraethylammonium monochloroacetate, Tetraethylammonium dichloroacetate, Tetraethylammonium trichloroacetate, Tetraethylammonium hydroxide, Tetraethylammonium nitrate, Tetraethylammonium chloride, Tetraethylammonium bromide, Tetraethylammonium iodide, Tetraethylammonium monomethylsulfate, Tetraethylammonium oxalate, Tetraethylammonium malonate, Tetraethylammonium maleate, Tetraethylammonium fumarate, Tetraethylammonium citrate, Tetraethylammonium carbonate, Tetraethylammonium oxalate, Tetraethylammonium malonate, Tetraethylammonium maleate, Tetraethylammonium fumarate, Tetraethylammonium citrate ... Tetraethylammonium citrate, tetraethylammonium carbonate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, tetrapropylammonium dichloroacetate, tetrapropylammonium trichloroacetate, tetrapropylammonium hydroxide, tetrapropylammonium nitrate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrapropylammonium monomethyl sulfate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium maleate, tetrapropylammonium fumarate, tetrapropylammonium citrate, tetrapropylammonium citrate, tetrapropylammonium carbonate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium maleate, tetrapropylammonium fumarate, tetrapropylammonium citrate, tetrapropylammonium citrate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium maleate, tetrapropylammonium fumarate, tetrapropylammonium citrate, tetrapropylammonium citrate Tetrapropylammonium, Tetrapropylammonium carbonate, Tetrabutylammonium formate, Tetrabutylammonium acetate, Tetrabutylammonium propionate, Tetrabutylammonium butyrate, Tetrabutylammonium benzoate, Tetrabutylammonium phthalate, Tetrabutylammonium isophthalate, Tetrabutylammonium terephthalate, Tetrabutylammonium salicylate, Tetrabutylammonium trifluoromethanesulfonate, Tetrabutylammonium trifluoroacetate, Tetrabutylammonium monochloroacetate, Tetrabutylammonium dichloroacetate, Tetrabutylammonium trichloroacetate, Tetrabutylammonium hydroxide, Tetrabutylammonium nitrate, Tetrabutylammonium chloride, Tetrabutylammonium bromide, Tetrabutylammonium iodide, Tetrabutylammonium methanesulfonate, Tetrabutylammonium monomethyl sulfate, Tetrabutylammonium oxalate, Tetrabutylammonium malonate, Tetrabutylammonium maleate, Tetrabutylammonium fumarate, Tetrabutylammonium citrate, Tetrabutylammonium citrate, Tetrabutylammonium carbonate, Tetrabutylammonium oxalate, Tetrabutylammonium malonate, Tetrabutylammonium maleate, Tetrabutylammonium fumarate, Tetrabutylammonium citrateBis(tetrabutylammonium) citrate, Bis(tetrabutylammonium) carbonate, Trimethylphenylammonium formate, Trimethylphenylammonium acetate, Trimethylphenylammonium propionate, Trimethylphenylammonium butyrate, Trimethylphenylammonium benzoate, Trimethylphenylammonium phthalate, Trimethylphenylammonium isophthalate, Trimethylphenylammonium terephthalate, Trimethylphenylammonium salicylate, Trimethylphenylammonium trifluoromethanesulfonate, Trimethylphenylammonium trifluoroacetate, Trimethylphenylammonium monochloroacetate, Trimethylphenylammonium dichloroacetate, Trimethylphenylammonium trichloroacetate, Trimethylphenylammonium hydroxide, Trimethylphenylammonium nitrate, Trimethylphenylammonium chloride, Trimethylphenylammonium bromide, Trimethylphenylammonium iodide, Trimethylphenylammonium methanesulfonate, Trimethylphenylammonium monomethylsulfate, Trimethylphenylammonium oxalate, Trimethylphenylammonium malonate Trimethylphenylammonium maleate, trimethylphenylammonium fumarate, trimethylphenylammonium citrate, trimethylphenylammonium citrate, trimethylphenylammonium carbonate, bis(trimethyl)phenylammonium oxalate, bis(trimethyl)phenylammonium malonate, bis(trimethyl)phenylammonium maleate, bis(trimethyl)phenylammonium fumarate, bis(trimethyl)phenylammonium citrate, bis(trimethyl)phenylammonium citrate, bis(trimethyl)phenylammonium carbonate, triethylphenylammonium formate, triethylphenylammonium acetate, triethylphenylammonium propionate, triethylphenylammonium butyrate, triethylphenylammonium benzoate, triethylphenylammonium phthalate, triethylphenylammonium isophthalate, triethylphenylammonium terephthalate, triethylphenylammonium salicylate, triethylphenylammonium trifluoromethanesulfonate, triethylphenylammonium trifluoroacetate, triethylphenylammonium monochloroacetate Triethylphenylammonium dichloroacetate, triethylphenylammonium trichloroacetate, triethylphenylammonium hydroxide, triethylphenylammonium nitrate, triethylphenylammonium chloride, triethylphenylammonium bromide, triethylphenylammonium iodide, triethylphenylammonium methanesulfonate, triethylphenylammonium monomethyl sulfate, triethylphenylammonium oxalate, triethylphenylammonium malonate, triethylphenylammonium maleate, triethylphenylammonium fumarate, triethylphenylammonium citrate, triethylphenylammonium citrate, triethylphenylammonium carbonate, bis(triethylphenylammonium) oxalate, bis(triethylphenylammonium) malonate, bis(triethylphenylammonium) maleate, bis(triethylphenylammonium) fumarate, bis(triethylphenylammonium) citrate, bis(triethylphenylammonium) citrate, bis(triethylphenylammonium) carbonate, benzyl dimethylphenylammonium formate Benzyl dimethyl phenyl ammonium acetate, benzyl dimethyl phenyl ammonium propionate, benzyl dimethyl phenyl ammonium butyrate, benzyl dimethyl phenyl ammonium benzoate, benzyl dimethyl phenyl ammonium phthalate, benzyl dimethyl phenyl ammonium isophthalate, benzyl dimethyl phenyl ammonium terephthalate, benzyl dimethyl phenyl ammonium salicylate, benzyl dimethyl phenyl ammonium trifluoromethanesulfonate, benzyl dimethyl phenyl ammonium trifluoroacetate, benzyl dimethyl phenyl ammonium monochloroacetate, benzyl dimethyl phenyl ammonium dichloroacetate, benzyl dimethyl phenyl ammonium dichloroacetate, benzyl dimethyl phenyl ammonium trichloroacetate, benzyl dimethyl phenyl ammonium hydroxide, benzyl dimethyl phenyl ammonium nitrate, benzyl dimethyl phenyl ammonium chloride, benzyl dimethyl phenyl ammonium bromide, benzyl dimethyl phenyl ammonium iodide, benzyl dimethyl phenyl ammonium methanesulfonate, benzyl dimethyl phenyl ammonium monomethyl sulfate.Benzyl dimethyl phenyl ammonium oxalate, benzyl dimethyl phenyl ammonium malonate, benzyl dimethyl phenyl ammonium maleate, benzyl dimethyl phenyl ammonium fumarate, benzyl dimethyl phenyl ammonium citrate, benzyl dimethyl phenyl ammonium citrate, benzyl dimethyl phenyl ammonium carbonate, dibenzyl dimethyl phenyl ammonium oxalate, dibenzyl dimethyl phenyl ammonium malonate, dibenzyl dimethyl phenyl ammonium maleate, dibenzyl dimethyl phenyl ammonium fumarate, dibenzyl dimethyl phenyl ammonium citrate, dibenzyl dimethyl phenyl ammonium carbonate, etc.

[0128] (alkali metal salts) Examples of alkali metal salts include: lithium formate, lithium acetate, lithium propionate, lithium butyrate, lithium benzoate, lithium phthalate, lithium isophthalate, lithium terephthalate, lithium salicylate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium monochloroacetate, lithium dichloroacetate, lithium trichloroacetate, lithium hydroxide, lithium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium methanesulfonate, lithium oxalate, lithium hydride malonate, lithium maleate, and lithium fumarate. Lithium citrate, lithium bicarbonate, lithium oxalate, lithium malonate, lithium maleate, lithium fumarate, lithium citrate, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butyrate, sodium benzoate, sodium phthalate, sodium isophthalate, sodium terephthalate, sodium salicylate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, sodium dichloroacetate, sodium trichloroacetate, sodium hydroxide, nitric acid Sodium, sodium chloride, sodium bromide, sodium iodide, sodium methanesulfonate, sodium oxalate, sodium hydrogen malonate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium citrate, sodium bicarbonate, sodium oxalate, sodium malonate, sodium maleate, sodium fumarate, sodium citrate, sodium citrate, sodium carbonate, potassium formate, potassium acetate, potassium propionate, potassium butyrate, potassium benzoate, potassium phthalate, potassium isophthalate, potassium terephthalate, water Potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, potassium trichloroacetate, potassium hydroxide, potassium nitrate, potassium chloride, potassium bromide, potassium iodide, potassium methanesulfonate, potassium hydrogen oxalate, potassium hydrogen malonate, potassium hydrogen maleate, potassium hydrogen fumarate, potassium hydrogen citrate, potassium hydrogen citrate, potassium bicarbonate, potassium oxalate, potassium malonate, potassium maleate, potassium fumarate, potassium citrate, potassium citrate, potassium carbonate, etc.

[0129] [Regarding the curing catalyst (Xc), it is a thermosetting polysiloxane having ammonium salt, strontium salt, phosphonium salt, or ferromonium salt as part of its structure.] The crosslinking catalyst (Xc) for polymerization in this invention can be exemplified by a thermosetting polysiloxane (Xc-10) having ammonium salt, strontium salt, phosphonium salt, or monazite salt as part of its structure.

[0130] The raw materials used to manufacture (Xc-10) used herein may be compounds represented by the following general formula (Xm). R1AA1R2AA2R3AA3Si(OR0A)(4-A1-A2-A3) (Xm) In the formula, R0A is a hydrocarbon group with 1 to 6 carbon atoms, at least one of R1A, R2A, and R3A is an organic group having an ammonium salt, strontium salt, phosphonium salt, or monazine salt, and the others are hydrogen atoms or monovalent organic groups with 1 to 30 carbon atoms. A1, A2, and A3 are 0 or 1, and 1 ≤ A1 + A2 + A3 ≤ 3. Here, R0A can be exemplified as: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl.

[0131] (A hydrolyzable silicon compound (Xm-1) with strontium salt as part of its structure) For example, hydrolyzable silicon compounds having strontium salts as part of their structure can be exemplified by the following general formula (Xm-1). [Chemistry 18]

[0132] In the formula, RSA1 and RSA2 represent linear, branched, or cyclic alkyl, alkenyl, alkylyl or alkenyl groups with 1 to 20 carbon atoms, substituted or unsubstituted aryl groups with 6 to 20 carbon atoms, or aralkyl or aryloxyalkyl groups with 7 to 20 carbon atoms, respectively. Some or all of the hydrogen atoms in these groups may be substituted with alkoxy, amino, alkylamino, halogen atoms, etc. Furthermore, RSA1 and RSA2 may also form a ring with the sulfur atoms they are bonded to, and when forming a ring, RSA1 and RSA2 represent alkyl groups with 1 to 6 carbon atoms, respectively. RSA3 is a linear, branched, or cyclic alkyl, alkenyl, substituted or unsubstituted aryl or arylalkyl group with 6 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with alkoxy, amino, alkylamino, etc. RSA1, RSA2, and RSA3 may also have oxygen or nitrogen atoms along their chain or ring.

[0133] In addition, in the above general formula (Xm-1), (Si) is recorded to indicate the bonding position with Si.

[0134] X- can be listed as: hydroxide ions, formic acid ions, acetate ions, propionic acid ions, butyrate ions, valeric acid ions, hexanoic acid ions, heptanoic acid ions, octanoic acid ions, nonanoic acid ions, decanoic acid ions, oleic acid ions, stearic acid ions, linolenic acid ions, linolenic acid ions, benzoic acid ions, p-methylbenzoic acid ions, p-terephthalic acid ions, phthalic acid ions, isophthalic acid ions, terephthalic acid ions, salicylic acid ions, trifluoroacetic acid ions, monochloroacetic acid ions, dichloroethyl... Acid ions, trichloroacetic acid ions, nitrate ions, chlorate ions, perchlorate ions, bromate ions, iodate ions, oxalate ions, malonic acid ions, methylmalonic acid ions, ethylmalonic acid ions, propylmalonic acid ions, butylmalonic acid ions, dimethylmalonic acid ions, diethylmalonic acid ions, succinate ions, methylsuccinate ions, glutaric acid ions, adipic acid ions, itconic acid ions, maleic acid ions, fumarate ions, citrate ions, citric acid ions, carbonate ions, etc.

[0135] The cation portion of the compound represented by the above general formula (Xm-1) is specifically exemplified by the following ions (X- is the same as above). [Chemistry 19]

[0136] (Hydrolytic silicon compounds with monazine salts as part of their structure) For example, hydrolyzable silicon compounds having monazite as part of their structure can be exemplified by the following general formula (Xm-2). [Chemistry 20]

[0137] In the formula, RIA1 represents a linear, branched, or cyclic alkyl, alkenyl, alkyl-oxyalkenyl, substituted or unsubstituted aryl group with 6 to 20 carbon atoms, or an aralkyl or aryl-oxyalkyl group with 7 to 20 carbon atoms. Some or all of the hydrogen atoms of these groups may be substituted with alkoxy, amino, alkylamino, halogen atoms, etc. Furthermore, RIA1 and RIA2 may form a ring together with the nitrogen atom to which they are bonded, and when forming a ring, RIA1 and RIA2 respectively represent alkyl groups with 1 to 6 carbon atoms. RIA2 is a linear, branched, or cyclic alkyl, alkenyl, substituted or unsubstituted aryl or arylalkyl group with 6 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy, amino, alkylamino, etc. RIA1 to RIA2 may also have oxygen or nitrogen atoms along their chain or ring.

[0138] Furthermore, in the above general formula (Xm-2), (Si) is recorded to indicate the bonding position with Si. X- is as described above.

[0139] The cation portion of the compound represented by the above general formula (Xm-2) is specifically exemplified by the following ions (X- is the same as above). [Chemistry 21]

[0140] (Hydrolytic silicon compounds with phosphonium salts as part of their structure) For example, hydrolyzable silicon compounds having phosphonium salts as part of their structure can be exemplified by the following general formula (Xm-3). [Chemistry 22]

[0141] In the formula, RPA1, RPA2, and RPA3 represent linear, branched, or cyclic alkyl, alkenyl, alkyl-oxyalkenyl, substituted or unsubstituted aryl groups with 6 to 20 carbon atoms, or aralkyl or aryl-oxyalkyl groups with 7 to 20 carbon atoms, respectively. Some or all of the hydrogen atoms of these groups may be substituted with alkoxy, amino, alkylamino, or halogen atoms. Furthermore, RPA1 and RPA2 may form a ring with the phosphorus atom they are bonded to, and when a ring is formed, RPA1 and RPA2 represent alkyl groups with 1 to 6 carbon atoms, respectively. RPA4 represents linear, branched, or cyclic alkyl, alkenyl, substituted or unsubstituted aryl or arylalkyl groups with 6 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy, amino, or alkylamino groups. RPA1~RPA4 may also have oxygen or nitrogen atoms in their chains or rings.

[0142] Furthermore, in the above general formula (Xm-3), (Si) is recorded to indicate the bonding position with Si. X- is as described above.

[0143] The cation portion of the compound represented by the above general formula (Xm-3) is specifically exemplified by the following ions (X- is the same as above).

[0144] [Chemistry 23]

[0145] (Hydrolytic silicon compounds with ammonium salts as part of their structure) For example, hydrolyzable silicon compounds having an ammonium salt as part of their structure can be exemplified by the following general formula (Xm-4). [Chemistry 24]

[0146] In the formula, RNA1, RNA2, and RNA3 represent hydrogen atoms, linear, branched, or cyclic alkyl, alkenyl, alkylyl or alkenylyl groups with 1 to 20 carbon atoms, substituted or unsubstituted aryl groups with 6 to 20 carbon atoms, or aralkyl or aryloxyalkyl groups with 7 to 20 carbon atoms, respectively. Some or all of the hydrogen atoms of these groups may be substituted with alkoxy, amino, alkylamino, etc., as monovalent organic groups. Furthermore, RNA1 and RNA2 may also form a ring with the nitrogen atom they are bonded to. When forming a ring, RNA1 and RNA2 represent alkyl groups with 1 to 6 carbon atoms or cyclic heterocycles or heteroaromatic rings containing nitrogen, respectively. RNA4 is a linear, branched, or cyclic alkyl, alkenyl, or substituted or unsubstituted aryl group with 6 to 29 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy, amino, alkylamino, etc. When RNA1 forms a circular structure with RNA2 or RNA4 and further contains unsaturated nitrogen, nNA3 = 0; otherwise, nNA3 = 1.

[0147] Furthermore, in the above general formula (Xm-4), (Si) is recorded to indicate the bonding position with Si. X- is as described above.

[0148] The cation portion of the compound represented by the above general formula (Xm-4) is specifically exemplified by the following ions (X- is the same as above). [Chemistry 25]

[0149] [Chemistry 26]

[0150] [Chemistry 27]

[0151] [Chemistry 28]

[0152] [Chemistry 29]

[0153] [Chemistry 30]

[0154] [Chemistry 31]

[0155] (Organic solvents) The silicon-containing resist lower film composition of this invention may contain a solvent. Ideal examples of the aforementioned solvent are alcohol-based organic solvents, more preferably monoalkyl ether derivatives such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, and ethylene glycol monopropyl ether are preferred.

[0156] If these solvents are the main components, non-alcoholic organic solvents can also be added as auxiliary solvents. Examples of such auxiliary solvents include: acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl pentyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0157] (water) Water can also be added to the silicon-containing resist lower layer film composition of the present invention. Adding water hydrates the polysiloxane compounds in the composition, thus improving lithography performance. The water content in the solvent component of the silicon-containing resist lower layer film composition of the present invention is preferably greater than 0% by mass and less than 50% by mass, more preferably 0.3% to 30% by mass, and even more preferably 0.5% to 20% by mass. If the water content is less than 50% by mass, the silicon-containing resist lower layer film exhibits good uniformity and does not experience pinholes.

[0158] The aforementioned silicon-containing inhibitor lower layer film composition should preferably contain a crosslinking catalyst (Xc) for siloxane polymerization, an alcohol-based organic solvent, and water.

[0159] (High-boiling-point solvent) Furthermore, the silicon-containing inhibitor lower film composition of the present invention may also incorporate a high-boiling-point solvent with a boiling point of 180°C or higher, as needed. Examples of such high-boiling-point solvents include: 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecylol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, γ-butyrolactone, and tripropylene glycol. Diethylene glycol monomethyl ether, diacetone alcohol, n-nonyl acetate, ethylene glycol monoethyl ether, 1,2-diethoxyethane, 1-ethoxy-2-methoxyethane, 1,2-diethoxypropane, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc. The proportion of high-boiling-point solvents in the solvent composition should preferably be 0-20% by mass, with 0-10% by mass being more preferable.

[0160] The total amount of solvent, including water, used is preferably 100 to 100,000 parts by mass or 200 to 50,000 parts by mass relative to 100 parts by mass of the polysiloxane compound, which is the base polymer.

[0161] [Other ingredients] (organic acids) To improve the stability of the silicon-containing inhibitor lower membrane composition of the present invention, it is advisable to add an organic acid with a carbon number of 1 to 30 and a valence of monovalent or divalent or higher. Examples of acids that can be added include: formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linolenic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itconic acid, maleic acid, fumaric acid, citrate, citric acid, etc. Oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid, etc. are particularly preferred. Furthermore, to maintain stability, two or more acids may be used in combination. The amount added is 0.001 to 25 parts by weight relative to 100 parts by weight of silicon contained in the composition, preferably 0.01 to 15 parts by weight, and more preferably 0.1 to 5 parts by weight.

[0162] (Photoacid generator) The present invention may also add a photoacid generator to the silicon-containing resistive lower layer film composition. Specifically, the photoacid generator used in the present invention may be the material described in paragraphs (0160) to (0179) of Japanese Patent Application Publication No. 2009-126940.

[0163] (A compound having both an anionic and a cationic portion in one molecule (photoacid generator (P-O))) In addition, the present invention may also contain one or more compounds (photoacid generators) having an anionic and a cationic portion in one molecule represented by the following general formula (P-O). [Chemistry 32] Here, R300 represents a divalent organic group substituted with one or more fluorine atoms. R301 and R302 independently represent monovalent hydrocarbon groups with 1 to 20 carbon atoms that can also be substituted with heteroatoms and can also have heteroatoms inserted. R303 represents a divalent hydrocarbon group with 1 to 20 carbon atoms that can also be substituted with heteroatoms and can also have heteroatoms inserted. Furthermore, R301 and R302, or R301 and R303, can also bond to each other and form a ring together with the sulfur atom in the formula. L304 represents a single bond or a divalent hydrocarbon group with 1 to 20 carbon atoms that can also be substituted with heteroatoms and can also have heteroatoms inserted.

[0164] Such a compound (photoacid generator) can be combined with the thermosetting silicon-containing material of the present invention to obtain a lower resist film that contributes to the rectangularization of the cross-sectional shape while maintaining the LWR of the upper resist.

[0165] In the above general formula (P-0), R300 is a divalent organic group substituted with one or more fluorine atoms. The aforementioned divalent organic group, for example, represents a linear, branched, or cyclic divalent hydrocarbon group such as an alkyl group, alkenyl group, or aryl group having 1 to 20 carbon atoms. Specific structures of R300 can be listed below.

[0166] [Chemistry 33]

[0167] Furthermore, in the above formula, (SO3-) is written to indicate the bonding position with the SO3- group in the above general formula (P-0). Also, (R350) is written to indicate the bonding position with the portion of the cation portion in the above general formula (P-0) that is bonded to R300 through L304.

[0168] R301 and R302 are independently monovalent hydrocarbon groups with 1 to 20 carbon atoms that can be substituted with or insert heteroatoms, and can be linear, branched, or cyclic, representing, for example, alkyl, alkenyl, aryl, and aralkyl. Examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, adamantyl, etc. Examples of alkenyl groups include: vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl, etc. Examples of alkyl groups with side oxy groups include: 2-side oxycyclopentyl, 2-side oxycyclohexyl, 2-side oxypropyl, 2-side oxyethyl, 2-cyclopentyl-2-side oxyethyl, 2-cyclohexyl-2-side oxyethyl, 2-(4-methylcyclohexyl)-2-side oxyethyl, etc. Aryl groups can be listed as: phenyl, naphthyl, thiophene, etc.; or alkoxyphenyls such as 4-hydroxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4-tert-butoxyphenyl, 3-tert-butoxyphenyl, etc.; alkylphenyls such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-n-butylphenyl, 2,4-dimethylphenyl, etc.; alkylnaphthyl such as methylnaphthyl, ethylnaphthyl, etc.; alkoxynaphthyl such as methoxynaphthyl, ethoxynaphthyl, n-propoxynaphthyl, n-butoxynaphthyl, etc.; dialkylnaphthyl such as dimethylnaphthyl, diethylnaphthyl, etc.; dialkoxynaphthyl such as dimethoxynaphthyl, diethoxynaphthyl, etc. Aryl alkyl groups can be listed as: benzyl, 1-phenylethyl, 2-phenylethyl, etc. Examples of aryl-oxyalkyl groups include: 2-phenyl-2-oxyethyl, 2-(1-naphthyl)-2-oxyethyl, 2-(2-naphthyl)-2-oxyethyl, etc. Furthermore, R301 and R302 can also bond to each other and form a ring together with the sulfur atom in the formula; in this case, groups represented by the following formulas can be listed.

[0169] [Chemistry 34] Dashed lines represent bonds.

[0170] In the above general formula (P-0), R303 represents a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms that can be substituted by heteroatoms and can also be inserted into heteroatoms. R303 can be specifically listed as: straight-chain alkyl diyl groups such as methylene, ethyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, and heptadecane-1,17-diyl; saturated cyclic hydrocarbon groups such as cyclopentanediyl, cyclohexanediyl, norcamphenediyl, and adamantanediyl; and unsaturated cyclic hydrocarbon groups such as phenyl and naphthyl. Furthermore, some of the hydrogen atoms in these groups can be replaced by alkyl groups such as methyl, ethyl, propyl, n-butyl, and tributyl. Alternatively, they can be replaced by heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, resulting in the formation of hydroxyl, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride, and haloalkyl groups. Additionally, R301 and R303 can also bond to each other and form a ring together with the sulfur atom in the formula; in this case, groups represented by the following formulas can be listed.

[0171] [Chemistry 35] Dashed lines represent bonds.

[0172] In the above general formula (P-0), L304 represents a single bond or a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms that can be substituted by heteroatoms and can also be inserted with heteroatoms. L304 can be specifically listed as: straight-chain alkyl diyl groups such as methylene, ethyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, and heptadecane-1,17-diyl; saturated cyclic hydrocarbon groups such as cyclopentanediyl, cyclohexanediyl, norcamphenediyl, and adamantanediyl; and unsaturated cyclic hydrocarbon groups such as phenyl and naphthyl. Furthermore, some of the hydrogen atoms in these groups can be substituted to form alkyl groups such as methyl, ethyl, propyl, n-butyl, and tributyl. Alternatively, they can be substituted to form heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, resulting in the formation of hydroxyl, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride, and haloalkyl groups.

[0173] The compound (photoacid generator) represented by the above general formula (P-0) should preferably be represented by the following general formula (P-1). [Chemistry 36] In the above general formula (P-1), X305 and X306 independently represent any one of hydrogen atom, fluorine atom, and trifluoromethyl group, but not all of them are hydrogen atom. n307 represents an integer from 1 to 4. R301, R302, R303, and L304 are as described above.

[0174] The photoacid generator represented by the above general formula (P-0) is preferably represented by the following general formula (P-1-1). [Chemistry 37]

[0175] In the above general formula (P-1-1), R308, R309, and R310 independently represent hydrogen atoms, or linear, branched, or cyclic monovalent hydrocarbon groups with 1 to 20 carbon atoms that may also have heteroatoms inserted. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, tertiary pentyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, oxanorbornel, tricyclo[5.2.1.02,6]decyl, adamantyl, etc. Furthermore, some of the hydrogen atoms in these groups can be substituted with heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and they can also be inserted into heteroatoms such as oxygen, sulfur, and nitrogen atoms. This can result in the formation or insertion of hydroxyl, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride, and haloalkyl groups. Methyl, methoxy, tributyl, and tributoxy groups are preferred.

[0176] In the above general formula (P-1-1), n308 and n309 represent integers from 0 to 5, and should preferably be 0 or 1. n310 represents integers from 0 to 4, and should preferably be 0 or 2. L304, X305, X306, and n307 are as described above.

[0177] The compound (photoacid generator) represented by the above general formula (P-0) is preferably represented by the following general formula (P-1-2). [Chemistry 38] In the above general formula (P-1-2), A311 represents a hydrogen atom or a trifluoromethyl group. R308, R309, R310, n308, n309, n310, and L304 are as described above.

[0178] The photoacid generators represented by the above general formulas (P-0), (P-1), (P-1-1), and (P-1-2) can be more specifically listed in the structures shown below. However, the above photoacid generators are not limited to these.

[0179] [Chemistry 39]

[0180] [Chemistry 40]

[0181] [Chemistry 41]

[0182] [Chemistry 42]

[0183] [Chemistry 43]

[0184] [Chemistry 44]

[0185] The amount of the compound represented by the above general formula (P-O) added relative to 100 parts by weight of thermally crosslinked polysiloxane is 0.001 to 40 parts by weight, preferably 0.1 to 40 parts by weight, and more preferably 0.1 to 20 parts by weight. By adding such a photoacid generator, residue in the exposed portion of the upper resist layer can be reduced, and a pattern with a small LWR can be formed.

[0186] (Stabilizer) Furthermore, the present invention allows the addition of a stabilizer to the silicon-containing inhibitor underlayer film composition. The stabilizer can be an alcohol with a monovalent or divalent or higher valence, having a cyclic ether as a substituent. In particular, the addition of the stabilizer described in paragraphs (0181) to (0182) of Japanese Patent Application Publication No. 2009-126940 can improve the stability of the silicon-containing inhibitor underlayer film composition. The amount of stabilizer added relative to 100 parts by weight of the thermally crosslinked polysiloxane is preferably 0.001 to 50 parts by weight, and more preferably 0.01 to 40 parts by weight.

[0187] (surfactants) Furthermore, the present invention allows for the incorporation of surfactants into the composition as needed. Specifically, such surfactants may be the materials described in paragraph (0185) of Japanese Patent Application Publication No. 2009-126940. The amount of surfactant added is preferably 0 to 10 parts by weight, and more preferably 0 to 5 parts by weight, relative to 100 parts by weight of the thermally crosslinked polysiloxane.

[0188] The aforementioned silicon-containing resist lower layer film, in the micro-patterning process of the multilayer resist method in the semiconductor device manufacturing steps, has the effect of suppressing micro-pattern collapse when forming line and spacing patterns, and has the effect of forming excellent CDU patterns when forming contact hole patterns.

[0189] When the aforementioned silicon-containing resist lower layer film has carboxyl groups protected by acid-instable groups, the acid-instable groups can be thermally decomposed during the baking step when the silicon-containing resist lower layer film is formed, and the carboxyl groups can appear on the surface of the silicon-containing resist lower layer film.

[0190] When the aforementioned silicon-containing inhibitor lower layer film has carboxyl groups protected by acid-instable groups, the silicon-containing inhibitor lower layer film composition, by containing a hot acid generating agent, can lower the thermal decomposition temperature of the aforementioned acid-instable groups and lower the processing temperature.

[0191] The high adhesion between the aforementioned silicon-containing resist underlayer film and the resist film stems from the presence of carboxyl groups in the silicon-containing resist underlayer film after the baking step. By using the resist composition described later, and through baking after coating, the carboxyl groups on the surface of the silicon-containing resist underlayer film and the carboxyl groups of the carboxyl-containing compounds contained in the resist composition cross-link through the supraatomic iodine compound. Since the resist composition described later is positive, cross-linking occurs between the unexposed pattern and the surface of the adhesive film, thereby resisting stress during development and suppressing the collapse of line and spacing patterns, which is useful in the fabrication of resist patterns with high aspect ratios. On the other hand, in the contact hole pattern, the high adhesion between the resist film and the silicon-containing resist underlayer film prevents developer from penetrating between the resist film and the resist underlayer film, thus preventing swelling and forming excellent contact hole patterns for CDUs.

[0192] [Resistant Film] The resist film used in this invention will be described. The aforementioned inhibitor film is obtained from an inhibitor composition containing a predetermined superatomic iodine compound, a carboxyl-containing compound, and a solvent.

[0193] [Suppurium valence iodine compounds] The aforementioned superatomic iodine compounds are tricoordinate superatomic iodine compounds represented by formulas (7), (8) or (9). [Chemistry 45]

[0194] In equations (7) to (9), m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4. However, 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4. However, 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4.

[0195] In equations (7) to (9), R11 to R18 are halogen atoms or hydrocarbon groups with 1 to 10 carbon atoms containing heteroatoms. Furthermore, R11 and R12, R13 and R14, R15 and R16, or R17 and R18 can also bond to each other and form a ring together with the carbon atoms they bond to and the atoms between those carbon atoms.

[0196] The halogen atoms represented by R11 to R18 can include: fluorine, chlorine, bromine, iodine, etc. The hydrocarbon groups with 1 to 10 carbon atoms represented by R11 to R18 can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, tripentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms, such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclo[5.2.1.02,6]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 group can be replaced by a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. This can result in the presence of hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulfonolactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc. R11 to R18 should preferably be hydrocarbon groups with 1 to 4 carbon atoms.

[0197] In equations (7) to (9), R21 to R24 are independently halogen atoms or hydrocarbon groups with 1 to 40 carbon atoms containing heteroatoms. When n2 is 2 or more, each R21 can be the same or different, and multiple R21s can bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R22 can be the same or different, and multiple R22s can bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R23 can be the same or different, and multiple R23s can bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R24 can be the same or different, and multiple R24s can bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to.

[0198] Examples of halogen atoms represented by R21 to R24 include fluorine, chlorine, bromine, and iodine atoms. The hydrocarbon groups represented by R21 to R24 with 1 to 40 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: alkyl groups with 1 to 40 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, tripentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclo[5.2.1.02,6]decyl, adamantyl, and adamantylmethyl; and 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 group can be replaced by a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. Also, some of the -CH2- group in the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, carbamate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), etc.

[0199] In formula (9), R25 is an (n8) valence hydrocarbon group with 1 to 40 carbon atoms or an (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R25 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, aminocarbamate bond, sulfinyl group, sulfonyl group, or thionyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be replaced by a group containing heteroatoms, and some of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be replaced by a group containing heteroatoms. R24 and R25 can also bond to each other and form a ring together with the carbon atoms they bond to and the atoms between the carbon atoms.

[0200] The (n8) valence hydrocarbon group represented by R25 can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned (n8) valence hydrocarbon group is derived from a hydrocarbon by removing (n8) hydrogen atoms. 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.

[0201] Specific examples of alkanes with 1 to 40 carbon atoms mentioned above include: methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[0202] Specific examples of the aforementioned enes with 2 to 40 carbon atoms include: ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and their structural isomers.

[0203] Specific examples of the aforementioned alkynes with 2 to 40 carbon atoms include: acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, and their structural isomers.

[0204] Specific examples of the aforementioned cyclic saturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norcamphene, etc.

[0205] Specific examples of the aforementioned cyclic unsaturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norcamphene.

[0206] Specific examples of aromatic hydrocarbons with 6 to 40 carbon atoms mentioned above include: benzene, naphthalene, biphenyl, etc.

[0207] R25 indicates an (n8) valence heterocyclic group, which is a group obtained by removing (n8) hydrogen atoms from a heterocyclic compound. Specific examples of the aforementioned heterocyclic compounds include: furan, pyridine, pyrazole, tetrahydrothiazole, etc.

[0208] The hydrogen atoms of the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be partially or completely replaced by a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, resulting in the presence of hydroxyl, cyano, fluorine, chlorine, bromine, or iodine atoms. Furthermore, a portion of the -CH2- group constituting the aforementioned (n8) valence hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms, resulting in the presence of carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone, sulfonate, or carboxylic anhydride (-C(=O)-OC(=O)-), etc.

[0209] Specific examples of superatomic iodine compounds represented by equation (7) are listed below, but are not limited to these. [Chemistry 46]

[0210] [Chemistry 47]

[0211] [Chemistry 48]

[0212] [Chemistry 49]

[0213] [Transformation 50]

[0214] [Chemistry 51]

[0215] [Chemistry 52]

[0216] [Chemistry 53]

[0217] [Chemistry 54]

[0218] [Chemistry 55]

[0219] [Chemistry 56]

[0220] [Chemistry 57]

[0221] Examples of superatomic iodine compounds represented by equation (8) are shown below, but are not limited thereto. [Chem.58]

[0222] [Chemistry 59]

[0223] [Transformation 60]

[0224] [Chemistry 61]

[0225] Specific examples of superatomic iodine compounds represented by equation (9) are listed below, but are not limited to these. [Chemistry 62]

[0226] [Chemistry 63]

[0227] [Chemistry 64]

[0228] [Chemistry 65]

[0229] [Chemistry 66]

[0230] [Chemistry 67]

[0231] The aforementioned carboxyl-containing compounds are preferably polymers containing repeating units represented by the following formula (10) or compounds represented by the following formula (11). [Chemistry 68]

[0232] In formula (10), RA is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. XA is a single bond, an phenyl group, a naphthyl group, or *-C(=O)-O-XA1-. XA1 is a saturated alkyl group with 1 to 10 carbon atoms, an phenyl group, or a naphthyl group, and the saturated alkyl group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. * indicates an atomic bond with a carbon atom of the main chain.

[0233] In equation (11), p is 1, 2, 3 or 4.

[0234] In formula (11), R31 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, R31 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, aminocarbamate 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 heteroatoms, and some of the -CH2- of the aforementioned p-valent hydrocarbon group can also be replaced by a group containing heteroatoms.

[0235] In formula (11), R32 is a single bond or an extended hydrocarbon group with 1 to 10 carbon atoms, and part or all of the hydrogen atoms of the extended hydrocarbon group may be replaced by a group containing heteroatoms, and part of the -CH2- of the extended hydrocarbon group may also be replaced by a group containing heteroatoms. When p is 2, 3 or 4, each R32 may be the same or different.

[0236] R31 indicates that the p-valent hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned p-valent hydrocarbon group is derived from a hydrocarbon by removing p hydrogen atoms. 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.

[0237] The aforementioned alkanes with 1 to 40 carbon atoms include: methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[0238] The aforementioned olefins with 2 to 40 carbon atoms include: ethylene, propylene, butene, pentene, hexene, hepten, octene, nonene, decene, and their structural isomers.

[0239] The aforementioned alkynes with 2 to 40 carbon atoms can be listed as follows: acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, and their structural isomers.

[0240] Examples of cyclic saturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, and norcamphene.

[0241] Examples of cyclic unsaturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropylene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norcamphene.

[0242] Aromatic hydrocarbons with 6 to 40 carbon atoms mentioned above include: benzene, naphthalene, biphenyl, etc.

[0243] R31 indicates a p-valent heterocyclic group, which is a group obtained by removing p hydrogen atoms from a heterocyclic compound. Examples of such heterocyclic compounds include furan, pyridine, pyrazole, and tetrahydrothiazole.

[0244] The hydrogen atoms of the aforementioned p-valent hydrocarbon groups or p-valent heterocyclic groups can be partially or completely 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, a portion of the -CH2- group constituting the aforementioned p-valent hydrocarbon 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, sulfonolactone rings, and carboxylic anhydrides (-C(=O)-OC(=O)-), etc.

[0245] R32 indicates that the alkyl 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 alkyl groups with 3 to 20 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norcamphenediyl, and adamantanediyl; unsaturated aliphatic alkyl groups with 2 to 20 carbon atoms, such as vinylene and propylene-1,3-diyl; aryl groups with 6 to 20 carbon atoms, such as phenylene and naphthyl; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned alkyl group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and a portion of the -CH2- group constituting the aforementioned alkyl group can 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, sulopentalide rings, carboxylic anhydrides, etc.

[0246] Among the carboxylic acid compounds represented by formula (11), those with p = 2, 3, or 4 are preferable. In this case, when mixed with superatomic iodine compounds, it is easy to form a strong resist film with high molecular weight, which is more ideal from the perspective of etching resistance and developer resistance.

[0247] In the carboxyl-containing polymer represented by formula (10), specific examples of the repeating unit containing a carboxyl group represented by formula (10) are listed below, but are not limited thereto. In addition, RA in the following formula is the same as that mentioned above. [Chemistry 69]

[0248] [Chemistry 70]

[0249] The carboxylic acid compounds represented by formula (11) can be listed below, but are not limited to these. [Chemistry 71]

[0250] [Chemistry 72]

[0251] [Chemistry 73]

[0252] [Chemistry 74]

[0253] [Chemistry 75]

[0254] [Chemistry 76]

[0255] Polymers containing carboxyl groups and repeating units represented by formula (10) may also contain repeating units other than those represented by formula (10) (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.

[0256] Specific examples of the other repeating units mentioned above can be listed below, but are not limited thereto. Additionally, in the following formula, RA is the same as described above, and XB is independently -CH2- or -O-. [Chemistry 77]

[0257] [Chemistry 78]

[0258] [Chemistry 79]

[0259] [Chemistry 80]

[0260] [Chemistry 81]

[0261] [Chemistry 82]

[0262] [Chemistry 83]

[0263] [Chemistry 84]

[0264] [Chemistry 85]

[0265] [Chemistry 86]

[0266] [Chemistry 87]

[0267] [Chemistry 88]

[0268] [Chemistry 89]

[0269] [Chemistry 90]

[0270] [Chemistry 91]

[0271] [Chemistry 92]

[0272] [Chemistry 93]

[0273] [Chemistry 94]

[0274] [Chem. 95]

[0275] [Chemistry 96]

[0276] [Chemistry 97]

[0277] [Chem. 98]

[0278] [Chemistry 99]

[0279] [Chemistry 100]

[0280] [Chemistry 101]

[0281] [Chemistry 102]

[0282] [Chemistry 103]

[0283] [Chemistry 104]

[0284] [Chemistry 105]

[0285] [Chemistry 106]

[0286] In the aforementioned inhibitor composition, the ratio of the aforementioned superatomic iodine compound to the aforementioned carboxyl-containing compound (or, when the aforementioned carboxyl-containing compound is a carboxyl-containing polymer, the ratio of the superatomic iodine compound to the repeating carboxylic acid units in the aforementioned polymer), in molar ratio, is preferably 10:90 to 90:10 for the superatomic iodine compound to the carboxyl-containing compound, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30. The aforementioned superatomic iodine compound may be used alone or in combination with two or more compounds having different compositional ratios, Mw, and / or Mw / Mn. The aforementioned carboxyl-containing polymer may be used alone or in combination with two or more compounds having different compositional ratios, Mw, and / or Mw / Mn.

[0287] In the aforementioned carboxyl-containing polymers, the ratio (molar ratio) of carboxyl-containing repeating units to other repeating units should preferably be carboxyl-containing repeating units: other repeating units = 10:90~90:10, preferably 15:85~85:15, and even more preferably 20:80~80:20.

[0288] 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, Mw is the polystyrene equivalent value determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0289] Furthermore, when the aforementioned carboxyl-containing polymers have a wide molecular weight distribution (Mw / Mn), the presence of both low and high molecular weight polymers may lead to concerns about foreign matter being observed on the pattern after exposure and deterioration of the pattern shape. Therefore, as the pattern becomes more regular and refined, the influence of Mw and Mw / Mn tends to increase. Thus, in order to obtain a resist composition that can be ideally used for fine pattern sizes, the aforementioned carboxyl-containing polymers should preferably have a narrow dispersion of Mw / Mn of 1.0 to 2.0.

[0290] Examples of methods for synthesizing the aforementioned carboxyl-containing polymers include: adding a free radical polymerization initiator to an organic solvent and heating the monomer that provides the aforementioned repeating unit to polymerize it.

[0291] Specific examples of organic solvents used in the polymerization reaction include: toluene, benzene, THF, diethyl ether, dialkylene, cyclohexane, cyclopentane, cyclopentanone, cyclohexanone, methyl ethyl ketone (MEK), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), etc. Specific examples of polymerization initiators include: 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis(2,4-dimethylpentanone), dimethyl-2,2-azobis(2-methylpropionate), 1,1-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, lauryl 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 moles. The reaction temperature should preferably be 50~150℃, preferably 60~100℃. The reaction time should be 2 to 24 hours, but considering production efficiency, 2 to 12 hours is even better.

[0292] The aforementioned polymerization initiator can be added to the aforementioned monomer solution and supplied to the reactor, or a separate initiator solution, different from the aforementioned monomer solution, can be prepared and supplied to the reactor independently. Since there is a possibility that polymerization may occur during the standby time due to the generation of free radicals from the initiator, resulting in the formation of ultra-high molecular weight polymers, from a quality control perspective, the monomer solution and initiator solution should preferably be prepared independently 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.

[0293] In addition, the amount of each monomer in the aforementioned monomer solution can be appropriately set to achieve the ideal content ratio of the aforementioned repeating units.

[0294] (solvent) The aforementioned inhibitor composition contains a solvent. There are no particular limitations on the solvent being capable of dissolving the aforementioned superatomic iodine compounds, carboxyl-containing compounds, and other components described below, and capable of forming a film. Such solvents are preferably organic solvents, 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. Ethers such as monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tributyl acetate, tributyl propionate, and propylene glycol monotert-butyl ether acetate; carboxylic acids such as formic acid, acetic acid, and propionic acid; lactones such as γ-butyrolactone; and their mixed solvents, etc.

[0295] In the aforementioned inhibitor composition, the content of the aforementioned solvent is preferably 0.1-20% by mass, more preferably 0.1-15% by mass, and even more preferably 0.1-10% by mass. Furthermore, in this invention, "solid component" refers to all components other than the solvent in the entire inhibitor composition. The aforementioned solvent may be used alone or in combination of two or more.

[0296] (surfactants) The aforementioned inhibitor composition may also contain a surfactant. The aforementioned surfactant is preferably a fluorinated and / or polysiloxane surfactant. Examples of such surfactants include those described in paragraph

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

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

[0297] When the aforementioned inhibitor composition contains the aforementioned surfactant, its content in the total solid components should preferably be 0.0001~2% by mass. The aforementioned surfactant can be used alone or in combination of two or more.

[0298] (Free radical scavenger) The aforementioned inhibitor composition may also contain more free radical scavengers. By adding free radical scavengers, the light response during photolithography can be controlled and the sensitivity adjusted.

[0299] The aforementioned free radical scavengers include hindered phenols, quinones, hindered amines, and thiols. Specifically, hindered phenols include butylated hydroxytoluene (BHT) and 2,2-methylenebis(4-methyl-6-tert-butylphenol). Quinones include 4-methoxyphenol and hydroquinone. Hindered amines include 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethylpiperidine-N-oxy radical. Thiols include dodecyl mercaptan and hexadecyl mercaptan.

[0300] When the aforementioned inhibitor composition contains the aforementioned free radical scavenger, its content in the total solid components should preferably be 0.01 to 10% by mass. The aforementioned free radical scavenger can be used alone or in combination of two or more.

[0301] (Cross-linking agent) The aforementioned inhibitor composition may also contain a crosslinking agent. By adding a crosslinking agent, the crosslinking reaction during photolithography can be promoted, the glass transfer points of the pattern can be improved, and a pattern with excellent resolution of fine lines can be obtained.

[0302] The aforementioned crosslinking agents can include compounds with carbon-carbon unsaturated bonds such as vinyl, (meth)acrylate, allyl, alkynyl, and aromatic rings as functional groups. Specifically, compounds with vinyl groups can include: chain alkenes, branched alkenes, cyclic alkenes, etc., which may also have substituents. Compounds with (meth)acrylate groups can include: acrylic acid, methacrylic acid, acrylates, methacrylates, etc., which may also have substituents. Compounds with allyl groups can include: allyl alcohol, allyl ether, allyl ester, allyl acetylamine, allylamine, isocyanurates containing allyl groups, etc. Compounds with alkynyl groups can include: chain alkynes, branched alkynes, cyclic alkynes, alkynyl alcohols, alkynyl ethers, alkynyl esters, alkynyl acetylamines, alkynylamines, isocyanurates containing alkynyl groups, etc. Compounds containing aromatic rings include: aromatic hydrocarbons, heteroaromatic hydrocarbons, styrene, stilbene, phenylacetylene, acenaphthene, chalcone, etc., which may also contain substituents. The crosslinking agent may contain only one or more of the above functional groups. Preferably, the crosslinking agent contains 1 or more and 10 or less of the above functional groups, and more preferably 2 or more and 8 or less.

[0303] When the aforementioned inhibitor composition contains the aforementioned crosslinking agent, its content in the total solid components should preferably be 0.01 to 50% by mass. The aforementioned crosslinking agent can be used alone or in combination of two or more.

[0304] (Photopolymerization initiator) When the aforementioned inhibitor composition contains the aforementioned crosslinking agent, it may also contain a photopolymerization initiator. The photopolymerization initiator can generate free radicals and promote the crosslinking of the aforementioned crosslinking agent by irradiation with high-energy rays.

[0305] Specific examples of the aforementioned photopolymerization initiators include: benzophenone, methyl O-benzoylbenzoate, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fentanyl ketone, and other benzophenone derivatives; 2,2-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-oxolinylpropane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropane)-benzyl]-phenyl}-2-methylpropane-1-one, methyl phenylglyoxylate, and other acetophenone derivatives; thioxanthone, 2-methylthioxanthone, etc. Thioxanone derivatives such as 2-isopropylthioxanone, 4-isopropylthioxanone, 2-chlorothioxanone, and diethylthioxanone; benzopyrene derivatives such as benzopyrene, benzopyrene dimethyl ketal, and benzopyrene-β-methoxyethyl acetal; benzopyrene derivatives such as benzoin, benzopyrene methyl ether, and 2-hydroxy-2-methyl-1-phenylpropane-1-one; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, and 1,3-diphenylpropanetrione. Oxime compounds such as ketone-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime-1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)] ethyl ketone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetylgoxime); α-hydroxy compounds such as 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropane)-benzyl]phenyl}-2-methylpropane. Ketone compounds; α-aminoalkylphenyl ketone compounds such as 2-benzyl-2-dimethylamino-1-(4-α-oxolinylphenyl)-butanone-1,2-dimethylamino-2-(4-methylbenzyl)-1-(4-α-oxolin-4-yl-phenyl)butane-1-one; phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and titanium cadmium compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium.

[0306] When the aforementioned inhibitor composition contains the aforementioned photopolymerization initiator, its content in the total solids composition should preferably be 0.1~10% by mass, more preferably 0.1~5% by mass, and optimally 0.1~1% by mass. If it is above 0.1% by mass, the blending effect can be fully obtained.

[0307] The aforementioned resist composition, as described above, contains a superatomic iodine compound and a carboxyl-containing compound as its main components, but does not contain polymers containing acid-instable groups or photoacid generators as found in conventional chemical amplification resist compositions. However, the resist composition of the present invention can form a positive pattern in which the exposed portion is soluble in the developer, especially when exposed to EB or EUV. The mechanism is not yet fully elucidated, but it is speculated to be as follows.

[0308] The superatomic iodine compounds represented by formulas (7), (8), or (9) are tricoordinate compounds with aryl and carboxylate ligands. It is believed that such tricoordinate iodine compounds, when mixed with carboxyl-containing compounds, will undergo an equilibrium reaction involving the exchange of carboxylate ligands. If the original carboxylate ligands can be removed by any method, a superatomic iodine compound with new ligands will be generated. For example, if 1-iodophryne diacetate, a superatomic iodine compound, is mixed with a carboxyl-containing compound, and the resulting low-boiling acetic acid is removed, the ligand exchange will be completed. Here, the carboxyl-containing compound will become a cross-linked polymer through the superatomic iodine compound.

[0309] The polymer system formed by crosslinking supraatomic iodine compounds is generated during film formation. This is because even when such crosslinked polymers are synthesized beforehand, they are insoluble in almost all organic solvents, making solution preparation impossible. It is speculated that this is because the supraatomic 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 resistive film.

[0310] In the resist film obtained from the aforementioned resist composition, the iodine compound containing superatomic valence, which is its main component, decomposes under light, thereby changing its polarity and forming a pattern using a development step. The mechanism is not yet fully elucidated, but it is speculated, for example, as follows.

[0311] The resist film obtained from the aforementioned resist composition contains polymers bonded by supraatomic iodine compounds during film formation. However, these polymers decompose under light, transforming into monovalent iodine compounds. Simultaneously, the bonds between carboxyl-containing compounds and supraatomic iodine compounds are released, and the molecular weight decreases. As a result, a positive pattern is formed where the exposed areas are removed by organic solvents.

[0312] Based on the foregoing, it can be inferred that the aforementioned inhibitor composition is a non-chemically amplified inhibitor composition. This inhibitor composition does not require polymers containing acid-inhibitory groups or photoacid generators, as is common in conventional chemically amplified inhibitor compositions. Therefore, adverse effects caused by acid diffusion (such as image blurring) will not occur, and fine patterns can be resolved.

[0313] The aforementioned resist composition is particularly effective in EUV lithography. This is due to the presence of iodine atoms, which have a high absorption capacity for EUV light. In other words, it reduces shot noise and achieves higher resolution and lower LWR.

[0314] Regarding EUV resist compositions 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 numerous problems, including insufficient solvent solubility, 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 offering advantages over metal resists in terms of defects and eliminating problems with solvent solubility. Furthermore, the resist composition of the present invention is applicable to positive patterns, thus broadening its applications. For example, in the contact hole formation step, metal resists implemented with negative pattern development require a reversal process after pillar pattern formation, while positive resists do not require such a step. Therefore, considering the viewpoint of process simplicity, the resist composition of the present invention can be considered more useful than metal resists.

[0315] The thickness of the aforementioned resist film should preferably be 10~70nm, and 20~50nm is even better.

[0316] [Resistor Lower Layer Film] The present invention provides a laminate having a resistive underlayer film between the aforementioned substrate and a silicon-containing resistive underlayer film.

[0317] The aforementioned resist underlayer film can be any known material used in micro-patterning processes employing multilayer resist methods. Specific examples of the aforementioned resist underlayer film include Shin-Etsu Chemical Co., Ltd.'s spin-coated carbon film ODL-301 (carbon content 88% by mass).

[0318] The thickness of the lower layer of the aforementioned resist should preferably be 40~200nm, and 40~150nm is even better.

[0319] The aforementioned resist lower layer film is preferably a resist lower layer film obtained by using a solution-like resist lower layer film forming composition, or a resist lower layer film formed by CVD or ALD methods. [Manufacturing Method of Laminated Structures] The present invention provides a method for manufacturing the following laminate. A method for manufacturing a laminated body, characterized by comprising the following steps: A resist lower layer film is formed on the substrate. On the resist lower layer film, a silicon-containing resist lower layer film is formed from a silicon-containing resist lower layer film composition containing any one or more repeating units represented by general formulas (1) to (3) and any one or more repeating units represented by general formulas (4) to (6) as described above, and A resistive composition containing at least one of the following: a superatomic iodine compound represented by formula (7), a superatomic iodine compound represented by formula (8), and a superatomic iodine compound represented by formula (9), a carboxyl-containing compound, and a solvent, is coated onto the silicon-containing resistive lower layer film, and then subjected to heat treatment to form a resistive film.

[0320] The method for manufacturing the laminate of the present invention for use in a two-layer resist process includes the following steps: The aforementioned silicon-containing resist lower layer film composition is coated onto a substrate and subjected to heat treatment to form a sealing film. The aforementioned resist composition is coated onto the silicon-containing resist lower layer film, and then subjected to heat treatment to form a resist film.

[0321] The present invention provides a method for manufacturing a stacked body as described above, wherein a lower layer film forming material is coated on a substrate and subjected to heat treatment, thereby forming the aforementioned resist lower layer film.

[0322] Methods for forming the aforementioned silicon-containing resist lower layer film include spin coating and other methods of coating the aforementioned silicon-containing resist lower layer film composition onto a substrate, followed by baking to evaporate the solvent and promote the crosslinking reaction. The baking temperature is preferably 100–400°C, and more preferably 150–300°C. The baking time is preferably 10–600 seconds, and more preferably 10–300 seconds.

[0323] Furthermore, the aforementioned silicon-containing resist lower layer film can also be formed by coating the aforementioned silicon-containing resist lower layer film composition onto a substrate using a spin coating method, as described above, and then baking the silicon-containing resist lower layer film composition in an environment with an oxygen concentration of 0.1% to 21% to harden it. By baking the aforementioned silicon-containing resist lower layer film composition in such an oxygen environment, a sufficiently hardened film can be obtained. In this case, the baking temperature and time can be set to be the same as described above.

[0324] Furthermore, the baking environment can be not only in the air, but also sealed with inert gases such as N2, Ar, and He. In this case, the environment can be set to have an oxygen concentration of less than 0.1%. Also, the baking temperature and time can be set to the same as mentioned above. Even if the substrate contains materials that are unstable when heated in an oxygen environment, it will not cause substrate degradation, and it can promote the cross-linking reaction during the formation of the silicon-containing resist underlayer film.

[0325] The inhibitor film can be formed by coating the aforementioned silicon-containing inhibitor underlayer film using appropriate coating methods such as spin coating, roller coating, flow coating, dip coating, spray coating, or blade coating, and then pre-baking it on a hot plate at a temperature preferably 60-200°C for 10-30 seconds, and more preferably 80-180°C for 30-20 seconds.

[0326] The method for manufacturing the laminate of the present invention for use in a 3-layer resist process includes the following steps: A resist underlayer film forming material is coated onto a substrate, and then subjected to heat treatment to form the resist underlayer film. A silicon-containing resist lower layer film composition is coated onto the resist lower layer film, and then subjected to heat treatment to form a silicon-containing resist lower layer film. The aforementioned resist composition is coated onto the silicon-containing resist lower layer film, and then subjected to heat treatment to form a resist film.

[0327] Methods for forming the aforementioned resist underlayer film include spin coating, where the resist underlayer film forming composition is coated onto a substrate, the solvent evaporates, and then baking is performed. The baking temperature depends on the type of resist underlayer film being formed and should be set appropriately, typically around 100-400°C, preferably around 150-300°C. The baking time also depends on the type of resist underlayer film being formed and should be set appropriately, typically around 10-600 seconds, preferably around 10-300 seconds.

[0328] The aforementioned lower layer film of the resist should be formed using CVD or ALD methods.

[0329] In the three-layer resist fabrication process, the silicon-containing resist lower layer film can be formed by coating the aforementioned silicon-containing resist lower layer film composition onto the resist lower layer film using a spin coating method, followed by baking to evaporate the solvent and promote the crosslinking reaction. In this case, the baking time and temperature can be set to the same as those in the method for forming the silicon-containing resist lower layer film in the two-layer resist fabrication process.

[0330] In the 3-layer resist process, the resist film can be formed using the same method as the resist film in the 2-layer resist process.

[0331] [Pattern Formation Method] This invention provides a pattern forming method, comprising the following steps: The resist film of the above-described multilayer structure was exposed to i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet light. The previously exposed resist film was developed using a developer.

[0332] When exposing with i-rays, KrF excimer lasers, ArF excimer lasers, or EUV, irradiation is performed directly or with a mask used to form the desired pattern, with an exposure dose preferably of about 1 to 300 mJ / cm², and more preferably about 10 to 200 mJ / cm². When exposing with EB, irradiation is performed directly or with a mask used to form the desired pattern, with an exposure dose preferably of about 0.1 to 8000 μC / cm², and more preferably about 0.5 to 5000 μC / cm². Furthermore, the pattern forming method of the present invention is particularly suitable for fine patterning using EB or EUV, especially in high-energy radiation.

[0333] After exposure, PEB should be applied as needed. In this case, it is advisable to apply the PEB on a heated plate or in an oven at 30~200℃ for 10 seconds to 30 minutes, or more preferably at 60~120℃ for 30 seconds to 20 minutes.

[0334] After exposure or PEB, patterning can be achieved by developing with a developer as needed. The developer used at this time should preferably be an organic solvent. After exposure or PEB, patterning can be achieved by developing with a developer as needed. The developing solutions used at this time can include: 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, 5-methyl-2-hexanone, methylcyclohexanone, acetophenone, methyl acetophenone, isopropanol, isoamyl alcohol, n-butanol, tributanol, triamyl alcohol, n-amyl alcohol, cyclohexanol, formic acid, acetic acid, propionic acid, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butyl acetate, isoamyl acetate, butyl acetate, isoamyl acetate, cyclohexyl acetate, 4-tributylcyclohexyl acetate, octyl acetate, isoborneol acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl valerate, methyl valerate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate. Organic solvents such as methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, ethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, 2-propanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methyl-1-butanol, diacetone alcohol, 4-methyl-2-pentanol, 3-methylcyclohexanol, 3,5,5-trimethylhexyl alcohol, 2,6-dimethyl-4-heptanol, toluene, anisole, and ε-caprolactone can be used. These developers can be used alone or in combination of two or more.

[0335] After development, rinsing should be performed as needed. The rinsing solution should be miscible with the developer and should not dissolve the resist film. Ideal solvents to use include: alcohols with 3 to 10 carbon atoms, ethers with 8 to 12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents with 6 to 12 carbon atoms.

[0336] 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. [Example]

[0337] The present invention will be specifically described below with examples of synthesis, comparative synthesis, preparation, examples, and comparative examples, but the present invention is not limited to the examples described below. In addition, the molecular weight was determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as the extraction solvent, and the weight average molecular weight (Mw) and number average molecular weight (Mn) of polystyrene were obtained, and the dispersity (Mw / Mn) was then obtained from them.

[0338] [1] Synthesis of polymers for silicon-containing inhibitor lower layer film composition [Synthesis Example 1-1] A mixture of 30.6 g of compound (101), 11.4 g of compound (102), and 4.3 g of compound (103) (mole ratio: 67 / 28 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25 °C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 240 g of PGEE solution of polysiloxane compound 1 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 1 was determined to be Mw = 2,750.

[0339] [Synthesis example 1-2] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 8.5 g of compound (103) (mole ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25 °C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 270 g of PGEE solution of polysiloxane compound 2 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 2 was determined to be Mw = 2,650.

[0340] [Synthesis Example 1-3] A mixture of 30.6 g of compound (101), 5.3 g of compound (102), and 17.1 g of compound (103) (mole ratio: 67 / 13 / 20) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was complete, 450 g of propylene glycol monoethyl ether (PGEE) and 1.4 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 280 g of PGEE solution of polysiloxane compound 3 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 3 was determined to be Mw = 2,700.

[0341] [Synthesis Example 1-4] A mixture of 30.6 g of compound (101), 1.2 g of compound (102), and 25.6 g of compound (103) (mole ratio: 67 / 3 / 30) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25 °C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.6 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 280 g of PGEE solution of polysiloxane compound 4 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 4 was determined to be Mw = 2,700.

[0342] [Synthesis Example 1-5] A mixture of 22.8 g of compound (101) and 42.7 g of compound (103) (mole ratio: 50 / 50) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25 °C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 2.0 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 300 g of PGEE solution of polysiloxane compound 5 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 5 was Mw = 2,650.

[0343] [Synthesis Example 1-6] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 9.1 g of compound (104) (mole ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was complete, 450 g of propylene glycol monoethyl ether (PGEE) and 1.2 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 240 g of PGEE solution of polysiloxane compound 6 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 6 was Mw = 2,650.

[0344] [Synthesis Example 1-7] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 9.8 g of compound (105) (mole ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was complete, 450 g of propylene glycol monoethyl ether (PGEE) and 1.2 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 250 g of PGEE solution of polysiloxane compound 7 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 7 was Mw = 2,700.

[0345] [Synthesis Example 1-8] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 9.8 g of compound (106) (mole ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was complete, 450 g of propylene glycol monoethyl ether (PGEE) and 1.2 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 255 g of PGEE solution of polysiloxane compound 8 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 8 was Mw = 2,730.

[0346] [Synthesis Example 1-9] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 6.3 g of compound (107) (mole ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25 °C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 220 g of PGEE solution of polysiloxane compound 9 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 9 was Mw = 2,550.

[0347] [Synthesis Example 1-10] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 6.9 g of compound (108) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25 °C for 24 hours to allow for hydrolysis and condensation. After the reaction was complete, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 255 g of PGEE solution of polysiloxane compound 10 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 10 was determined to be Mw = 3,600.

[0348] [Synthesis Example 1-11] A mixture of 30.6 g of compound (101), 5.3 g of compound (102), and 13.8 g of compound (108) (mole ratio: 67 / 13 / 20) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was complete, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 270 g of PGEE solution of polysiloxane compound 11 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 11 was determined to be Mw = 3,600.

[0349] [Synthesis Example 1-12] A mixture of 30.6 g of compound (101), 1.2 g of compound (102), and 20.7 g of compound (108) (mole ratio: 67 / 3 / 30) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.2 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 310 g of PGEE solution of polysiloxane compound 12 (compound concentration 10%). The polystyrene molecular weight of polysiloxane compound 12 was determined to be Mw = 7,000.

[0350] [Comparative Synthesis Examples 1-13] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 5.9 g of compound (109) (mole ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was complete, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% maleic acid aqueous solution were added, and the water and by-product alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 210 g of PGEE solution of polysiloxane compound 13 (compound concentration 10%). The converted molecular weight of polystyrene of polysiloxane compound 13 was determined to be Mw = 2,600.

[0351] Using the monomers shown in Table 1, and following the methods described in [Synthesis Examples 1-1] to [Synthesis Examples 1-12] and [Comparative Synthesis Examples 1-13], the target compounds were obtained as polysiloxane compounds 1 to 13, respectively.

[0352] [Table 1] Feed rate of each monomer (mol%) Mw 101 102 103 104 105 106 107 108 109 Compound 1 67 28 5 - - - - - - 2750 Compound 2 67 twenty three 10 - - - - - - 2650 Compound 3 67 13 20 - - - - - - 2700 Compound 4 67 3 30 - - - - - - 2700 Compound 5 50 - 50 - - - - - - 2650 Compound 6 67 twenty three - 10 - - - - - 2650 Compound 7 67 twenty three - - 10 - - - - 2700 Compound 8 67 twenty three - - - 10 - - - 2730 Compound 9 67 twenty three - - - - 10 - - 2550 Compound 10 67 twenty three - - - - - 10 - 3600 Compound 11 67 13 - - - - - 20 - 3600 Compound 12 67 3 - - - - - 30 - 7000 Compound 13 67 twenty three - - - - - - 10 2600 [Chemistry 107]

[0353] [2] Preparation of silicon-containing inhibitor lower layer film composition The polysiloxane compounds 1-13 obtained in the above synthesis examples 1-1 to 1-13, crosslinking catalyst, acid, solvent, and water were mixed in the proportions shown in Table 2 and filtered using a 0.1 μm fluororesin filter to obtain polysiloxane lower membrane composition solutions, which were designated as Sol.1 to 13 respectively.

[0354] [Table 2] Polysiloxane (parts by weight) Crosslinking catalyst (parts by weight) acid (parts by weight) solvent (parts by weight) water (parts by weight) Sol. 1 Compound 1(1) QBANO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 2 Compound 2(1) QBANO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 3 Compound 3(1) QBANO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 4 Compound 4(1) QBANO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 5 Compound 5(1) QBANO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 6 Compound 6(1) TPSNO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 7 Compound 7(1) TPSNO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 8 Compound 8(1) TPSNO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 9 Compound 9(1) TPSNO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 10 Compound 10(1) QBANO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 11 Compound 11(1) QBANO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 12 Compound 12(1) QBANO3 (0.03) Maleic acid (0.01) PGEE (100) water (10) Sol. 13 Compound 13(1) QBANO3 (0.03) Maleic acid (0.01) PGEE (100) water (10)

[0355] TPSNO3: Triphenylsilane nitrate QBANO3: Tetrabutylammonium nitrate PGEE: Propylene Glycol Monoethyl Ether

[0356] [3] Synthesis of polymers used for inhibitor components The inhibitor components are synthesized using polymers P-1 to P-5 using the compounds shown below. [Chemistry 108]

[0357] [Chemistry 109]

[0358] [Chemical 110]

[0359] [Synthetic Example 2-1] Synthesis of Polymer P-1 Under nitrogen atmosphere, monomers b-1 (56g), c-1 (36g), V-601 (manufactured by Fujifilm and Koei Tecmo Chemicals), 5.4g, and MEK (180g) were measured in a flask to prepare a monomer-polymerization initiator solution. In another flask conditioned under nitrogen atmosphere, MEK (55g) was measured, and the mixture was heated to 80°C with stirring. The aforementioned monomer-polymerization initiator solution was then added dropwise over 4 hours. After the addition was complete, the temperature of the polymerization solution was maintained at 80°C and stirred continuously for 2 hours, then cooled to room temperature. The resulting polymerization solution was added dropwise to 4000g of vigorously stirred hexane, and the precipitated polymer was filtered and separated. The obtained polymer was washed twice with hexane (1200g) and then vacuum dried at 50°C for 20 hours to obtain a white powder polymer P-1 (yield 90g, 98% yield). The Mw of polymer P-1 was 8000, and the Mw / Mn ratio was 1.42. In addition, Mw is the polystyrene conversion value determined by GPC using THF as a solvent. [Chemistry 111]

[0360] [Synthetic Examples 2-2~2-5] Synthesis of Polymers P-2~P-5 By changing the types and blending ratios of the monomers, the polymers shown in Table 3 below were synthesized using the same method as in Synthesis Example 2-1.

[0361] [Table 3] polymer Unit 1 Import ratio (mol%) Unit 2 Import ratio (mol%) Mw Mw / Mn P-1 b-1 65 c-1 35 8000 1.42 P-2 b-1 50 c-2 50 8400 1.51 P-3 b-1 60 c-3 40 8100 1.42 P-4 b-1 60 d-3 40 8100 1.42 P-5 d-1 65 d-2 35 8000 1.44

[0362] [4] Preparation of inhibitor composition [Preparation Examples 2-1 to 2-10, Comparative Preparation Examples 1-1 to 1-2] The superatomic iodine compound and the carboxyl-containing compound were dissolved in a solvent containing 0.01% by mass of surfactant (PF-636, manufactured by OMNOVA) according to the composition shown in Table 4 below. The resulting solution was filtered through a 0.2 μm Teflon (registered trademark) filter to obtain the inhibitor compositions (R-01 to R-10). Furthermore, the polymer, photoacid generator, and sensitivity modifier were dissolved in a solvent containing 0.01% by mass of surfactant (PF-636, manufactured by OMNOVA) according to the composition shown in Table 5 below. The resulting solution was filtered through a 0.2 μm Teflon (registered trademark) filter to obtain the inhibitor compositions (CR-01 and CR-02).

[0363] [Table 4] inhibitor Composition Superatomic iodine Compound 1 (parts by weight) Superatomic iodine Compound 2 (parts by weight) Carboxyl group compound (parts by weight) Solvent 1 (parts by weight) Solvent 2 (parts by weight) Preparation Example 2-1 R-01 I-1 (12) - P-1 (9) PGMEA (800) AcOH (200) Preparation Example 2-2 R-02 I-2 (10) - P-1 (9) PGMEA (800) AcOH (200) Preparation Examples 2-3 R-03 I-3 (10) - P-1 (9) PGMEA (800) AcOH (200) Preparation Examples 2-4 R-04 I-1 (6) I-2 (5) P-1 (9) PGMEA (800) AcOH (200) Preparation Examples 2-5 R-05 I-1 (12) - P-2 (17) PGMEA (800) AcOH (200) Preparation Examples 2-6 R-06 I-1 (12) - P-3 (11) PGMEA (800) AcOH (200) Preparation Examples 2-7 R-07 I-1 (12) - P-4 (17) PGMEA (800) AcOH (200) Preparation Examples 2-8 R-08 I-1 (12) - m-1 (7) PGMEA (800) AcOH (200) Preparation Examples 2-9 R-09 I-1 (12) - m-2 (4) PGMEA (800) AcOH (200) Preparation Example 2-10 R-10 I-1 (12) - m-3 (7) PGMEA (800) AcOH (200)

[0364] [Table 5] inhibitor Composition polymer (parts by weight) Photoacid generator (parts by weight) Sensitivity modifier (parts by weight) Solvent 1 (parts by weight) Solvent 2 (parts by weight) Comparative Preparation Example 1-1 CR-01 P-5 (80) PAG-1 (19) Q-1 (6) PGMEA (1890) GBL (210) Comparative preparation examples 1-2 CR-02 P-5 (80) PAG-1 (19) I-1 (5) PGMEA (1890) GBL (210)

[0365] In Tables 4 and 5, the superatomic iodine compounds I-1 to I-3, the carboxyl-containing compounds m-1 to m-3, the photoacid generator PAG-1, the sensitivity modifier Q-1, and the solvent are described below. [Chemistry 112]

[0366] [Chemistry 113]

[0367] [Chemistry 114]

[0368] [Chemistry 115]

[0369] Solvent: AcOH (acetic acid) GBL (γ-butyrolactone)

[0370] [5] Fabrication and EUV lithography evaluation of laminates (2-layer resist process, line and spacing pattern) [Examples 1-1 to 1-21, Comparative Examples 1-1 to 1-4] Each silicon-containing resist underlayer film composition (Sol.1~Sol.13) was spin-coated onto a silicon substrate, and baked for 60 seconds at the temperature recorded in Table 6 using a heating plate to form a silicon-containing resist underlayer film with a film thickness of 40 nm. Then, each resist component (R-01~R-10, CR-01~CR-02) was spin-coated onto the aforementioned film, and pre-baked (PAB) for 60 seconds at the temperature recorded in Table 6 using a heated plate to obtain a resist film with a thickness of 40 nm. The aforementioned resist film was exposed to a 36 nm line and spacing (LS) 1:1 pattern using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9, 90-degree dipole illumination), and then PEB was performed on the heated plate at the temperature recorded in Table 6 for 60 seconds. After that, development was performed with the developer recorded in Table 6 for 30 seconds to form an LS pattern with a spacing width of 18 nm and a pitch of 36 nm.

[0371] The obtained resist patterns were evaluated as follows. The results are shown in Table 6.

[0372] [Sensitivity Evaluation] The aforementioned LS pattern was observed using a Hitachi Advanced Technology Co., Ltd. (CG-6300) measuring SEM. The optimal exposure Eop (mJ / cm2) for obtaining an LS pattern with a spacing width of 18nm and a pitch of 36nm was determined and set as the sensitivity.

[0373] [LWR Evaluation] The dimensions of 10 points on an LS pattern obtained by exposure to the optimal exposure along the length 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.

[0374] [Ultimate Resolution Evaluation] Using a Hitachi Advanced Technologies (AGT) CG-6300 long-range SEM, the limiting linewidth (nm) was determined by gradually increasing the exposure amount to form the aforementioned LS pattern from the optimal exposure amount, and this value was designated as the limiting resolution (nm). The smaller this value, the better the limiting resolution, and the finer the pattern can be formed.

[0375] [Table 6] Silicon-containing inhibitors Lower membrane formation Material composition Silicon-containing inhibitors Baking of the lower membrane (°C) inhibitor composition PAB / PEB (°C) Developer EoP (mJ / cm2) LWR (nm) limit Resolution (nm) Evaluation of Example 1-1 Sol.1 240 R-01 110 / 90 nBA 40 3.5 15 Evaluation of Examples 1-2 Sol.2 240 R-01 110 / 90 nBA 40 3.5 15 Evaluation of Examples 1-3 Sol.3 240 R-01 110 / 90 nBA 40 3.6 13 Evaluation of Examples 1-4 Sol.4 240 R-01 110 / 90 nBA 40 3.5 13 Evaluation of Examples 1-5 Sol.5 240 R-01 110 / 90 nBA 40 3.4 13 Evaluation of Examples 1-6 Sol.6 240 R-01 110 / 90 nBA 40 3.5 15 Evaluation of Examples 1-7 Sol.7 240 R-01 110 / 90 nBA 40 3.6 15 Evaluation of Examples 1-8 Sol.8 240 R-01 110 / 90 nBA 40 3.5 15 Evaluation of Examples 1-9 Sol.9 240 R-01 110 / 90 nBA 40 3.6 15 Evaluation of Examples 1-10 Sol.10 240 R-01 110 / 90 nBA 40 3.5 15 Evaluation of Examples 1-11 Sol.11 240 R-01 110 / 90 nBA 40 3.6 13 Evaluation of Examples 1-12 Sol.12 240 R-01 110 / 90 nBA 40 3.5 13 Evaluation Examples 1-13 Sol.11 240 R-02 110 / 90 nBA 43 3.5 13 Evaluation Examples 1-14 Sol.11 240 R-03 110 / 90 nBA 45 3.5 13 Evaluation Examples 1-15 Sol.11 240 R-04 110 / 90 nBA 42 3.6 13 Evaluation Examples 1-16 Sol.11 240 R-05 110 / 90 nBA 39 3.5 13 Evaluation Examples 1-17 Sol.11 240 R-06 110 / 90 nBA 42 3.6 13 Evaluation Examples 1-18 Sol.11 240 R-07 110 / 90 nBA 38 3.5 13 Evaluation Examples 1-19 Sol.11 240 R-08 110 / 90 nBA 44 3.6 13 Evaluation of Examples 1-20 Sol.11 240 R-09 110 / 90 nBA 44 3.5 13 Evaluation of Examples 1-21 Sol.11 240 R-10 110 / 90 nBA 46 3.5 13 Comparative Evaluation Example 1-1 Sol.13 240 R-01 110 / 90 nBA 40 3.5 16 Comparative Evaluation Example 1-2 Sol.13 240 R-10 110 / 90 nBA 40 3.5 16 Comparative Evaluation Examples 1-3 Sol.11 240 CR-01 105 / 90 TMAH 85 5.0 18 Comparative Evaluation Examples 1-4 Sol.11 240 CR-02 105 / 90 TMAH 85 5.0 18

[0376] Developer: nBA (Butyl acetate) TMAH (2.38% by mass tetramethylammonium hydroxide aqueous solution)

[0377] As shown in Table 6, comparing Comparative Examples 1-1 and 1-2 with the Example, excellent resolution can be obtained in the two-layer resist process by using the aforementioned silicon-containing resist lower film composition. Furthermore, it is evident that even compared to Comparative Examples 1-3 and 1-4, which used chemically amplified resist compositions utilizing acid catalyst reactions, excellent sensitivity, resolution, and LWR are still achieved. Therefore, it is clear that in the two-layer resist process using the stack of the present invention, excellent resolution is achieved during the formation of LS patterns by EUV exposure. [6] Fabrication and EUV lithography evaluation of the laminate (3-layer resist process, contact hole pattern) [Examples 2-1 to 2-21, Comparative Examples 2-1 to 2-4] A spin-coated carbon film ODL-301 (88% by mass carbon content) manufactured by Shin-Etsu Chemical Industry Co., Ltd. was coated onto a silicon substrate and baked at 350°C for 60 seconds to form a resist lower layer film with a thickness of 200 nm. Various silicon-containing resist lower layer film compositions (Sol.1~Sol.13) were spin-coated onto the substrate and baked at the temperatures listed in Table 7 for 60 seconds using a heating plate to form a silicon-containing resist lower layer film with a thickness of 40 nm. Then, each resist component (R-01~R-10, CR-01~CR-02) was spin-coated onto the aforementioned film, and pre-baked (PAB) for 60 seconds at the temperature recorded in Table 7 using a heated plate to obtain a resist film with a thickness of 50 nm. Next, the resist film was exposed using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, mask for a 64 nm pitch hole pattern on the wafer, +20% offset) with PEB performed at the temperature recorded in Table 7 on a heated plate for 60 seconds, followed by development for 30 seconds using the developer recorded in Table 7 to obtain a hole pattern with a size of 32 nm.

[0378] The obtained resist patterns were evaluated as follows. The results are shown in Table 7.

[0379] [Sensitivity Evaluation] The aforementioned contact hole pattern was observed using a Hitachi Advanced Technology Co., Ltd. (CG-6300) measuring SEM. The optimal exposure value Eop (mJ / cm2) for obtaining a hole pattern with a size of 22nm was determined and set as the sensitivity.

[0380] [CDU Evaluation] 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 pattern can be obtained.

[0381] [Ultimate Resolution Evaluation] Using a Hitachi Advanced Technologies (AGT) CG-6300 long-range SEM, the limiting aperture diameter (nm) was determined by progressively decreasing the exposure amount to form the aforementioned aperture pattern, starting from the optimal exposure. This value was then designated as the limiting resolution (nm). The smaller the value, the better the limiting resolution, and the more finer the aperture pattern could be formed.

[0382] [Table 7] Silicon-containing inhibitors Lower membrane formation Material composition Silicon-containing inhibitors Baking of the lower membrane (°C) inhibitor Composition PAB / PEB (°C) Developer EoP (mJ / cm2) CDU (nm) limit Resolution (nm) Evaluation of Example 2-1 Sol.1 240 R-01 110 / 90 nBA 44 2.5 25 Evaluation of Example 2-2 Sol.2 240 R-01 110 / 90 nBA 44 2.5 25 Evaluation of Examples 2-3 Sol.3 240 R-01 110 / 90 nBA 44 2.2 25 Evaluation of Examples 2-4 Sol.4 240 R-01 110 / 90 nBA 44 2.3 25 Evaluation of Examples 2-5 Sol.5 240 R-01 110 / 90 nBA 44 2.2 25 Evaluation of Examples 2-6 Sol.6 240 R-01 110 / 90 nBA 44 2.4 25 Evaluation of Examples 2-7 Sol.7 240 R-01 110 / 90 nBA 44 2.4 25 Evaluation of Examples 2-8 Sol.8 240 R-01 110 / 90 nBA 44 2.5 25 Evaluation of Examples 2-9 Sol.9 240 R-01 110 / 90 nBA 44 2.5 25 Evaluation of Examples 2-10 Sol.10 240 R-01 110 / 90 nBA 44 2.4 25 Evaluation of Example 2-11 Sol.11 240 R-01 110 / 90 nBA 44 2.3 25 Evaluation of Examples 2-12 Sol.12 240 R-01 110 / 90 nBA 44 2.3 25 Evaluation of Examples 2-13 Sol.11 240 R-02 110 / 90 nBA 46 2.2 25 Evaluation of Examples 2-14 Sol.11 240 R-03 110 / 90 nBA 48 2.2 25 Evaluation of Examples 2-15 Sol.11 240 R-04 110 / 90 nBA 45 2.3 25 Evaluation of Examples 2-16 Sol.11 240 R-05 110 / 90 nBA 42 2.3 25 Evaluation of Examples 2-17 Sol.11 240 R-06 110 / 90 nBA 45 2.3 25 Evaluation of Examples 2-18 Sol.11 240 R-07 110 / 90 nBA 42 2.3 25 Evaluation of Example 2-19 Sol.11 240 R-08 110 / 90 nBA 48 2.3 25 Evaluation of Examples 2-20 Sol.11 240 R-09 110 / 90 nBA 48 2.2 25 Evaluation of Example 2-21 Sol.11 240 R-10 110 / 90 nBA 48 2.3 25 Comparative Evaluation Example 2-1 Sol.13 240 R-01 110 / 90 nBA 44 2.8 25 Comparative Evaluation Example 2-2 Sol.13 240 R-10 110 / 90 nBA 46 2.8 25 Comparative Evaluation Example 2-3 Sol.11 240 CR-01 105 / 90 TMAH 50 4.2 27 Comparative Evaluation Example 2-4 Sol.11 240 CR-02 105 / 90 TMAH 50 4.2 27

[0383] As shown in Table 7, comparing Comparative Examples 2-1 and 2-2 with the Example, excellent CDU patterns can be obtained in the 3-layer resist process by using the aforementioned silicon-containing resist lower film composition. Furthermore, even compared with Comparative Examples 2-3 and 2-4, which used chemically amplified resist compositions utilizing acid catalyst reactions, excellent sensitivity, resolution, and LWR are still achieved. Therefore, it can be concluded that in the 3-layer resist process using the stack of the present invention, excellent CDU is achieved during contact hole pattern formation by EUV exposure.

[0384] This specification includes the following inventions.

[0385] [1] A stacked body, characterized by comprising, in sequence: substrate, The silicon-containing inhibitor lower layer film is obtained from a silicon-containing inhibitor lower layer film composition containing a thermally crosslinked polysiloxane, wherein the thermally crosslinked polysiloxane contains any one or more repeating units represented by general formulas (1) to (3) below, and any one or more repeating units represented by general formulas (4) to (6) below, and The inhibitor film is derived from an inhibitor composition containing at least one superatomic iodine compound selected from the following formula (7), the following formula (8), the following formula (9), a carboxyl-containing compound, and a solvent. [Chemistry 116] In the formula, R1 is an organic group with a carboxyl group or an organic group with a carboxyl group that is replaced by an acid-instable group, and R2, R3 and R4 are monovalent organic groups with 1 to 30 carbon atoms that may be the same or different. [Chemistry 117] In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, or 5, and 1 ≤ n1 + n2 ≤ 6. When m is 1, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1 ≤ n1 + n2 ≤ 8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1 ≤ n1 + n2 ≤ 10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4. However, 1 ≤ n3 + n4 ≤ 5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4. However, 1 ≤ n5 + n6 ≤ 5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R11 to R18 are halogen atoms, or may contain hydrocarbon groups with 1 to 10 carbon atoms. Furthermore, R11 and R12, R13 and R14, R15 and R16, or R17 and R18 may also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between those carbon atoms. R21 to R24 are each independently a halogen atom, or may contain heteroatoms and be hydrocarbon groups with 1 to 40 carbon atoms. When n2 is 2 or more, each R21 can be the same or different, and multiple R21s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R22 can be the same or different, and multiple R22s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R23 can be the same or different, and multiple R23s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R24 can be the same or different, and multiple R24s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. R25 is an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R25 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned (n8) valent hydrocarbon group or (n8) valent heterocyclic group can be substituted by a group containing heteroatoms, and part of the -CH2- of the aforementioned (n8) valent hydrocarbon group can also be substituted by a group containing heteroatoms. R24 and R25 can also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between the carbon atoms. [2] As described in [1], a resistive underlayer is provided between the aforementioned substrate and the silicon-containing resistive underlayer. [3] As described in [1] or [2], the aforementioned silicon-containing inhibitor lower film composition contains a crosslinking catalyst (Xc) for siloxane polymerization, an alcohol-based organic solvent, and water. [4] As described in any of [1] to [3], the aforementioned carboxyl-containing compound in the aforementioned inhibitor composition is a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11). [Chemistry 118] In the formula, RA is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. XA represents a single bond, an enylphenyl group, an enylnaphthyl group, or *-C(=O)-O-XA1-. XA1 represents a saturated enylalkyl group, an enylphenyl group, or an enylnaphthyl group with 1 to 10 carbon atoms, and this saturated enylalkyl group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. * indicates an atomic bond with a carbon atom in the main chain. p can be 1, 2, 3 or 4. R31 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, R31 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, aminocarbamate 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 substituted by a group containing heteroatoms, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be substituted by a group containing heteroatoms. R32 is a single bond or an elongated hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the elongated hydrocarbon group may be replaced by a group containing heteroatoms, and part of the -CH2- of the elongated hydrocarbon group may also be replaced by a group containing heteroatoms. When p is 2 to 4, each R32 may be the same or different. [5] A method for manufacturing a laminated body, characterized by comprising the following steps: A resist lower layer film is formed on the substrate. On the resist lower layer film, a silicon-containing resist lower layer film is formed from a silicon-containing resist lower layer film composition containing any one or more repeating units represented by general formulas (1) to (3) and any one or more repeating units represented by general formulas (4) to (6) below, and A resistive composition containing at least one superatomic iodine compound selected from the following formula (7), superatomic iodine compound represented by the following formula (8) and superatomic iodine compound represented by the following formula (9), a carboxyl-containing compound, and a solvent is coated onto the silicon-containing resistive lower layer film, and then subjected to heat treatment to form a resistive film. [Chemistry 119] In the formula, R1 is an organic group with a carboxyl group or an organic group with a carboxyl group that is replaced by an acid-instable group, and R2, R3 and R4 are monovalent organic groups with 1 to 30 carbon atoms that may be the same or different. [Chemistry 120] In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, or 5, and 1 ≤ n1 + n2 ≤ 6. When m is 1, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1 ≤ n1 + n2 ≤ 8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1 ≤ n1 + n2 ≤ 10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4. However, 1 ≤ n3 + n4 ≤ 5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4. However, 1 ≤ n5 + n6 ≤ 5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R11 to R18 are halogen atoms, or may contain hydrocarbon groups with 1 to 10 carbon atoms. Furthermore, R11 and R12, R13 and R14, R15 and R16, or R17 and R18 may also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between those carbon atoms. R21 to R24 are each independently a halogen atom, or may contain heteroatoms and be hydrocarbon groups with 1 to 40 carbon atoms. When n2 is 2 or more, each R21 can be the same or different, and multiple R21s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R22 can be the same or different, and multiple R22s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R23 can be the same or different, and multiple R23s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R24 can be the same or different, and multiple R24s can bond together and form a ring with the carbon atoms of the aromatic rings they are bonded to. R25 is an (n8) valent hydrocarbon group with 1 to 40 carbon atoms or an (n8) valent heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R25 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned (n8) valent hydrocarbon group or (n8) valent heterocyclic group can be substituted by a group containing heteroatoms, and part of the -CH2- of the aforementioned (n8) valent hydrocarbon group can also be substituted by a group containing heteroatoms. R24 and R25 can also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between the carbon atoms. [6] The manufacturing method of the stack described in [5] involves coating a lower film forming material onto a substrate and then heating it to form the aforementioned resist lower film. [7] The manufacturing method of the laminate described in [5] involves forming the aforementioned resist lower layer film using CVD or ALD methods. [8] The method for manufacturing a multilayer as described in any of [5] to [7] defines the aforementioned carboxyl-containing compound as a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11). [Chemistry 121] In the formula, RA is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. XA represents a single bond, an enylphenyl group, an enylnaphthyl group, or *-C(=O)-O-XA1-. XA1 represents a saturated enylalkyl group, an enylphenyl group, or an enylnaphthyl group with 1 to 10 carbon atoms, and this saturated enylalkyl group may also contain a hydroxyl group, an ether bond, an ester bond, or an lactone ring. * indicates an atomic bond with a carbon atom in the main chain. p can be 1, 2, 3 or 4. R31 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, R31 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, aminocarbamate 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 substituted by a group containing heteroatoms, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be substituted by a group containing heteroatoms. R32 is a single bond or an elongated hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the elongated hydrocarbon group may be replaced by a group containing heteroatoms, and part of the -CH2- of the elongated hydrocarbon group may also be replaced by a group containing heteroatoms. When p is 2 to 4, each R32 may be the same or different. [9] A method for forming a pattern includes the following steps: Exposure of the resist film of the multilayer structure described in any of [1] to [4] to i-rays, KrF excimer lasers, ArF excimer lasers, electron beams or extreme ultraviolet light, and The previously exposed resist film was developed using a developer.

[10] The pattern forming method described in [9] is an organic solvent.

[0386] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative examples, and those having a structure that is substantially the same as the technical concept described in the claims of the present invention and performing the same effect are all intended to be included within the technical scope of the present invention.

Claims

1. A laminate, characterized in that it comprises, in sequence: a substrate; a silicon-containing resist lower film derived from a silicon-containing resist lower film composition containing a thermally crosslinked polysiloxane, the thermally crosslinked polysiloxane containing any one or more repeating units represented by general formulas (1) to (3) and any one or more repeating units represented by general formulas (4) to (6); and a resist film derived from a resist composition containing at least one superatomic iodine compound selected from superatomic iodine compounds represented by formula (7), superatomic iodine compounds represented by formula (8), and superatomic iodine compounds represented by formula (9), a carboxyl-containing compound, and a solvent; wherein R1 is an organic group having a carboxyl group or an organic group having a carboxyl group substituted by an acid-instable group, and R2, R3, and R4 are monovalent organic groups with 1 to 30 carbon atoms that may be the same or different; In the formula, m is 1 or 2; when m is 1, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4, 5, 6 or 7, and 1≦n1+n2≦8; when m is 2, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and 1≦n1+n2≦10; n3 is 1 or 2; n4 is 0, 1, 2, 3 or 4; only, 1≦n3+n4≦5; n5 is 1 or 2; n6 is 0, 1, 2, 3 or 4; only, 1≦n5+n6≦5; n7 is 0, 1, 2, 3 or 4; n8 is 1, 2, 3 or 4; R11 to R18 are halogen atoms or hydrocarbon groups with 1 to 10 carbon atoms that may contain heteroatoms; furthermore, R11 and R12, R13 and R14, R15 and R16, or R17 and R18 may also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between those carbon atoms. R21 to R24 are each independently a halogen atom, or may contain heteroatoms and be hydrocarbon groups with 1 to 40 carbon atoms; when n2 is 2 or more, each R21 can be the same or different, and multiple R21s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to; when n4 is 2 or more, each R22 can be the same or different, and multiple R22s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to; when n6 is 2 or more, each R23 can be the same or different, and multiple R23s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to; when n7 is 2 or more, each R24 can be the same or different, and multiple R24s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. R25 is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R25 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl group.Furthermore, some or all of the hydrogen atoms in the (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be replaced by a group containing heteroatoms, and part of the -CH2- of the (n8) valence hydrocarbon group can also be replaced by a group containing heteroatoms. R24 and R25 can also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between the carbon atoms.

2. As in request item 1, the stack-up, wherein, An underlayer resist is provided between the substrate and the silicon-containing underlayer resist.

3. As in request item 1, the stack-up, wherein, The silicon-containing inhibitor lower layer film composition contains a crosslinking catalyst (Xc) for siloxane polymerization, an alcohol-based organic solvent, and water.

4. As in request item 1, the stack-up, wherein, The carboxyl-containing compound in the inhibitor composition is a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11); where RA is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group; XA is a single bond, a phenyl group, a naphthyl group, or *-C(=O)-O-XA1-; XA1 is a saturated alkyl group with 1 to 10 carbon atoms, a phenyl group, or a naphthyl group, and the saturated alkyl group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring; * represents an atomic bond with a carbon atom of the main chain; p is 1, 2, 3, or 4; R31 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, R31 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, aminocarbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group can be substituted by a group containing heteroatoms, and some of the -CH2- of the p-valent hydrocarbon group can also be substituted by a group containing heteroatoms. R32 is a single bond or an extended hydrocarbon group with 1 to 10 carbon atoms. Some or all of the hydrogen atoms of the extended hydrocarbon group can be substituted by a group containing heteroatoms, and some of the -CH2- of the extended hydrocarbon group can also be substituted by a group containing heteroatoms. When p is 2 to 4, each R32 can be the same or different.

5. A method for manufacturing a laminate, characterized by comprising the following steps: forming a resist lower layer film on a substrate; forming a silicon-containing resist lower layer film on the resist lower layer film from a silicon-containing resist lower layer film composition containing any one or more repeating units represented by the following general formulas (1) to (3) and any one or more repeating units represented by the following general formulas (4) to (6); coating the silicon-containing resist lower layer film with a resist composition containing at least one superatomic iodine compound selected from the following superatomic iodine compound represented by formula (7), the following superatomic iodine compound represented by formula (8) and the following superatomic iodine compound represented by formula (9), a carboxyl-containing compound, and a solvent; and performing a heat treatment to form a resist film. In the formula, R1 is an organic group with a carboxyl group or an organic group with a carboxyl group that is replaced by an acid-instable group, and R2, R3 and R4 are monovalent organic groups with 1 to 30 carbon atoms that may be the same or different. In the formula, m is 1 or 2; when m is 1, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4, 5, 6 or 7, and 1≦n1+n2≦8; when m is 2, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and 1≦n1+n2≦10; n3 is 1 or 2; n4 is 0, 1, 2, 3 or 4; only, 1≦n3+n4≦5; n5 is 1 or 2; n6 is 0, 1, 2, 3 or 4; only, 1≦n5+n6≦5; n7 is 0, 1, 2, 3 or 4; n8 is 1, 2, 3 or 4; R11 to R18 are halogen atoms or hydrocarbon groups with 1 to 10 carbon atoms that may contain heteroatoms; furthermore, R11 and R12, R13 and R14, R15 and R16, or R17 and R18 may also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between those carbon atoms. R21 to R24 are each independently a halogen atom, or may contain heteroatoms and be hydrocarbon groups with 1 to 40 carbon atoms; when n2 is 2 or more, each R21 can be the same or different, and multiple R21s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to; when n4 is 2 or more, each R22 can be the same or different, and multiple R22s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to; when n6 is 2 or more, each R23 can be the same or different, and multiple R23s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to; when n7 is 2 or more, each R24 can be the same or different, and multiple R24s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. R25 is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R25 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl group.Furthermore, some or all of the hydrogen atoms in the (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be replaced by a group containing heteroatoms, and part of the -CH2- of the (n8) valence hydrocarbon group can also be replaced by a group containing heteroatoms. R24 and R25 can also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between the carbon atoms.

6. The method for manufacturing the stack as claimed in claim 5, wherein a lower film forming material is coated onto a substrate and subjected to heat treatment, thereby forming the resist lower film.

7. The method for manufacturing the laminate as described in claim 5, wherein the resist lower layer film is formed by CVD or ALD.

8. A method for manufacturing a multilayer as claimed in any of claims 5 to 7, wherein the carboxyl-containing compound is defined as a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11); wherein RA is a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group; XA is a single bond, an phenyl group, a naphthyl group or *-C(=O)-O-XA1-; XA1 is a saturated alkyl group with 1 to 10 carbon atoms, an phenyl group or a naphthyl group, and the saturated alkyl group may also contain a hydroxyl group, an ether bond, an ester bond or a lactone ring; * represents an atomic bond with a carbon atom of the main chain; p is 1, 2, 3 or 4; R31 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, R31 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, aminocarbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group can be substituted by a group containing heteroatoms, and some of the -CH2- of the p-valent hydrocarbon group can also be substituted by a group containing heteroatoms. R32 is a single bond or an extended hydrocarbon group with 1 to 10 carbon atoms. Some or all of the hydrogen atoms of the extended hydrocarbon group can be substituted by a group containing heteroatoms, and some of the -CH2- of the extended hydrocarbon group can also be substituted by a group containing heteroatoms. When p is 2 to 4, each R32 can be the same or different.

9. A pattern forming method comprising the following steps: exposing a resist film of a multilayer as claimed in any one of claims 1 to 4 to an i-ray, a KrF excimer laser, an ArF excimer laser, an electron beam, or extreme ultraviolet light to the resist film, and developing the exposed resist film using a developer.

10. The pattern forming method as described in claim 9, wherein, The developer is an organic solvent.

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