Laminate, method for manufacturing laminate, and method for forming pattern

Abstract

The invention relates to a laminate, a method for manufacturing the laminate, and a method for forming a pattern. The invention provides a laminate, a method for manufacturing the laminate, and a method for forming a pattern, wherein the laminate has both high sensitivity and high resolution and forms a fine pattern in optical lithography using high-energy rays. [Solution] This laminate is characterized by comprising, in this order, a substrate, a silicon-containing resist underlayer film, and a silicon-containing resist underlayer film composition obtained from a thermally crosslinkable polysiloxane, the thermally crosslinkable polysiloxane contains any one or more of repeating units represented by formulae (1)-(3) and any one or more of repeating units represented by formulae (4)-(6), and the resist film is obtained from the resist composition. The present invention relates to a liquid crystal composition containing: at least one type of super-atomic iodine compound selected from the group consisting of super-atomic iodine compounds represented by formula (7), super-atomic iodine compounds represented by formula (8), and super-atomic iodine compounds represented by formula (9); a carboxyl group-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. Background Technology

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

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

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

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

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

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

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

[0009] Patent Document 2 proposes a negative resist composition using tin compounds. This composition uses tin, which has high absorption under EUV light, as the main component, thus improving 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, making it insoluble in the developer, an additional inversion process is required when using it for patterning contact holes, raising concerns about cost.

[0010] Existing technical documents

[0011] Patent documents

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

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

[0014] [Non-Patent Literature 1] SPIE Vol.5039p1 (2003)

[0015] [Non-Patent Literature 2] SPIE Vol.6520p65203L-1(2007) Summary of the Invention

[0016] [The problem that the invention aims to solve]

[0017] The present invention was made in view of the foregoing circumstances, and aims to provide a laminate having a resist film and a silicon-containing resist underlayer film located below the resist film, the resist film being derived from a non-chemically amplified resist composition with excellent sensitivity and limiting resolution suitable for optical lithography using high-energy rays, especially electron beam (EB) lithography and EUV lithography; and to provide a method for patterning the upper layer of the laminate.

[0018] [Methods for solving the problem]

[0019] To address the aforementioned issues, the present invention provides a laminated body characterized by comprising, in sequence:

[0020] substrate,

[0021] A silicon-containing photoresist underlayer film is obtained from a silicon-containing photoresist underlayer 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

[0022] 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), superatomic iodine compounds represented by formula (9), a carboxyl-containing compound, and a solvent.

[0023] [Chemistry 1]

[0024]

[0025] In the formula, R 1 R is an organic group having a carboxyl group or an organic group having a carboxyl group substituted by an acid-labile group. 2 R 3 and R 4 These are monovalent organic groups with 1 to 30 carbon atoms, which may be the same or different.

[0026] [Chemistry 2]

[0027]

[0028] 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.

[0029] R 11 ~R 18 Each group consists independently of a halogen atom, or may contain heteroatoms, and is a hydrocarbon group with 1 to 10 carbon atoms. Also, R 11 and R 12 R 13 and R 14 R 15 and R 16 、or R 17 and R 18 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0030] R 21 ~R 24 Each R is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms. When n2 is 2 or more, each R 21 They can be the same or different, and there are multiple Rs. 21 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R 22 They can be the same or different, and there are multiple Rs. 22 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R 23 They can be the same or different, and there are multiple Rs. 23 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R 24 They can be the same or different, and there are multiple Rs. 24 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0031] R 25 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 25It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl bond. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 24 and R 25 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0032] Such a stacked structure would be suitable for optical lithography 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.

[0033] At this time, it is advisable to have a photoresist underlayer between the aforementioned substrate and the silicon-containing photoresist underlayer.

[0034] Such a stack can precisely transfer the pattern of the resist film with excellent resolution to the substrate, which is extremely effective for micro-processing.

[0035] The aforementioned silicon-containing photoresist lower film composition preferably contains a crosslinking catalyst (Xc) for siloxane polymerization, an alcohol-based organic solvent, and water.

[0036] If such a silicon-containing photoresist underlayer composition is used, it will become a stable and well-operated silicon-containing photoresist underlayer composition, and the patterning ability and film strength of the prepared silicon-containing photoresist underlayer film will be ideal.

[0037] The aforementioned carboxyl-containing compound in the aforementioned resist composition is preferably a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11).

[0038] [Chemistry 3]

[0039]

[0040] In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group.

[0041] X A It is a single bond, phenylene, naphthylene, or *-C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0042] p can be 1, 2, 3 or 4.

[0043] R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms; when p is 2, R 31 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing heteroatoms, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be replaced by a group containing heteroatoms.

[0044] R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group can be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group can also be replaced by a group containing a heteroatom. When p is 2 to 4, each R 32 They can be the same or different.

[0045] Compounds containing carboxyl groups with such a structure have high solubility in solvents, are easy to form into compositions, and can achieve high etch resistance due to their rigid framework.

[0046] Furthermore, the present invention provides a method for manufacturing a laminate, characterized by comprising the following steps:

[0047] A resist underlayer film is formed on the substrate.

[0048] On the resist underlayer film, a silicon-containing resist underlayer film is formed from a silicon-containing resist underlayer 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

[0049] A resist 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 resist lower layer film, and then subjected to heat treatment to form a resist film.

[0050] [Chemistry 4]

[0051]

[0052] In the formula, R 1 R is an organic group having a carboxyl group or an organic group having a carboxyl group substituted by an acid-labile group. 2 R 3 and R 4These are monovalent organic groups with 1 to 30 carbon atoms, which may be the same or different.

[0053] [Chemistry 5]

[0054]

[0055] 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.

[0056] R 11 ~R 18 Each group consists independently of a halogen atom, or may contain heteroatoms, and is a hydrocarbon group with 1 to 10 carbon atoms. Also, R 11 and R 12 R 13 and R 14 R 15 and R 16 、or R 17 and R 18 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0057] R 21 ~R 24 Each R is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms. When n2 is 2 or more, each R 21 They can be the same or different, and there are multiple Rs. 21 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R 22 They can be the same or different, and there are multiple Rs. 22 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R 23 They can be the same or different, and there are multiple Rs. 23 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R 24 They can be the same or different, and there are multiple Rs. 24 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0058] R 25 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 25 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl bond. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 24 and R 25 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0059] By forming a silicon-containing photoresist lower layer and then forming a photoresist film on top of it, which is composed of a photoresist composition with superatomic iodine compounds and carboxyl-containing compounds as the main components, a photoresist film with excellent resolution can be formed, and a laminate that is extremely effective for precision micro-machining can be manufactured.

[0060] 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.

[0061] Alternatively, the aforementioned resist underlayer film can also be formed using CVD or ALD methods.

[0062] In addition, the aforementioned carboxyl-containing compounds may also be defined as polymers containing repeating units represented by formula (10) or compounds represented by formula (11).

[0063] [Chemistry 6]

[0064]

[0065] In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group.

[0066] X A It is a single bond, phenylene, naphthylene, or *-C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0067] p can be 1, 2, 3 or 4.

[0068] R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms; when p is 2, R 31It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing heteroatoms, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be replaced by a group containing heteroatoms.

[0069] R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group can be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group can also be replaced by a group containing a heteroatom. When p is 2 to 4, each R 32 They can be the same or different.

[0070] 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.

[0071] This invention provides a pattern forming method, comprising the following steps:

[0072] The resist film of the above-described laminate was exposed using i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet light.

[0073] The previously exposed resist film was developed using a developer.

[0074] This invention utilizes exposure to high-energy rays on an anti-photoresist film and development with a developing solution to form high-sensitivity and high-resolution micro-patterns.

[0075] The aforementioned developing solution can be an organic solvent.

[0076] The resist film of the present invention is robust due to the effects of the superatomic iodine compound and the carboxylic acid compound, and has excellent etching resistance and developer resistance to solvent developer. Therefore, it can be ideally used in pattern forming methods that use organic solvent developer.

[0077] [The effects of the invention]

[0078] The laminates of the present invention are 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. Detailed Implementation

[0079] As mentioned above, there is a need to develop high-sensitivity and high-resolution photolithography materials suitable for forming fine patterns, which have excellent dimensional uniformity (CDU), low linewidth roughness (LWR), and are not prone to causing micro-hole blockage.

[0080] 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 photoresist underlayer film beneath a photoresist film derived from a photoresist composition consisting mainly of a predetermined superatomic iodine compound and a carboxyl-containing compound, it is highly effective for providing a photoresist film exhibiting excellent resolution and for precise micromachining.

[0081] The laminate of the present invention is extremely useful as a laminate for multilayer photoresist processes, such as three-layer photoresist processes using a photoresist underlayer film and a silicon-containing photoresist underlayer film.

[0082] The present invention will now be described in detail, but it is not limited thereto.

[0083] That is, the present invention is a laminate comprising a substrate, a silicon-containing photoresist lower layer film, and a photoresist film in sequence.

[0084] [Layered Body]

[0085] The laminate of the present invention is characterized by comprising, in sequence:

[0086] substrate,

[0087] A silicon-containing photoresist underlayer film is obtained from a silicon-containing photoresist underlayer 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

[0088] 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), superatomic iodine compounds represented by formula (9), a carboxyl-containing compound, and a solvent.

[0089] [Chemistry 7]

[0090]

[0091] In the formula, R 1 R is an organic group having a carboxyl group or an organic group having a carboxyl group substituted by an acid-labile group. 2 R 3 and R 4 These are monovalent organic groups with 1 to 30 carbon atoms, which may be the same or different.

[0092] [Chemistry 8]

[0093]

[0094] 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.

[0095] R 11 ~R 18 Each group consists independently of a halogen atom, or may contain heteroatoms, and is a hydrocarbon group with 1 to 10 carbon atoms. Also, R 11 and R 12 R 13 and R 14 R 15 and R 16 、or R 17 and R 18 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0096] R 21 ~R 24 Each R is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms. When n2 is 2 or more, each R 21 They can be the same or different, and there are multiple Rs. 21 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R 22 They can be the same or different, and there are multiple Rs. 22 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R 23 They can be the same or different, and there are multiple Rs. 23 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R 24 They can be the same or different, and there are multiple Rs. 24 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0097] R 25 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 25It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl bond. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 24 and R 25 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0098] The following sections will describe the substrate, the silicon-containing photoresist underlayer, and the photoresist film in that order.

[0099] [Substrate]

[0100] The aforementioned substrates are preferably substrates used for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, etc.) or substrates used for shielding circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.).

[0101] [Silicone-containing photoresist underlayer]

[0102] The aforementioned silicon-containing photoresist underlayer film is obtained from a silicon-containing photoresist underlayer film composition containing a thermally crosslinked polysiloxane with a specific structure as described below.

[0103] [Thermocrosslinkable polysiloxane]

[0104] The thermally crosslinked polysiloxane of the present invention will be described below.

[0105] 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).

[0106] [Chemistry 9]

[0107]

[0108] In the formula, R 1 R is an organic group having a carboxyl group or an organic group having a carboxyl group substituted by an acid-labile group. 2 R 3 and R 4 These are monovalent organic groups with 1 to 30 carbon atoms, which may be the same or different.

[0109] R in the above general formulas (1) to (3) 1 Examples include, but are not limited to, those listed below. Additionally, in the following formula, (Si) is used to indicate the bond position with Si.

[0110] [Chemistry 10]

[0111]

[0112] [Chemistry 11]

[0113]

[0114] In the formula, R 2 R 3 and R 4 These are monovalent organic groups with 1 to 30 carbon atoms, which may be the same or different. R 2 R 3 It should be a saturated or unsaturated organic group having 1 to 20 carbon atoms, and may also have substituents. Examples of organic groups include: substituted or unsubstituted chain, branched, or cyclic alkyl groups having 1 to 20 carbon atoms; substituted or unsubstituted chain, branched, or cyclic alkenyl groups having 2 to 20 carbon atoms; and substituted or unsubstituted aryl groups having 6 to 20 carbon atoms. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl; vinyl, allyl, propenyl; phenyl, tolyl, etc.

[0115] R 2 R 3 and R 4 Other examples of the represented organic groups include organic groups having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, it refers to 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).

[0116] (P-Q1-(S1) v1 -Q2-) u -(T) v2 -Q3-(S2)v3-Q4-

[0117] (Sm-R)

[0118] 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, and 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.

[0119] Examples of alicyclic, aromatic, or heterocyclic rings that may also contain heteroatoms such as oxygen atoms are shown below as T. In T, the bonding 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.

[0120] [Chemistry 12]

[0121]

[0122] Ideal examples of organic groups 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.

[0123] [Chemistry 13]

[0124]

[0125] [Chemistry 14]

[0126]

[0127] Also, R 2 R 3 and R 4 Examples of organic groups that can be used include organic groups containing silicon-silicon bonds. Specific examples are listed below.

[0128] [Chemistry 15]

[0129]

[0130] In addition, R 2 R 3 and R 4 Examples of organic groups may also be organic groups having fluorine atoms. Specifically, examples can be found in the organic groups of silicon compounds shown in paragraphs (0059) to (0065) of Japanese Patent Application Publication No. 2012-53253.

[0131] The aforementioned hydrolyzable monomer (Sm) has one, two, or three chlorine, bromine, iodine, acetoxy, methoxy, ethoxy, propoxy, or butoxy groups bonded to silicon (Si) in the aforementioned partial structure as hydrolyzable groups.

[0132] [Synthesis method of thermocrosslinkable polysiloxanes (raw materials)]

[0133] The thermally crosslinked polysiloxanes in formulas (4) to (6) can be manufactured, for example, by hydrolyzing and condensing the following hydrolyzable monomer (Sm).

[0134] Hydrolyzable monomers (Sm) can be specifically exemplified as follows: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyl Tripropoxysilane, isopropyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltriisopropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, isobutyltriisopropoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltripropoxysilane, sec-butyltriisopropoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butyltripropoxysilane, tert-butyltriisopropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, allyltriisopropoxysilane, cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane, cyclopropyltripropoxysilane Cyclopropyltriisopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyltripropoxysilane, cyclobutyltriisopropoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltripropoxysilane, cyclopentyltriisopropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, cyclohexyltriisopropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane Oxysilanes, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, dicycloheptenyltrimethoxysilane, dicycloheptenyltriethoxysilane, dicycloheptenyltripropoxysilane, dicycloheptenyltriisopropoxysilane, dicycloheptenyltrimethoxysilane, dicycloheptenyltriethoxysilane, dicycloheptenyltripropoxysilane, dicycloheptenyltriisopropoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyltripropoxysilane, adamantyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilanePhenyltriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltripropoxysilane, benzyltriisopropoxysilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltripropoxysilane, methoxybenzyltriisopropoxysilane, toluenetrimethoxysilane, toluenetriethoxysilane, toluenetripropoxysilane, toluenetriisopropoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltripropoxysilane, phenethyltriisopropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltripropoxysilane, naphthyltriisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methyl Diethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, dipropyldiisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxysilane, dibutyldiisopropoxysilane, di(sec-butyl)dimethoxysilane, di(sec-butyl)diethoxysilane, di(sec-butyl)dipropoxysilane, di(sec-butyl)diisopropoxysilane Silane oxyalkylene, di(tert-butyl)dimethoxysilane, di(tert-butyl)diethoxysilane, di(tert-butyl)dipropoxysilane, di(tert-butyl)diisopropoxysilane, dicyclopropyldimethoxysilane, dicyclopropyldiethoxysilane, dicyclopropyldipropoxysilane, dicyclopropyldiisopropoxysilane, dicyclobutyldimethoxysilane, dicyclobutyldiethoxysilane, dicyclobutyldipropoxysilane, dicyclobutyldiisopropoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentyldipropoxysilane, dicyclopentyldiisopropoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane, dicyclohexyldiisopropoxysilane, dicyclohexenyldimethoxysilane Silane, dicyclohexenyldiethoxysilane, dicyclohexenyldiepropoxysilane, dicyclohexenyldieisopropoxysilane, dicyclohexenylethyldimethoxysilane, dicyclohexenylethyldiethoxysilane, dicyclohexenylethyldipropoxysilane, dicyclohexenylethyldiisopropoxysilane, dicyclooctyldimethoxysilane, dicyclooctyldiethoxysilane, dicyclooctyldipropoxysilane, dicyclooctyldiisopropoxysilane, dicyclopentadienylpropyldimethoxysilane, dicyclopentadienylpropyldiethoxysilane, dicyclopentadienylpropyldipropoxysilane, dicyclopentadienylpropyldiisopropoxysilane, bis(biscycloheptenyl)dimethoxysilane, bis(biscycloheptenyl)diethoxysilane, bis(biscycloheptenyl)dipropoxysilane,Bis(bicycloheptenyl)diisopropoxysilane, bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis(bicycloheptenyl)dipropoxysilane, bis(bicycloheptenyl)diisopropoxysilane, dadamantyldimethoxysilane, dadamantyldiethoxysilane, dadamantyldipropoxysilane, dadamantyldiisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethylbenzylmethoxysilane, dimethylbenzylethoxysilane, dimethylphenylethylmethoxysilane, dimethylphenylethoxysilane, dimethylbenzylmethoxysilane, dimethylphenylethylmethoxysilane, dimethylphenylethoxysilane, etc.

[0135] 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, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethylethyldimethoxysilane, dimethylethyldimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane, etc.

[0136] [Synthesis method (reaction) of thermocrosslinked polysiloxanes]

[0137] (Synthesis Method 1: Acid Catalyst)

[0138] The thermally crosslinked polysiloxane used in this invention can be manufactured by hydrolyzing and condensing one or more hydrolyzable monomers (Sm) in the presence of an acid catalyst.

[0139] 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 mole of monomer should preferably be 1 × 10⁻⁶. -6 ~10 moles, which is 1×10 -5 ~5 moles is better, which is 1×10 -4 ~1 mole is even better.

[0140] When obtaining thermally crosslinked polysiloxanes from these monomers via hydrolysis-condensation, the amount of water added per mole of the hydrolytic substituents bonded to the monomers is preferably 0.01–100 moles, more preferably 0.05–50 moles, and even more preferably 0.1–30 moles. If the amount is less than 100 moles, the equipment used for the reaction is smaller and more economical. If the amount is 0.01 moles or more, the reaction will proceed fully.

[0141] The procedure involves adding the monomer to an aqueous catalyst solution to initiate the hydrolysis-condensation reaction. Alternatively, an organic solvent can be added to the catalyst 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.

[0142] 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, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, and mixtures thereof.

[0143] 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.

[0144] Furthermore, the optimal amount of organic solvent used relative to 1 mole 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.

[0145] 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 basic substance used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used in the catalyst. This basic substance can be any substance that is alkaline in water.

[0146] 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. Determining the exact amount of alcohol to be removed at this time is not easy, but removing approximately 80% or more of the generated alcohols is ideal.

[0147] The acid catalyst used in the hydrolysis-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, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0148] 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.

[0149] 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 is preferably 0.1 to 1,000 parts by mass, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass per 100 parts by mass.

[0150] Then, neutral water can be used for rinsing. Deionized water or ultrapure water is suitable. The volume of this 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.

[0151] Other methods for removing acid catalysts include methods using ion exchange resins and methods involving neutralization with epoxides such as ethylene oxide and propylene oxide. These methods can be appropriately selected based on the acid catalyst used in the reaction.

[0152] 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 classification 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 classification effect.

[0153] The desired thermally crosslinked polysiloxane solution can be obtained 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, followed by solvent exchange under reduced pressure. 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. 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, and is preferably below atmospheric pressure, more preferably below 80 kPa, and even more preferably below 50 kPa.

[0154] 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 solvent exchange operation can be performed after adding a mono- or di-ortho-ol having a cyclic ether as a substituent to the solution before solvent exchange.

[0155] 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.

[0156] 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, butanediol, etc. 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.

[0157] 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, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0158] Another reaction 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 a rise to 20–80°C to allow it to mature.

[0159] 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.

[0160] The optimal amount of organic solvent used relative to 1 mole 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. The resulting aqueous reaction mixture can be post-treated using the same method as described above to obtain thermally crosslinked polysiloxanes.

[0161] (Synthesis Method 2: Alkali Catalyst)

[0162] Furthermore, thermally crosslinked polysiloxanes can be manufactured by hydrolyzing and condensing one or more hydrolyzable monomers (Sm) in the presence of an alkaline catalyst. Examples of alkaline catalysts used 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, piperazine, 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 mole of monomer should preferably be 1 × 10⁻⁶. -6 1 mole ~ 10 moles, which is 1 × 10 -5 1 × 10⁻⁵ moles is preferred. -4 One mole is even better.

[0163] When obtaining thermally crosslinked polysiloxanes from the above monomers via hydrolysis-condensation, the amount of water added should be 0.1 to 50 moles per mole of the hydrolytic substituents bonded to the monomer. If the amount is less than 50 moles, the equipment used for the reaction is smaller and more economical. If the amount is 0.1 moles or more, the reaction will proceed fully.

[0164] The procedure involves adding the monomer to an aqueous catalyst solution to initiate the hydrolysis-condensation reaction. Alternatively, an organic solvent can be added to the catalyst 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.

[0165] Organic solvents that can be added to aqueous solutions of alkaline catalysts, or organic solvents that can dilute monomers, are preferably used, as exemplified by organic solvents that can be added to aqueous solutions of acid catalysts. Furthermore, for economical reaction implementation, the amount of organic solvent used is preferably 0 to 1,000 ml relative to 1 mole of monomer.

[0166] 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 is preferably 0.1 to 2 equivalents relative to the basic substance used for the catalyst. This acidic substance can be any substance that is acidic in water.

[0167] Then, byproducts such as alcohols generated during the hydrolysis and condensation reaction are removed 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.

[0168] 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, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0169] Alternatively, a mixture of water-soluble organic solvents and water-insoluble organic solvents can be used.

[0170] 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.

[0171] In addition, the mixing ratio of water-soluble organic solvent and water-poorly soluble organic solvent can be appropriately selected. It is preferable to use 0.1 to 1,000 parts by mass of water-soluble organic solvent relative to 100 parts by mass of water-poorly soluble organic solvent, preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0172] Then, rinse with neutral water. Deionized water or ultrapure water can be used. The volume of this 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 can be achieved by placing both solutions in the same container, stirring, and 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.

[0173] 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.

[0174] The final solvent added to the thermally crosslinked polysiloxane solution should preferably be an alcohol-based solvent, with monoalkyl ether derivatives of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc. being particularly preferred. Specifically, 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., are preferred.

[0175] 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.

[0176] Organic solvents that can be used as monomers, 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.

[0177] The molecular weight of the thermally crosslinked polysiloxane obtained by the above synthesis methods 1 or 2 can be adjusted not only by selecting the monomer 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, and polystyrene as the standard substance, with molecular weight expressed in polystyrene form.

[0178] The physical properties of the thermally crosslinked polysiloxane used in this invention vary depending on the type of acid or base 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 resist film intended for use.

[0179] In addition, a polysiloxane derivative manufactured by mixing one or more hydrolyzable monomers (Sm) with a hydrolyzable metal compound represented by the following general formula (Mm) under the aforementioned conditions using an acid or base catalyst can be used as a component of the composition for forming the resist underlayer film.

[0180] U(OR 7 )m7(OR 8 )m8(Mm)

[0181] In the general formula (Mm), R 7 and R 8 Each is an organic group with 1 to 30 carbon atoms, m7+m8 and the valence number determined by the type of U are the same, m7 and m8 are integers greater than 0, and U is an element of group III, IV or V of the periodic table excluding carbon and silicon.

[0182] Examples of hydrolyzable metal compounds represented by the general formula (Mm) used here include the following. When U is boron, examples of hydrolyzable metal compounds represented by the general formula (Mm) include methoxyboron, ethoxyboron, propoxyboron, butoxyboron, pentoxyboron, hexoxyboron, cyclopentoxyboron, cyclohexyloxyboron, allyloxyboron, phenoxyboron, methoxyethoxyboron, boric acid, boron oxide, etc.

[0183] When U is aluminum, examples of hydrolyzable metal compounds represented by the general formula (Mm) include aluminum methoxy, aluminum ethoxy, aluminum propoxy, aluminum butoxy, aluminum pentoxy, aluminum hexoxy, aluminum cyclopentoxy, aluminum cyclohexoxy, aluminum allyloxy, aluminum phenoxy, aluminum methoxyethoxy, aluminum ethoxyethoxy, aluminum dipropoxyethyl acetoacetate, aluminum dibutoxyethyl acetoacetate, aluminum propoxydiethyl acetoacetate, aluminum butoxydiethyl acetoacetate, aluminum 2,4-pentanedione, aluminum 2,2,6,6-tetramethyl-3,5-heptadecanedione, etc.

[0184] 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, dipropoxyethyl acetoacetate gallium, dibutoxyethyl acetoacetate gallium, propoxydiethyl acetoacetate gallium, butoxydiethyl acetoacetate gallium, 2,4-pentanedione gallium, 2,2,6,6-tetramethyl-3,5-heptanedione gallium, etc.

[0185] 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, dipropoxyethylacetoacetate yttrium, dibutoxyethylacetoacetate yttrium, propoxydiethylacetoacetate yttrium, butoxydiethylacetoacetate yttrium, 2,4-pentanedione acid yttrium, 2,2,6,6-tetramethyl-3,5-heptadecanedione acid yttrium, etc.

[0186] When U is germanium, the hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified as 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.

[0187] When U is titanium, the 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, cyclohexoxy titanium, allyloxy titanium, phenoxy titanium, methoxyethoxy titanium, ethoxyethoxy titanium, dipropoxybis(ethyl)acetoacetate titanium, dibutoxybis(ethyl)acetoacetate titanium, dipropoxybis(2,4-pentanedione) titanium, dibutoxybis(2,4-pentanedione) titanium, etc.

[0188] When U is hafnium, the hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified as methoxyhafnium, ethoxyhafnium, propoxyhafnium, butoxyhafnium, pentooxyhafnium, hexoxyhafnium, cyclopentoxyhafnium, cyclohexoxyhafnium, allyloxyhafnium, phenoxyhafnium, methoxyethoxyhafnium, ethoxyethoxyhafnium, dipropoxybis(ethyl)acetoacetate hafnium, dibutoxybis(ethyl)acetoacetate hafnium, dipropoxybis(2,4-pentanedione) hafnium, dibutoxybis(2,4-pentanedione) hafnium, etc.

[0189] 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.

[0190] When U is arsenic, the hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified by methoxyarsenic, ethoxyarsenic, propoxyarsenic, butoxyarsenic, phenoxyarsenic, etc.

[0191] 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.

[0192] When U is niobium, the hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified by methoxyniobium, ethoxyniobium, propoxyniobium, butoxyniobium, phenoxyniobium, etc.

[0193] When U is tantalum, the hydrolytic metal compounds represented by the general formula (Mm) can be exemplified by methoxy tantalum, ethoxy tantalum, propoxy tantalum, butoxy tantalum, phenoxy tantalum, etc.

[0194] When U is bismuth, the hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified by methoxybismuth, ethoxybismuth, propoxybismuth, butoxybismuth, phenoxybismuth, etc.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] [Amount of thermally crosslinked polysiloxane added]

[0199] In the silicon-containing photoresist 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.

[0200] Crosslinking catalyst for siloxane polymerization

[0201] The silicon-containing photoresist 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 is sometimes referred to below as a crosslinking catalyst for siloxane polymerization or simply as a crosslinking catalyst.

[0202] In this invention, the crosslinking catalyst for the aforementioned siloxane polymerization can be a sulfonium salt, monazine salt, phosphonium salt, ammonium salt, or a polysiloxane having them as part of its structure, or an alkali metal salt.

[0203] Crosslinking catalysts (Xc) for siloxane polymerization can be listed as compounds represented by the following general formula (Xc0).

[0204] LaHbA(Xc0)

[0205] In the formula, L is lithium, sodium, potassium, rubidium, cesium, sulfonium, monium, 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.

[0206] Specific examples of (Xc0) include sulfonium salts of the general formula (Xc-1), monium salts of (Xc-2), phosphonium salts of (Xc-3), ammonium salts of (Xc-4), alkali metal salts, etc.

[0207] Sulfonium salt (Xc-1), monazine salt (Xc-2), and phosphorus salt (Xc-3) are exemplified below.

[0208] [Chemistry 16]

[0209]

[0210] Furthermore, ammonium salts (Xc-4) are exemplified below.

[0211] [Chemistry 17]

[0212]

[0213] In the formula, R 204 R 205 R 206 R 207These groups respectively represent linear, branched, or cyclic alkyl, alkenyl, oxoalkyl, or oxoalkenyl groups having 1 to 12 carbon atoms; substituted or unsubstituted aryl groups having 6 to 20 carbon atoms; or aralkyl or aryloxoalkyl groups having 7 to 12 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with alkoxy groups, etc. Furthermore, R 205 With R 206 It can also form a ring, and when a ring is formed, R 205 R 206 These represent alkylene groups having 1 to 6 carbon atoms. A- represents a non-nucleophilic relative ion. R 208 R 209 R 210 R 211 and R 204 R 205 R 206 R 207 Similarly, it can also be a hydrogen atom. R 208 With R 209 R 208 With R 209 With R 210 It can also form a ring, and when a ring is formed, R 208 and R 209 and R 208 and R 209 and R 210 Indicates an alkylene group having 3 to 10 carbon atoms.

[0214] The above R 204 R 205 R 206 R 207 R 208 R 209 R 210 R 211Alkyl groups can be the same as or different from each other. Specifically, examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-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 oxoalkyl groups include: 2-oxocyclopentyl, 2-oxocyclohexyl, etc., and also include: 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, 2-(4-methylcyclohexyl)-2-oxoethyl, 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. Aryloxoalkyl groups can be listed as: 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, 2-(2-naphthyl)-2-oxoethyl, etc., 2-aryl-2-oxoethyl, etc.

[0215] Non-nucleophilic relative ions of A- include: hydroxide ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleic acid ion, stearate ion, linoleic acid ion, and linolenic acid ion. Monovalent ions include: 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, chlorate 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, 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, sulfate ions, etc.

[0216] Alkali metal salts include: hydroxides, formates, acetates, propionates, butyrates, valerates, hexanoates, heptanoates, octanoates, nonanoates, decanoates, oleates, stearates, linoleic acid oleate, linolenic acid alpha-linolenic acid oleate, benzoates, phthalates, isophthalates, terephthalates, salicylates, trifluoroacetates, monochloroacetates, dichloroacetates, trichloroacetates, etc. (monovalent salts); and monovalent or divalent oxalates, malonates, methylmalonate, ethylmalonate, propylmalonate, butylmalonate, dimethylmalonate, diethylmalonate, succinate, methylsuccinate, glutarate, adipate, iconate, maleate, fumarate, citrate, citrate, carbonates, etc.

[0217] (Sumine salt (Xc-1))

[0218] Specifically, sulfonium salts (Xc-1) can be listed as follows: triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionate, triphenylsulfonium butyrate, triphenylsulfonium benzoate, triphenylsulfonium phthalate, triphenylsulfonium isophthalate, triphenylsulfonium terephthalate, triphenylsulfonium salicylate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium monochloroacetate, triphenylsulfonium dichloroacetate, triphenylsulfonium trichloroacetate, triphenylsulfonium hydroxide, triphenylsulfonium nitrate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium oxalate, triphenylsulfonium malonate, and triphenylsulfonium methylmalonate. Triphenylsulfonium methylsulfonium, triphenylsulfonium ethylmalonic acid, triphenylsulfonium propylmalonic acid, triphenylsulfonium butylmalonic acid, triphenylsulfonium dimethylmalonic acid, triphenylsulfonium diethylmalonic acid, triphenylsulfonium succinate, triphenylsulfonium methylsuccinate, triphenylsulfonium glutarate, triphenylsulfonium adipic acid, triphenylsulfonium iconate, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylsulfonium citrate, triphenylsulfonium citrate, triphenylsulfonium carbonate, bis(triphenylsulfonium oxalate), bis(triphenylsulfonium maleate), bis(triphenylsulfonium fumarate), bis(triphenylsulfonium citrate), bis(triphenylsulfonium citrate), bis(triphenylsulfonium citrate), bis(triphenylsulfonium carbonate), etc.

[0219] (Fossilized Salt (Xc-2))

[0220] 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.

[0221] (phosphonium salt (Xc-3))

[0222] 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.

[0223] (Ammonium salt (Xc-4))

[0224] 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.

[0225] (alkali metal salts)

[0226] 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.

[0227] [Regarding the curing catalyst (Xc), there are thermosetting polysiloxanes with ammonium salts, sulfonium salts, phosphonium salts, and ferrophosphate salts as part of their structure.]

[0228] The crosslinking catalyst (Xc) for polymerization in this invention can be exemplified by a thermosetting polysiloxane (Xc-10) having ammonium salt, sulfonium salt, phosphonium salt, or monazite salt as part of its structure.

[0229] The raw materials used to manufacture (Xc-10) used herein may be compounds represented by the following general formula (Xm).

[0230] R1AA1R2AA2R3AA3Si(OR0A)(4-A1-A2-A3)(Xm)

[0231] 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, sulfonium 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.

[0232] Here, R0A can be exemplified as: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl.

[0233] (Hydrolytic silicon compounds with sulfonium salts as part of their structure (Xm-1))

[0234] For example, hydrolyzable silicon compounds having a sulfonium salt as part of their structure can be exemplified by the following general formula (Xm-1).

[0235] [Chemistry 18]

[0236]

[0237] In the formula, R SA1 R SA2 These groups represent linear, branched, or cyclic alkyl, alkenyl, oxoalkyl, or oxoalkenyl 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, wherein some or all of the hydrogen atoms in these groups may be substituted with alkoxy, amino, alkylamino, or halogen atoms. Furthermore, R... SA1 With R SA2 It can also form a ring with the sulfur atoms it is bonded to, and when forming a ring, R SA1 R SA2 These represent alkylene groups having 1 to 6 carbon atoms, respectively. R SA3 It is a straight-chain, branched, or cyclic alkylene or alkenylene group with 1 to 20 carbon atoms, or a 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 by alkoxy, amino, alkylamino, etc. R SA1 R SA2 R SA3 It may also contain oxygen or nitrogen atoms along its chain or ring.

[0238] In addition, in the above general formula (Xm-1), (Si) is recorded to indicate the bonding position with Si.

[0239] X- can be listed as follows: 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-tert-butylbenzoic 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.

[0240] The cation moiety of the compound represented by the above general formula (Xm-1) is specifically exemplified by the following ions (X- is the same as above).

[0241] [Chemistry 19]

[0242]

[0243] (Hydrolytic silicon compounds with monazine salts as part of their structure)

[0244] For example, hydrolyzable silicon compounds having monazite as part of their structure can be exemplified by the following general formula (Xm-2).

[0245] [Chemistry 20]

[0246]

[0247] In the formula, R IA1 This refers to a linear, branched, or cyclic alkyl, alkenyl, oxoalkyl, or oxoalkenyl group having 1 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; or an aralkyl or aryloxoalkyl group having 7 to 20 carbon atoms, wherein some or all of the hydrogen atoms in these groups may be substituted with alkoxy, amino, alkylamino, or halogen atoms. Furthermore, R... IA1 With R IA2 They can also form rings together with the nitrogen atoms they are bonded to, and when forming rings, R IA1 R IA2 These represent alkylene groups having 1 to 6 carbon atoms, respectively. R IA2 It is a straight-chain, branched, or cyclic alkylene or alkenylene group with 1 to 20 carbon atoms, or a 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 by alkoxy, amino, alkylamino, etc. RIA1 ~R IA2 It may also contain oxygen or nitrogen atoms along its chain or ring.

[0248] Furthermore, in the above general formula (Xm-2), (Si) is used to indicate the bonding position with Si. X- is as described above.

[0249] The cation moiety of the compound represented by the above general formula (Xm-2) is specifically exemplified by the following ions (X- is the same as above).

[0250] [Chemistry 21]

[0251]

[0252] (Hydrolytic silicon compounds with phosphonium salts as part of their structure)

[0253] For example, hydrolyzable silicon compounds having phosphonium salts as part of their structure can be exemplified by the following general formula (Xm-3).

[0254] [Chemistry 22]

[0255]

[0256] In the formula, R PA1 R PA2 R PA3 These groups represent linear, branched, or cyclic alkyl, alkenyl, oxoalkyl, or oxoalkenyl groups with 1 to 20 carbon atoms, substituted or unsubstituted aryl groups with 6 to 20 carbon atoms, or aralkyl or aryloxoalkyl groups with 7 to 20 carbon atoms, wherein some or all of the hydrogen atoms in these groups may be substituted with alkoxy, amino, alkylamino, or halogen atoms. Furthermore, R... PA1 With R PA2 They can also form rings together with the phosphorus atoms they are bonded to, and when forming rings, R PA1 R PA2 These represent alkylene groups having 1 to 6 carbon atoms, respectively. R PA4 It is a straight-chain, branched, or cyclic alkylene or alkenylene group with 1 to 20 carbon atoms, or a 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 by alkoxy, amino, alkylamino, etc. R PA1 ~R PA4 It may also contain oxygen or nitrogen atoms along its chain or ring.

[0257] Furthermore, in the above general formula (Xm-3), (Si) is used to indicate the bonding position with Si. X- is as described above.

[0258] The cation moiety of the compound represented by the above general formula (Xm-3) is specifically exemplified by the following ions (X- is the same as above).

[0259] [Chemistry 23]

[0260]

[0261] (Hydrolytic silicon compounds with ammonium salts as part of their structure)

[0262] For example, hydrolyzable silicon compounds having an ammonium salt as part of their structure can be exemplified by the following general formula (Xm-4).

[0263] [Chemistry 24]

[0264]

[0265] In the formula, R NA1 R NA2 R NA3 These represent monovalent organic groups, namely, a hydrogen atom, a straight-chain, branched, or cyclic alkyl, alkenyl, oxoalkyl, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl or aryloxyalkyl group having 7 to 20 carbon atoms, wherein some or all of the hydrogen atoms of these groups may be substituted by alkoxy, amino, alkylamino, etc. Also, R NA1 With R NA2 They can also form rings together with the nitrogen atoms they are bonded to, and when forming rings, R NA1 R NA2 R represents an alkylene group having 1 to 6 carbon atoms, or a nitrogen-containing cyclic heterocycle or heteroaromatic ring. NA4 It is a linear, branched, or cyclic alkylene or alkenylene group having 1 to 23 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 29 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by alkoxy, amino, alkylamino, etc. R NA1 With R NA2 R NA1 With R NA4 When a cyclic structure is formed and further contains unsaturated nitrogen, n NA3 =0, except for n NA3 =1.

[0266] Furthermore, in the above general formula (Xm-4), (Si) is used to indicate the bonding position with Si. X- is as described above.

[0267] The cation moiety of the compound represented by the above general formula (Xm-4) is specifically exemplified by the following ions (X- is the same as above).

[0268] [Chemistry 25]

[0269]

[0270] [Chemistry 26]

[0271]

[0272] [Chemistry 27]

[0273]

[0274] [Chemistry 28]

[0275]

[0276] [Chemistry 29]

[0277]

[0278] [Chemistry 30]

[0279]

[0280] [Chemistry 31]

[0281]

[0282] (Organic solvents)

[0283] The silicon-containing photoresist lower film composition of the present 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.

[0284] 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, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0285] (water)

[0286] Water can also be added to the silicon-containing photoresist underlayer composition of the present invention. Adding water hydrates the polysiloxane compounds in the composition, thus improving photolithography performance. The water content in the solvent component of the silicon-containing photoresist underlayer 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 photoresist underlayer film exhibits good uniformity and does not experience pinholes.

[0287] The aforementioned silicon-containing photoresist lower film composition preferably contains a crosslinking catalyst (Xc) for siloxane polymerization, an alcohol-based organic solvent, and water.

[0288] (High-boiling-point solvent)

[0289] Furthermore, the silicon-containing photoresist 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-diacetoxyethane, 1-acetoxy-2-methoxyethane, 1,2-diacetoxypropane, 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.

[0290] 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 as the base polymer.

[0291] [Other ingredients]

[0292] (Organic acids)

[0293] To improve the stability of the silicon-containing photoresist lower film composition of the present invention, it is preferable to add an organic acid with a carbon number of 1 to 30, which has a monovalent or divalent or higher oxidation state. 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, alpha-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 preferable. Furthermore, to maintain stability, two or more acids may be used in combination. The amount added is 0.001 to 25 parts by mass relative to 100 parts by mass of silicon contained in the composition, preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 5 parts by mass.

[0294] (Photoacid generator)

[0295] The present invention may also add a photoacid generating agent to the silicon-containing photoresist underlayer film composition. Specifically, the photoacid generating agent used in the present invention may be the material described in paragraphs (0160) to (0179) of Japanese Patent Application Publication No. 2009-126940.

[0296] (A compound having both an anionic and a cationic portion in one molecule (photoacid generator (P-O)))

[0297] In addition, the present invention may also contain one or more compounds (photoacid generators) represented by the following general formula (P-O) having an anionic and a cationic portion in one molecule.

[0298] [Chemistry 32]

[0299]

[0300] Here, R 300 R is a divalent organic group substituted with one or more fluorine atoms. 301 and R 302 Each of the following can be independently represented as a linear, branched, or cyclic monovalent hydrocarbon group with 1 to 20 carbon atoms that can be substituted for or have heteroatoms inserted. 303 This refers to a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms that can be substituted for or insert heteroatoms. Also, R 301 With R 302 、or R 301 With R 303 They can also bond with each other and form a ring together with the sulfur atoms in the formula. L 304It represents a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms, which may be single-bonded or may be substituted with heteroatoms and may also have heteroatoms inserted.

[0301] Such a compound (photoacid generator) can be combined with the thermosetting silicon-containing material of the present invention to obtain a resist underlayer film that contributes to the rectangularization of the cross-sectional shape while maintaining the LWR of the upper resist.

[0302] In the above general formula (P-0), R 300 A divalent organic group substituted with one or more fluorine atoms. Examples of such divalent organic groups include linear, branched, or cyclic divalent hydrocarbon groups such as alkylene, alkenyl, and aryl groups having 1 to 20 carbon atoms. R 300 The specific structures can be listed below.

[0303] [Chemistry 33]

[0304]

[0305] Furthermore, in the above formula, (SO3-) is used to indicate the bonding position with the SO3- group in the above general formula (P-0). Also, (R 350 ) is to indicate the interval L between the cation portion and the above general formula (P-0). 304 Bonded to R 300 It is recorded based on the location of the bonds in the part.

[0306] R 301 and R 302Each of these can be independently a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, which can be substituted with or have heteroatoms inserted. Examples include alkyl, alkenyl, aryl, and aralkyl. Examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-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 oxoalkyl groups include: 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxopropyl, 2-oxoethyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, 2-(4-methylcyclohexyl)-2-oxoethyl, 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. Arylalkyl groups can be listed as: benzyl, 1-phenylethyl, 2-phenylethyl, etc. Examples of aryl oxoalkyl groups include: 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, 2-(2-naphthyl)-2-oxoethyl, etc. Also, R... 301 With R 302 They can also bond with each other and form a ring together with the sulfur atoms in the formula. In this case, the groups represented by the following formulas can be listed.

[0307] [Chemistry 34]

[0308]

[0309] Dashed lines represent bonds.

[0310] In the above general formula (P-0), R 303 R represents a linear, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms that can be substituted by heteroatoms and can also have heteroatoms inserted. 303Specifically, examples include: straight-chain alkyl diyl groups such as methylene, ethylene, 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 phenylene and naphthylene. Furthermore, some of the hydrogen atoms in these groups can be replaced by alkyl groups such as methyl, ethyl, propyl, n-butyl, and tert-butyl. 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. Also, R 301 With R 303 They can also bond with each other and form a ring together with the sulfur atoms in the formula. In this case, the groups represented by the following formulas can be listed.

[0311] [Chemistry 35]

[0312]

[0313] Dashed lines represent bonds.

[0314] In the above general formula (P-0), L 304 L represents a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms, which may be single-bonded or can be substituted with heteroatoms and may also have heteroatoms inserted. 304 Specifically, examples include: straight-chain alkyl diyl groups such as methylene, ethylene, 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 phenylene and naphthylene. Furthermore, some of the hydrogen atoms in these groups can be substituted to form alkyl groups such as methyl, ethyl, propyl, n-butyl, and tert-butyl. 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.

[0315] The compound (photoacid generator) represented by the above general formula (P-0) should preferably be represented by the following general formula (P-1).

[0316] [Chemistry 36]

[0317]

[0318] In the above general formula (P-1), X 305 X 306 Each of the following can be independently represented: a hydrogen atom, a fluorine atom, or a trifluoromethyl atom, but not all of them can be hydrogen atoms. 307 Represents integers from 1 to 4. R 301 R 302 R 303 and L 304 As stated above.

[0319] The photoacid generator represented by the above general formula (P-0) is preferably represented by the following general formula (P-1-1).

[0320] [Chemistry 37]

[0321]

[0322] In the above general formula (P-1-1), R 308 R 309 and R 310 Each group represents a single-chain, branched, or cyclic monovalent hydrocarbon group with 1 to 20 carbon atoms, independently representing a hydrogen atom or possibly containing a heteroatom. Examples include: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, oxanorbornel, tricyclic [5.2.1.0] 2,6 Decyl, adamantyl, etc. Furthermore, a portion of the hydrogen atom in these groups can be substituted with heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and oxygen, sulfur, or nitrogen atoms can also be inserted. This can result in the formation or insertion of hydroxyl, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride, or haloalkyl groups. Methyl, methoxy, tert-butyl, and tert-butoxy groups are preferred.

[0323] In the above general formula (P-1-1), n 308 and n 309 These represent integers from 0 to 5, preferably 0 or 1. 310 Represents integers from 0 to 4, preferably 0 or 2. L 304 X 305 X 306 n307 As stated above.

[0324] The compound (photoacid generator) represented by the above general formula (P-0) is preferably represented by the following general formula (P-1-2).

[0325] [Chemistry 38]

[0326]

[0327] In the above general formula (P-1-2), A 311 Represents a hydrogen atom or a trifluoromethyl group. R 308 R 309 R 310 n 308 n 309 n 310 L 304 As stated above.

[0328] The photoacid generators represented by the above general formulas (P-0), (P-1), (P-1-1), and (P-1-2) can be more specifically illustrated by the structures shown below. However, the above photoacid generators are not limited to these.

[0329] [Chemistry 39]

[0330]

[0331] [Chemistry 40]

[0332]

[0333] [Chemistry 41]

[0334]

[0335] [Chemistry 42]

[0336]

[0337] [Chemistry 43]

[0338]

[0339] [Chemistry 44]

[0340]

[0341] The amount of the compound represented by the above general formula (P-O) added relative to 100 parts by weight of the 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 areas of the upper resist layer can be reduced, and a pattern with a small LWR can be formed.

[0342] (Stabilizer)

[0343] Furthermore, the present invention allows the addition of a stabilizer to the silicon-containing photoresist underlayer film composition. The stabilizer can be a monovalent or divalent alcohol 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 photoresist underlayer film formation composition. The amount of stabilizer added is preferably 0.001 to 50 parts by weight, and more preferably 0.01 to 40 parts by weight, relative to 100 parts by weight of the thermally crosslinked polysiloxane.

[0344] (surfactant)

[0345] Furthermore, the present invention can incorporate a surfactant into the composition as needed. Specifically, such a surfactant can be the material 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.

[0346] The aforementioned silicon-containing photoresist underlayer film, in the micro-patterning process using the multilayer photoresist method in the semiconductor device manufacturing step, 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.

[0347] When the aforementioned silicon-containing photoresist underlayer film has carboxyl groups protected by acid-instable groups, the acid-instable groups can be thermally decomposed during the baking step of forming the silicon-containing photoresist underlayer film, and the carboxyl groups can appear on the surface of the silicon-containing photoresist underlayer film.

[0348] When the aforementioned silicon-containing photoresist underlayer film has carboxyl groups protected by acid-instable groups, the silicon-containing photoresist underlayer 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.

[0349] The high adhesion between the aforementioned silicon-containing photoresist underlayer and the photoresist film stems from the presence of carboxyl groups in the silicon-containing photoresist underlayer after the baking step. By using the photoresist composition described later, and through baking after coating, the carboxyl groups on the surface of the silicon-containing photoresist underlayer and the carboxyl groups of the carboxyl-containing compounds contained in the photoresist composition cross-link through the supraatomic iodine compound. Since the photoresist composition described later is positive, cross-linking occurs between the unexposed pattern and the surface of the adhesive film, thereby enabling it to withstand stress during development and suppressing the collapse of line and spacing patterns, which is useful in the fabrication of high aspect ratio photoresist patterns. On the other hand, in contact hole patterns, the high adhesion between the photoresist film and the silicon-containing photoresist underlayer prevents developer from penetrating between the photoresist film and the photoresist underlayer, thus preventing swelling and forming excellent contact hole patterns for CDUs.

[0350] [Resist film]

[0351] The resist film used in this invention will be described.

[0352] The aforementioned resist film is obtained from a resist composition containing a predetermined superatomic iodine compound, a carboxyl-containing compound, and a solvent.

[0353] [Supramatomic iodine compounds]

[0354] The aforementioned superatomic iodine compounds are tricoordinate superatomic iodine compounds represented by formulas (7), (8) or (9).

[0355] [Chemistry 45]

[0356]

[0357] 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.

[0358] In equations (7) to (9), R 11 ~R 18 Each group consists independently of a halogen atom, or may contain heteroatoms, and is a hydrocarbon group with 1 to 10 carbon atoms. Also, R 11 and R 12 R13 and R 14 R 15 and R 16 、or R 17 and R 18 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0359] R 11 ~R 18 Examples of halogen atoms that can be represented include: fluorine, chlorine, bromine, and iodine atoms. R 11 ~R 18 The hydrocarbon groups representing 1 to 10 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 10 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms, such as decyl and adamantyl; alkenyl groups such as vinyl and allyl; aryl groups with 6 to 10 carbon atoms, such as phenyl and naphthyl; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.] 11 ~R 18 It should preferably be a hydrocarbon group with 1 to 4 carbon atoms.

[0360] In equations (7) to (9), R 21 ~R 24 Each R is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms. When n2 is 2 or more, each R 21 They can be the same or different, and there are multiple Rs. 21 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R 22 They can be the same or different, and there are multiple Rs. 22 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R 23 They can be the same or different, and there are multiple Rs. 23They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R 24 They can be the same or different, and there are multiple Rs. 24 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0361] R 21 ~R 24 Specific examples of halogen atoms that can be represented include: fluorine, chlorine, bromine, and iodine atoms. R 21 ~R 24 The hydrocarbon groups representing 1 to 40 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl, adamantyl, and adamantylmethyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and a portion of the -CH2- group in the aforementioned hydrocarbon groups may also be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, these groups may contain hydroxyl, cyano, halogen, carbonyl, ether, thioether, ester, sulfonate, carbonate, carbamate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), etc.]

[0362] In equation (9), R 25 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 25 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl bond. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 24 and R 25 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0363] R 25The (n8) valence hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned (n8) valence hydrocarbon group is obtained by removing (n8) hydrogen atoms from a hydrocarbon. Examples of such hydrocarbons include: alkanes with 1-40 carbon atoms, alkenes with 2-40 carbon atoms, alkynes with 2-40 carbon atoms, cyclic saturated hydrocarbons with 3-40 carbon atoms, cyclic unsaturated hydrocarbons with 3-40 carbon atoms, and aromatic hydrocarbons with 6-40 carbon atoms.

[0364] Specific examples of alkanes with 1 to 40 carbon atoms include: methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[0365] Specific examples of the aforementioned alkenes with 2 to 40 carbon atoms include: ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and their structural isomers.

[0366] 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.

[0367] Specific examples of the aforementioned cyclic saturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norcamphene, etc.

[0368] Specific examples of the aforementioned cyclic unsaturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropylene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norcamphene.

[0369] Specific examples of aromatic hydrocarbons with 6 to 40 carbon atoms mentioned above include: benzene, naphthalene, biphenyl, etc.

[0370] R 25 The (n8) valence heterocyclic group 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.

[0371] The hydrogen atoms of the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group 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 (n8) valence 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, sulfonyl lactone rings, and carboxylic anhydrides (-C(=O)-OC(=O)-), etc.

[0372] Specific examples of superatomic iodine compounds represented by equation (7) are listed below, but are not limited thereto.

[0373] [Chemistry 46]

[0374]

[0375] [Chemistry 47]

[0376]

[0377] [Chemistry 48]

[0378]

[0379] [Chemistry 49]

[0380]

[0381] [Transformation 50]

[0382]

[0383] [Chemistry 51]

[0384]

[0385] [Chemistry 52]

[0386]

[0387] [Chemistry 53]

[0388]

[0389] [Chemistry 54]

[0390]

[0391] [Chemistry 55]

[0392]

[0393] [Chemistry 56]

[0394]

[0395] [Chemistry 57]

[0396]

[0397] Specific examples of superatomic iodine compounds represented by equation (8) are listed below, but are not limited thereto.

[0398] [Chem.58]

[0399]

[0400] [Chemistry 59]

[0401]

[0402] [Transformation 60]

[0403]

[0404] [Chemistry 61]

[0405]

[0406] Specific examples of superatomic iodine compounds represented by equation (9) are listed below, but are not limited thereto.

[0407] [Chemistry 62]

[0408]

[0409] [Chemistry 63]

[0410]

[0411] [Chemistry 64]

[0412]

[0413] [Chemistry 65]

[0414]

[0415] [Chemistry 66]

[0416]

[0417] [Chemistry 67]

[0418]

[0419] The aforementioned carboxyl-containing compounds are preferably polymers containing repeating units represented by formula (10) or compounds represented by formula (11).

[0420] [Chemistry 68]

[0421]

[0422] In equation (10), R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A It is a single bond, phenylene, naphthylene, or *-C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0423] In equation (11), p is 1, 2, 3 or 4.

[0424] In equation (11), R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms; when p is 2, R 31 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing heteroatoms, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be replaced by a group containing heteroatoms.

[0425] In equation (11), R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group can be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group can also be replaced by a group containing a heteroatom. When p is 2, 3 or 4, each R 32 They can be the same or different.

[0426] R 31 The p-valent hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. The aforementioned p-valent hydrocarbon group is obtained by removing p hydrogen atoms from a hydrocarbon. Examples of such hydrocarbons include: alkanes with 1-40 carbon atoms, alkenes with 2-40 carbon atoms, alkynes with 2-40 carbon atoms, cyclic saturated hydrocarbons with 3-40 carbon atoms, cyclic unsaturated hydrocarbons with 3-40 carbon atoms, and aromatic hydrocarbons with 6-40 carbon atoms.

[0427] The aforementioned alkanes with 1 to 40 carbon atoms include: methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and their structural isomers.

[0428] The aforementioned alkenes with 2 to 40 carbon atoms include: ethylene, propylene, butene, pentene, hexene, hepten, octene, nonene, decene, and their structural isomers.

[0429] 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.

[0430] Examples of cyclic saturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, norcamphene, etc.

[0431] Examples of cyclic unsaturated hydrocarbons with 3 to 40 carbon atoms include: cyclopropylene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norcamphene.

[0432] Aromatic hydrocarbons with 6 to 40 carbon atoms mentioned above include: benzene, naphthalene, biphenyl, etc.

[0433] R 31 The p-valent heterocyclic group represents a group obtained by removing p hydrogen atoms from a heterocyclic compound. Examples of such heterocyclic compounds include furan, pyridine, pyrazole, and tetrahydrothiazole.

[0434] 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, in the aforementioned p-valent hydrocarbon groups, a portion of the -CH2- group can be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms, resulting in the presence of carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, carbamate bonds, lactone rings, sulopentalide rings, and carboxylic anhydrides (-C(=O)-OC(=O)-), etc.

[0435] R 32 The derivatized hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include: methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1, Alkyl groups with 1 to 20 carbon atoms, such as 11-diyl and dodecane-1,12-diyl; cyclic saturated alkylene groups with 3 to 20 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norcamphenediyl, and adamantanediyl; unsaturated aliphatic alkylene groups with 2 to 20 carbon atoms, such as vinylene and propylene-1,3-diyl; aryl groups with 6 to 20 carbon atoms, such as phenylene and naphthylene; and groups obtained by combining them. Furthermore, some or all of the hydrogen atoms in the aforementioned alkylene group may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and a portion of the -CH2- constituting the aforementioned alkylene group may also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, carbamate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides, etc.

[0436] 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 high molecular weight, strong resist film, which is ideal considering etching resistance and developer resistance.

[0437] In the carboxyl-containing polymers represented by formula (10), specific examples of the repeating carboxyl-containing units represented by formula (10) are listed below, but are not limited thereto. Additionally, in the following formula, R... A Same as above.

[0438] [Chemistry 69]

[0439]

[0440] [Chemistry 70]

[0441]

[0442] The carboxylic acid compounds represented by formula (11) can be listed below, but are not limited thereto.

[0443] [Chemistry 71]

[0444]

[0445] [Chemistry 72]

[0446]

[0447] [Chemistry 73]

[0448]

[0449] [Chemistry 74]

[0450]

[0451] [Chemistry 75]

[0452]

[0453] [Chemistry 76]

[0454]

[0455] A carboxyl-containing polymer containing a repeating unit 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 only repeating units with carboxyl groups are present. 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.

[0456] Specific examples of the aforementioned repeating units may be listed below, but are not limited to these. Additionally, in the following formula, R... A As mentioned above, X B They are either -CH2- or -O-, respectively.

[0457] [Chemistry 77]

[0458]

[0459] [Chemistry 78]

[0460]

[0461] [Chemistry 79]

[0462]

[0463] [Chemistry 80]

[0464]

[0465] [Chemistry 81]

[0466]

[0467] [Chemistry 82]

[0468]

[0469] [Chemistry 83]

[0470]

[0471] [Chemistry 84]

[0472]

[0473] [Chemistry 85]

[0474]

[0475] [Chemistry 86]

[0476]

[0477] [Chemistry 87]

[0478]

[0479] [Chemistry 88]

[0480]

[0481] [Chemistry 89]

[0482]

[0483] [Chemistry 90]

[0484]

[0485] [Chemistry 91]

[0486]

[0487] [Chemistry 92]

[0488]

[0489] [Chemistry 93]

[0490]

[0491] [Chemistry 94]

[0492]

[0493] [Chemistry 95]

[0494]

[0495] [Chemistry 96]

[0496]

[0497] [Chemistry 97]

[0498]

[0499] [Chem. 98]

[0500]

[0501] [Chemistry 99]

[0502]

[0503] [Chemistry 100]

[0504]

[0505] [Chemistry 101]

[0506]

[0507] [Chemistry 102]

[0508]

[0509] [Chemistry 103]

[0510]

[0511] [Chemistry 104]

[0512]

[0513] [Chemistry 105]

[0514]

[0515] [Chemistry 106]

[0516]

[0517] In the aforementioned resist composition, the molar 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 molar ratio of the superatomic iodine compound to the repeating carboxylic acid units in the aforementioned polymer) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30. The aforementioned superatomic iodine compound can be used alone or in combination with two or more compounds having different compositional ratios, Mw, and / or Mw / Mn. The aforementioned carboxyl-containing polymer can be used alone or in combination with two or more compounds having different compositional ratios, Mw, and / or Mw / Mn.

[0518] In the aforementioned carboxyl-containing polymers, the molar ratio of carboxyl-containing repeating units to other repeating units should preferably be 10:90 to 90:10, more preferably 15:85 to 85:15, and even more preferably 20:80 to 80:20.

[0519] The weight-average molecular weight (Mw) of the aforementioned carboxyl-containing polymers is preferably between 1,000 and 500,000, and more preferably between 3,000 and 100,000. Furthermore, in this invention, Mw is the converted value of polystyrene determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0520] 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.

[0521] Examples of methods for synthesizing the aforementioned carboxyl-containing polymers include: polymerizing a monomer that provides the aforementioned repeating unit in an organic solvent by adding a free radical polymerization initiator and heating it.

[0522] Specific examples of organic solvents used in the polymerization reaction include: toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, cyclopentanone, cyclohexanone, methyl ethyl ketone (MEK), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), etc. Specific examples of polymerization initiators include: 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis(2,4-dimethylpentanonitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, lauroyl peroxide, etc. The amount of the aforementioned polymerization initiator added, relative to the total amount of monomers used to polymerize, should preferably be 0.01–25 mol%. The reaction temperature should preferably be 50–150 °C, preferably 60–100 °C. The reaction time should be 2 to 24 hours, but from the perspective of production efficiency, 2 to 12 hours is better.

[0523] 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 proceed and generate ultra-high molecular weight polymers due to the generation of free radicals from the initiator during the standby time, from a quality management 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 it, should preferably be 0.01 to 20 mol%.

[0524] 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.

[0525] (solvent)

[0526] The aforementioned resist composition contains a solvent. There are no particular limitations on the solvent if it is capable of dissolving the aforementioned superatomic iodine compounds, carboxyl-containing compounds, and other components described below, and can form 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, etc. Ethers such as glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; carboxylic acids such as formic acid, acetic acid, and propionic acid; lactones such as γ-butyrolactone; and their mixed solvents, etc.

[0527] In the aforementioned resist composition, the content of the aforementioned solvent is preferably such that the concentration of the solid component in the resist composition is 0.1% to 20% by mass, more preferably 0.1% to 15% by mass, and even more preferably 0.1% to 10% by mass. Furthermore, in this invention, the solid component refers to the total components of the resist composition other than the solvent. The aforementioned solvent may be used alone or in combination of two or more.

[0528] (surfactant)

[0529] The aforementioned resist composition may also contain a surfactant. The surfactant is preferably a fluorinated and / or polysiloxane surfactant. Examples of such surfactants include those described in paragraph

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

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

[0530] When the aforementioned resist composition contains the aforementioned surfactant, its content in the total solid components should preferably be 0.0001 to 2% by mass. The aforementioned surfactant may be used alone or in combination of two or more.

[0531] (Free radical scavenger)

[0532] The aforementioned resist composition may also contain more free radical scavengers. By adding free radical scavengers, the photoresist reaction during optical lithography can be controlled and the sensitivity adjusted.

[0533] 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.

[0534] When the aforementioned corrosion resist composition contains the aforementioned free radical scavenger, its content in the total solid components should preferably be 0.01 to 10% by mass. The aforementioned free radical scavenger can be used alone or in combination of two or more.

[0535] (Cross-linking agent)

[0536] The aforementioned resist composition may also contain more crosslinking agents. By adding crosslinking agents, the crosslinking reaction during optical lithography can be promoted, the glass transfer points of the pattern can be improved, and patterns with excellent fine line resolution can be obtained.

[0537] The aforementioned crosslinking agents can include compounds with carbon-carbon unsaturated bonds as functional groups, such as vinyl, (meth)acrylate, allyl, alkynyl, and aromatic rings. Specifically, compounds with vinyl groups can include: chain alkenes, branched alkenes, cyclic alkenes, etc., which may also have substituents. Compounds with (meth)acrylate groups can include: acrylic acid, methacrylic acid, acrylates, methacrylates, etc., which may also have substituents. Compounds with allyl groups can include: allyl alcohols, allyl ethers, allyl esters, allyl amides, allylamines, isocyanurates containing allyl groups, etc. Compounds with alkynyl groups can include: chain alkynes, branched alkynes, cyclic alkynes, alkynyl alcohols, alkynyl ethers, alkynyl esters, alkynyl amides, alkynylamines, isocyanurates containing alkynyl groups, etc., which may also have substituents. Compounds containing aromatic rings include: aromatic hydrocarbons, heteroaromatic hydrocarbons, styrene, stilbene, phenylacetylene, acenaphthene, chalcone, etc., which may also contain substituents. Crosslinking agents may contain only one or more of the above functional groups. The number of the above functional groups in the crosslinking agent is preferably 1 or more and 10 or less, and more preferably 2 or more and 8 or less.

[0538] When the aforementioned resist composition contains the aforementioned crosslinking agent, its content in the total solid components should preferably be 0.01 to 50% by mass. The aforementioned crosslinking agent can be used alone or in combination of two or more.

[0539] (Photopolymerization initiator)

[0540] When the aforementioned resist composition contains the aforementioned crosslinking agent, it may also contain a photopolymerization initiator. The photopolymerization initiator can generate free radicals by irradiation with high-energy rays and promote the crosslinking of the aforementioned crosslinking agent.

[0541] Specific examples of the aforementioned photopolymerization initiators include: benzophenone, methyl O-benzoylbenzoate, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, and other benzophenone derivatives; 2,2-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)-benzyl]-phenyl}-2-methylpropane-1-one, methyl phenylglyoxylate, and other acetophenone derivatives; thioxanthone, 2-methylthioxanthone, etc. Thioxanone derivatives such as 2-isopropylthioxanone, 4-isopropylthioxanone, 2-chlorothioxanone, and diethylthioxanone; benzoyl derivatives such as benzoyl, benzoyl dimethyl ketal, and benzoyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin 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-acetyloxime); 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-methylpropanoyl)-benzyl]phenyl}-2-methylpropane. Ketone compounds; α-aminoalkylphenyl ketone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butane-1-one; phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and 2,4,6-trimethylbenzoyl diphenylphosphine oxide; and titanium cadmium compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium.

[0542] When the aforementioned photopolymerization initiator is present in the aforementioned resist composition, its content in the total solids component is preferably 0.1–10% by mass, more preferably 0.1–5% by mass, and optimally 0.1–1% by mass. If it is 0.1% by mass or higher, the blending effect can be fully obtained.

[0543] The aforementioned resist composition, as described above, contains superatomic iodine compounds and carboxyl-containing compounds as main components, but does not contain polymers containing acid-instable groups or photoacid generators as found in known chemically amplified resist compositions. However, the resist composition of the present invention, in particular, can form positive patterns in which the exposed portion is soluble in the developer when exposed by EB or EUV exposure. The mechanism is not fully elucidated, but is speculated to be as follows.

[0544] 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, 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-iodonaphthyl diacetate, which is a superatomic iodine compound, is mixed with a carboxyl-containing compound, and the resulting low-boiling acetic acid is removed, ligand exchange will be completed. Here, the carboxyl-containing compound becomes a cross-linked polymer through the superatomic iodine compound.

[0545] The polymer 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 resist film.

[0546] In the resist film obtained from the aforementioned resist composition, the main component, a superatomic iodine compound, decomposes under light, thereby changing its polarity and forming a pattern using a development step. The mechanism is not fully understood, but it is hypothesized, for example, as follows.

[0547] The resist film obtained from the aforementioned resist composition contains polymers bonded by superatomic iodine compounds during film formation. However, these polymers decompose under light, transforming into monovalent iodine compounds. Simultaneously, the bonds between carboxyl-containing compounds and superatomic 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.

[0548] Based on the foregoing, the aforementioned resist composition can be considered a non-chemically amplified resist composition. This resist composition does not require polymers containing acid-labile groups or photoacid generators, as is the case with known chemically amplified resist compositions. Therefore, adverse effects caused by acid diffusion (such as image blurring) will not occur, and fine patterns can be resolved.

[0549] The aforementioned resist composition is particularly effective in EUV lithography. This is due to the presence of iodine atoms with high absorption capacity for EUV light. In other words, it reduces shot noise and achieves higher resolution and lower LWR.

[0550] 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, poor storage stability, and defects caused by etching residues due to the presence of metal elements. On the other hand, the resist composition of the present invention does not use metal elements, thus 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 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 is arguably more useful than metal resists.

[0551] The thickness of the aforementioned resist film should preferably be 10–70 nm, with 20–50 nm being even better.

[0552] [Resist underlayer film]

[0553] The present invention provides a laminate having a photoresist underlayer between the aforementioned substrate and a silicon-containing photoresist underlayer.

[0554] The aforementioned resist underlayer film can be used in known processes for fine patterning using 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).

[0555] The thickness of the lower layer of the aforementioned resist should preferably be 40–200 nm, with 40–150 nm being even better.

[0556] The aforementioned photoresist underlayer film is preferably a photoresist underlayer film obtained by using a solution-like composition for forming a photoresist underlayer film, or a photoresist underlayer film formed by CVD or ALD methods.

[0557] [Manufacturing method of laminated bodies]

[0558] The present invention provides a method for manufacturing the following laminate.

[0559] A method for manufacturing a laminate, characterized by comprising the following steps:

[0560] A resist underlayer film is formed on the substrate.

[0561] On the resist underlayer film, a silicon-containing resist underlayer film is formed from a silicon-containing resist underlayer film composition containing any one or more repeating units represented by general formulas (1) to (3) as described above, and any one or more repeating units represented by general formulas (4) to (6) as described above, and

[0562] A resist composition containing at least one superatomic iodine compound selected from the superatomic iodine compound represented by formula (7), the superatomic iodine compound represented by formula (8), and the superatomic iodine compound represented by formula (9), a carboxyl-containing compound, and a solvent is coated onto the silicon-containing resist lower layer film, and then subjected to heat treatment to form a resist film.

[0563] The method for manufacturing the laminate of the present invention, used in a two-layer resist process, comprises the following steps:

[0564] The aforementioned silicon-containing photoresist lower layer composition is coated onto a substrate and subjected to heat treatment to form an adhesive film.

[0565] 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.

[0566] The present invention provides a method for manufacturing a laminate described above, characterized by coating a lower film forming material onto a substrate and subjecting it to heat treatment, thereby forming the aforementioned resist lower film.

[0567] Methods for forming the aforementioned silicon-containing photoresist underlayer film include applying the aforementioned silicon-containing photoresist underlayer film composition onto a substrate using spin coating or similar methods, 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.

[0568] Furthermore, the aforementioned silicon-containing photoresist underlayer film can also be formed by coating the aforementioned silicon-containing photoresist underlayer film composition onto a substrate using a spin coating method or similar method, as described above, and then baking the silicon-containing photoresist underlayer film composition in an environment with an oxygen concentration of 0.1% to 21% to harden it. By baking the aforementioned silicon-containing photoresist underlayer 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.

[0569] Furthermore, the baking environment can be not only in 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 as described 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 photoresist underlayer film.

[0570] The resist film can be formed by coating the aforementioned silicon-containing resist underlayer film using appropriate coating methods such as spin coating, roll 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 to 30 seconds, and more preferably 80–180°C for 30 to 20 seconds.

[0571] The method for manufacturing the laminate of the present invention, used in a 3-layer resist process, comprises the following steps:

[0572] A photoresist underlayer film forming material is coated onto a substrate, and then subjected to heat treatment to form the photoresist underlayer film.

[0573] A silicon-containing photoresist underlayer composition is coated onto the photoresist underlayer film, and then subjected to heat treatment to form a silicon-containing photoresist underlayer film.

[0574] 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.

[0575] Methods for forming the aforementioned photoresist underlayer film include spin coating, where the composition for forming the photoresist underlayer film is coated onto a substrate, the solvent evaporates, and then baking is performed. The baking temperature depends on the type of photoresist underlayer film being formed and can be appropriately set, typically approximately 100–400°C, preferably approximately 150–300°C. The baking time also depends on the type of photoresist underlayer film being formed and can be appropriately set, typically approximately 10–600 seconds, preferably approximately 10–300 seconds.

[0576] The aforementioned photoresist underlayer film should be formed using CVD or ALD methods.

[0577] In the three-layer resist 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 or the like, 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 process.

[0578] In a 3-layer resist process, the resist film can be formed using the same method as in a 2-layer resist process.

[0579] [Pattern Formation Method]

[0580] This invention provides a pattern forming method, comprising the following steps:

[0581] The resist film of the above-described laminate was exposed using i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet light.

[0582] The previously exposed resist film was developed using a developer.

[0583] When using i-rays, KrF excimer lasers, ArF excimer lasers, or EUV for exposure, either directly or with a shield used to form the desired pattern, the exposure dose should be approximately 1–300 mJ / cm². 2 And preferably, it should be approximately 10–200 mJ / cm³. 2 Irradiation is performed in the manner described above. When using EB for exposure, either directly or using a shield to form the desired pattern, the exposure dose should be approximately 0.1–8000 μC / cm. 2 And preferably, it is about 0.5 to 5000 μC / cm. 2 The patterning process is described. Furthermore, the patterning method of the present invention is particularly suitable for fine patterning under high-energy radiation, such as EB or EUV.

[0584] After exposure, PEB should be applied as needed. In this case, it is advisable to apply the PEB on a heated plate or in an oven at 30–200°C for 10 to 30 seconds, or more preferably at 60–120°C for 30 to 20 seconds.

[0585] After exposure or PEB, patterning can be achieved by developing with a developer as needed.

[0586] The developer used at this time should preferably be an organic solvent.

[0587] 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, tert-butanol, tert-amyl alcohol, n-amyl alcohol, cyclohexanol, formic acid, acetic acid, propionic acid, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butyl acetate, isoamyl acetate, cyclohexyl acetate, 4-tert-butylcyclohexyl acetate, octyl acetate, isoborneol acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl valerate, methyl valerate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate. 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. These developers can be used alone or in combination of two or more.

[0588] After development, rinsing should be performed as needed. The rinsing solution should be a solvent that is miscible with the developer and does not dissolve the resist film. Ideal solvents to use include: alcohols with 3 to 10 carbon atoms, ether compounds with 8 to 12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents with 6 to 12 carbon atoms.

[0589] By performing rinsing, the collapse of the resist pattern and the occurrence of defects can be reduced. Furthermore, rinsing is not necessary, and by not performing rinsing, the amount of solvent used can be reduced.

[0590] Example

[0591] The present invention will be specifically described below by example synthesis, comparative synthesis, preparation, examples, and comparative examples, but the present invention is not limited to the following examples. Furthermore, 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) converted from polystyrene were obtained, from which the dispersity (Mw / Mn) was calculated.

[0592] [1] Synthesis of polymers for silicon-containing photoresist underlayer composition

[0593] [Synthesis example 1-1]

[0594] A mixture of 30.6 g of compound (101), 11.4 g of compound (102), and 4.3 g of compound (103) (molar ratio: 67 / 28 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid. The mixture was 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. The water and byproduct 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 polystyrene-converted molecular weight of polysiloxane compound 1 was determined to be Mw = 2,750.

[0595] [Synthesis example 1-2]

[0596] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 8.5 g of compound (103) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid. The mixture was 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. The water and byproduct 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 polystyrene-converted molecular weight of polysiloxane compound 2 was determined to be Mw = 2,650.

[0597] [Synthesis Example 1-3]

[0598] A mixture of 30.6 g of compound (101), 5.3 g of compound (102), and 17.1 g of compound (103) (molar 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 polystyrene-converted molecular weight of polysiloxane compound 3 was determined to be Mw = 2,700.

[0599] [Synthesis Example 1-4]

[0600] A mixture of 30.6 g of compound (101), 1.2 g of compound (102), and 25.6 g of compound (103) (molar 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 complete, 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 polystyrene-converted molecular weight of polysiloxane compound 4 was determined to be Mw = 2,700.

[0601] [Synthesis Example 1-5]

[0602] A mixture of 22.8 g of compound (101) and 42.7 g of compound (103) (molar 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 polystyrene-converted molecular weight of polysiloxane compound 5 was determined to be Mw = 2,650.

[0603] [Synthesis Example 1-6]

[0604] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 9.1 g of compound (104) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid. The mixture was 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. The water and byproduct 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 polystyrene-converted molecular weight of polysiloxane compound 6 was determined to be Mw = 2,650.

[0605] [Synthesis Example 1-7]

[0606] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 9.8 g of compound (105) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid. The mixture was 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. The water and byproduct 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 polystyrene-converted molecular weight of polysiloxane compound 7 was determined to be Mw = 2,700.

[0607] [Synthesis Example 1-8]

[0608] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 9.8 g of compound (106) (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 1.2 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 polystyrene-converted molecular weight of polysiloxane compound 8 was determined to be Mw = 2,730.

[0609] [Synthesis Example 1-9]

[0610] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 6.3 g of compound (107) (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 1.0 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 polystyrene-converted molecular weight of polysiloxane compound 9 was determined to be Mw = 2,550.

[0611] [Synthesis Example 1-10]

[0612] 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. The mixture was 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. The water and byproduct 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 polystyrene-converted molecular weight of polysiloxane compound 10 was determined to be Mw = 3,600.

[0613] [Synthesis Example 1-11]

[0614] A mixture of 30.6 g of compound (101), 5.3 g of compound (102), and 13.8 g of compound (108) (molar 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 polystyrene-converted molecular weight of polysiloxane compound 11 was determined to be Mw = 3,600.

[0615] [Synthesis Example 1-12]

[0616] A mixture of 30.6 g of compound (101), 1.2 g of compound (102), and 20.7 g of compound (108) (molar 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 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 310 g of PGEE solution of polysiloxane compound 12 (compound concentration 10%). The polystyrene-converted molecular weight of polysiloxane compound 12 was determined to be Mw = 7,000.

[0617] [Comparative Synthesis Examples 1-13]

[0618] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 5.9 g of compound (109) (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 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 210 g of PGEE solution of polysiloxane compound 13 (compound concentration 10%). The polystyrene-converted molecular weight of polysiloxane compound 13 was determined to be Mw = 2,600.

[0619] Using the monomers shown in Table 1, and following the methods described in [Synthetic Examples 1-1] to [Synthetic Examples 1-12] and [Comparative Synthetic Examples 1-13], the target compounds were obtained as polysiloxane compounds 1 to 13, respectively.

[0620] [Table 1]

[0621]

[0622]

[0623] [Chemistry 107]

[0624] Si(OMe)4…Compound 101

[0625]

[0626] [2] Preparation of silicon-containing photoresist underlayer composition

[0627] The polysiloxane compounds 1 to 13 obtained in the above synthesis examples 1-1 to 1-13, the crosslinking catalyst, the acid, the solvent, and the water were mixed in the proportions shown in Table 2 and filtered using a 0.1 μm fluororesin filter to prepare polysiloxane lower membrane composition solutions, which were designated as Sol. 1 to 13 respectively.

[0628] [Table 2]

[0629]

[0630] TPSNO3: Triphenylsulfonium nitrate

[0631] QBANO3: Tetrabutylammonium nitrate

[0632] Synthesis of polymers for PGEE: Propylene glycol monoethyl ether [3] resist composition

[0633] The polymers P-1 to P-5 used to synthesize the resist composition use the compounds shown below.

[0634] [Chemistry 108]

[0635]

[0636] [Chemistry 109]

[0637]

[0638] [Chemical 110]

[0639]

[0640] [Synthetic Example 2-1] Synthesis of Polymer P-1

[0641] Under nitrogen atmosphere, monomer b-1 (56g), monomer c-1 (36g), V-601 (manufactured by Fujifilm and Koimitsu Chemical Co., Ltd.) 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. Additionally, Mw is the polystyrene conversion value determined by GPC using THF as a solvent.

[0642] [Chemistry 111]

[0643]

[0644] [Synthetic Examples 2-2 to 2-5] Synthesis of Polymers P-2 to P-5

[0645] 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.

[0646] [Table 3]

[0647]

[0648] [4] Preparation of the resist composition

[0649] [Preparation Examples 2-1 to 2-10, Comparative Preparation Examples 1-1 to 1-2]

[0650] The superatomic iodine compound and the carboxyl-containing compound were dissolved in a solvent containing 0.01% by mass of a 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 resist 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 a 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 resist compositions (CR-01 and CR-02).

[0651] [Table 4]

[0652]

[0653] [Table 5]

[0654]

[0655] 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.

[0656] [Chemistry 112]

[0657]

[0658] [Chemistry 113]

[0659]

[0660] [Chemistry 114]

[0661]

[0662] [Chemistry 115]

[0663]

[0664] Solvent: AcOH (acetic acid)

[0665] GBL (γ-butyrolactone)

[0666] [5] Fabrication and EUV lithography evaluation of the laminate (2-layer resist process, line and spacing pattern)

[0667] [Examples 1-1 to 1-21, Comparative Examples 1-1 to 1-4]

[0668] Each silicon-containing photoresist underlayer composition (Sol.1 to 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 photoresist underlayer film with a thickness of 40 nm.

[0669] Then, each resist composition (R-01 to R-10, CR-01 to CR-02) was spin-coated onto the aforementioned film, and pre-baked (PAB) for 60 seconds at the temperature specified in Table 6 using a heated plate to obtain a resist film with a thickness of 40 nm. The aforementioned resist film was then exposed to a 36 nm line-to-spacing (LS) 1:1 pattern using an ASML EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9, 90-degree dipole illumination). PEB was then performed on the heated plate at the temperature specified in Table 6 for 60 seconds, followed by development with the developer specified in Table 6 for 30 seconds to form an LS pattern with a spacing width of 18 nm and a pitch of 36 nm.

[0670] The obtained resist patterns were evaluated as follows. The results are shown in Table 6.

[0671] [Sensitivity Evaluation]

[0672] The aforementioned LS pattern was observed using a Hitachi Advanced Technology & Materials Co., Ltd. (HIT) CG-6300 measuring SEM, and the optimal exposure Eop (mJ / cm²) for obtaining an LS pattern with a spacing width of 18nm and a pitch of 36nm was determined. 2 And make it a sensitivity.

[0673] [LWR Evaluation]

[0674] The dimensions of 10 points on an LS pattern obtained by exposure to the optimal amount of light along the length direction of the spacing 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 pattern with a wide spacing width can be obtained.

[0675] [Evaluation of Extreme Resolution]

[0676] Using a Hitachi Advanced Technologies (AGT) CG-6300 long-range SEM, the limiting linewidth (nm) that can be resolved by gradually increasing the exposure amount to form the aforementioned LS pattern from the optimal exposure amount is determined, and this is set as the limiting resolution (nm). The smaller this value, the better the limiting resolution, and the finer the pattern can be formed.

[0677] [Table 6]

[0678]

[0679]

[0680] Developer: nBA (Butyl acetate)

[0681] TMAH (2.38% by mass tetramethylammonium hydroxide aqueous solution)

[0682] As shown in Table 6, comparing Comparative Examples 1-1 and 1-2 with the Examples, excellent resolution can be obtained in the two-layer resist process by using the aforementioned silicon-containing resist lower layer 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 laminate of the present invention, excellent resolution is achieved during LS pattern formation under EUV exposure.

[0683] [6] Fabrication and EUV lithography evaluation of the laminate (3-layer resist process, contact hole pattern)

[0684] [Examples 2-1 to 2-21, Comparative Examples 2-1 to 2-4]

[0685] 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 200 nm thick photoresist underlayer film. Various silicon-containing photoresist underlayer film compositions (Sol.1 to Sol.13) were then spin-coated onto this film and baked at the temperatures listed in Table 7 for 60 seconds using a heating plate to form a 40 nm thick silicon-containing photoresist underlayer film.

[0686] Then, each resist composition (R-01 to R-10, CR-01 to CR-02) was spin-coated onto the aforementioned film, and pre-baked (PAB) for 60 seconds at the temperature listed in Table 7 using a hot 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, wafer-scale hole pattern with a pitch of 64 nm, +20% offset shielding). PEB was performed on the hot plate at the temperature listed in Table 7 for 60 seconds, followed by development for 30 seconds using the developer listed in Table 7, to obtain a hole pattern with a size of 32 nm.

[0687] The obtained resist pattern was evaluated as follows. The results are shown in Table 7.

[0688] [Sensitivity Evaluation]

[0689] The aforementioned contact hole pattern was observed using a Hitachi Advanced Technology Co., Ltd. (HIT) CG-6300 SEM, and the optimal exposure value (Eop, mJ / cm²) for obtaining a hole pattern with a size of 22 nm was determined. 2 And make it a sensitivity.

[0690] [CDU Evaluation]

[0691] The dimensions of 50 hole patterns obtained by irradiation with the optimal exposure were measured, and the standard deviation (σ) of the results was defined as three times the value of 3σ (CDU). The smaller this value, the more uniform the hole diameter of the pattern can be obtained.

[0692] [Evaluation of Extreme Resolution]

[0693] Using a Hitachi Advanced Technologies (AGT) CG-6300 long-range SEM, the limiting aperture diameter (nm) that can be resolved by gradually reducing the exposure amount to form the aforementioned aperture pattern from the optimal exposure amount is determined, and this value is set as the limiting resolution (nm). The smaller this value, the better the limiting resolution, and the more fine the aperture diameter pattern can be formed.

[0694] [Table 7]

[0695]

[0696]

[0697] 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 layer composition. Furthermore, even compared to 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 is evident that in the 3-layer resist process using the laminate of the present invention, excellent CDU is achieved during contact hole pattern formation under EUV exposure.

[0698] This specification includes the following inventions. [1]

[0700] A stacked body, characterized by comprising, in sequence:

[0701] substrate,

[0702] A silicon-containing photoresist underlayer film is obtained from a silicon-containing photoresist underlayer 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

[0703] 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), superatomic iodine compounds represented by formula (9), a carboxyl-containing compound, and a solvent.

[0704] [Chemistry 116]

[0705]

[0706] In the formula, R 1 R is an organic group having a carboxyl group or an organic group having a carboxyl group substituted by an acid-labile group. 2 R 3 and R 4 These are monovalent organic groups with 1 to 30 carbon atoms, which may be the same or different.

[0707] [Chemistry 117]

[0708]

[0709] 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.

[0710] R 11 ~R 18 Each group consists independently of a halogen atom, or may contain heteroatoms, and is a hydrocarbon group with 1 to 10 carbon atoms. Also, R 11 and R 12 R 13 and R 14 R 15 and R 16 、or R 17 and R 18 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0711] R 21 ~R 24 Each R is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms. When n2 is 2 or more, each R21 They can be the same or different, and there are multiple Rs. 21 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R 22 They can be the same or different, and there are multiple Rs. 22 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R 23 They can be the same or different, and there are multiple Rs. 23 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R 24 They can be the same or different, and there are multiple Rs. 24 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0712] R 25 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 25 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl bond. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 24 and R 25 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms. [2]

[0714] As described in [1], a layered structure is provided between the aforementioned substrate and the silicon-containing photoresist underlayer. [3]

[0716] As described in [1] or [2], the aforementioned silicon-containing photoresist lower film composition contains a crosslinking catalyst (Xc) for siloxane polymerization, an alcohol-based organic solvent, and water. [4]

[0718] As described in any of [1] to [3], the aforementioned carboxyl-containing compound in the aforementioned resist composition is a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11).

[0719] [Chemistry 118]

[0720]

[0721] In the formula, R AIt can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group.

[0722] X A It is a single bond, phenylene, naphthylene, or *-C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0723] p can be 1, 2, 3 or 4.

[0724] R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms; when p is 2, R 31 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing heteroatoms, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be replaced by a group containing heteroatoms.

[0725] R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group can be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group can also be replaced by a group containing a heteroatom. When p is 2 to 4, each R 32 They can be the same or different. [5]

[0727] A method for manufacturing a laminate, characterized by comprising the following steps:

[0728] A resist underlayer film is formed on the substrate.

[0729] On the resist underlayer film, a silicon-containing resist underlayer film is formed from a silicon-containing resist underlayer 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

[0730] A resist 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 resist lower layer film, and then subjected to heat treatment to form a resist film.

[0731] [Chemistry 119]

[0732]

[0733] In the formula, R 1 R is an organic group having a carboxyl group or an organic group having a carboxyl group substituted by an acid-labile group. 2 R 3 and R 4 These are monovalent organic groups with 1 to 30 carbon atoms, which may be the same or different.

[0734] [Chemistry 120]

[0735]

[0736] 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.

[0737] R 11 ~R 18 Each group consists independently of a halogen atom, or may contain heteroatoms, and is a hydrocarbon group with 1 to 10 carbon atoms. Also, R 11 and R 12 R 13 and R 14 R 15 and R 16 、or R 17 and R 18 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

[0738] R 21 ~R 24 Each R is a hydrocarbon group with 1 to 40 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms. When n2 is 2 or more, each R 21 They can be the same or different, and there are multiple Rs. 21 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R 22 They can be the same or different, and there are multiple Rs. 22 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R 23 They can be the same or different, and there are multiple Rs. 23They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R 24 They can be the same or different, and there are multiple Rs. 24 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to.

[0739] R 25 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 25 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl bond. Furthermore, some or all of the hydrogen atoms in the aforementioned (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be substituted by a group containing a heteroatom, and part of the -CH2- of the aforementioned (n8) valence hydrocarbon group can also be substituted by a group containing a heteroatom, R 24 and R 25 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms. [6]

[0741] The method for manufacturing a laminate as described in [5] involves coating a lower film forming material onto a substrate and then subjecting it to heat treatment, thereby forming the aforementioned resist lower film. [7]

[0743] The method of manufacturing the laminate as described in [5] involves forming the aforementioned resist underlayer film using CVD or ALD. [8]

[0745] The method for manufacturing a laminate 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).

[0746] [Chemistry 121]

[0747]

[0748] In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group.

[0749] X A It is a single bond, phenylene, naphthylene, or *-C(=O)-OX A1 -. X A1 It is a saturated hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms, and the saturated hydrocarbon group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring. * indicates an atomic bond with a carbon atom in the main chain.

[0750] p can be 1, 2, 3 or 4.

[0751] R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms; when p is 2, R 31 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the aforementioned p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing heteroatoms, and part of the -CH2- of the aforementioned p-valent hydrocarbon group can also be replaced by a group containing heteroatoms.

[0752] R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group can be replaced by a group containing a heteroatom, and part of the -CH2- of the hydrocarbon group can also be replaced by a group containing a heteroatom. When p is 2 to 4, each R 32 They can be the same or different. [9]

[0754] A method for forming a pattern includes the following steps:

[0755] Expose the resist film of the laminate described in any of [1] to [4] to the i-ray, KrF excimer laser, ArF excimer laser, electron beam or extreme ultraviolet light, and

[0756] The previously exposed resist film was developed using a developer.

[10]

[0758] The pattern forming method described in [9], wherein the aforementioned developing solution is an organic solvent.

[0759] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative examples, and those having substantially the same structure and performing the same effects as the technical concept described in the claims of the present invention are all intended to be included within the technical scope of the present invention.

Claims

1. A layered body, characterized by comprising, in sequence: substrate, A silicon-containing photoresist underlayer film is obtained from a silicon-containing photoresist underlayer 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 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), superatomic iodine compounds represented by formula (9), a carboxyl-containing compound, and a solvent; In the formula, R 1 R is an organic group having a carboxyl group or an organic group having a carboxyl group substituted by an acid-labile group. 2 R 3 and R 4 These are monovalent organic groups with 1 to 30 carbon atoms, which may be the same or different; 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; but 1 ≤ n3 + n4 ≤ 5; n5 is 1 or 2; n6 is 0, 1, 2, 3, or 4; but 1 ≤ n5 + n6 ≤ 5; n7 is 0, 1, 2, 3, or 4; n8 is 1, 2, 3, or 4. R 11 ~R 18 Each of the following groups is a hydrocarbon group consisting of 1 to 10 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms; furthermore, R 11 and R 12 R 13 and R 14 R 15 and R 16 、or R 17 and R 18 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms; R 21 ~R 24 Each R is an independent hydrocarbon group consisting of halogen atoms, or may contain heteroatoms, with 1 to 40 carbon atoms; when n2 is 2 or more, each R 21 They can be the same or different, and there are multiple Rs. 21 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n4 is 2 or more, each R 22 They can be the same or different, and there are multiple Rs. 22 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n6 is 2 or more, each R 23 They can be the same or different, and there are multiple Rs. 23 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n7 is 2 or more, each R 24 They can be the same or different, and there are multiple Rs. 24 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; R 25 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 25 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl bond; furthermore, part or all of the hydrogen atoms of the (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be replaced by a group containing a heteroatom, and part of the -CH2- of the (n8) valence hydrocarbon group can also be replaced by a group containing a heteroatom, R 24 and R 25 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

2. The laminated body according to claim 1, wherein, A photoresist underlayer is provided between the substrate and the silicon-containing photoresist underlayer.

3. The laminated body according to claim 1, wherein, The silicon-containing photoresist lower film composition contains a crosslinking catalyst (Xc) for siloxane polymerization, an alcohol-based organic solvent, and water.

4. The laminated body according to claim 1, wherein, The carboxyl-containing compound in the resist composition is a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11); In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group; X A It is a single bond, phenylene, naphthylene, or *-C(=O)-OX A1 -;X A1 It is a saturated alkylene group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring; * indicates an atomic bond with a carbon atom in the main chain; p is 1, 2, 3 or 4; R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms; when p is 2, R 31 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group or sulfonyl group; furthermore, part or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing heteroatoms, and part of the -CH2- of the p-valent hydrocarbon group can also be replaced by a group containing heteroatoms. R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group can be replaced by a group containing heteroatoms, and part of the -CH2- of the hydrocarbon group can also be replaced by a group containing heteroatoms; when p is 2 to 4, each R 32 They can be the same or different.

5. A method for manufacturing a laminate, characterized by comprising the following steps: A resist underlayer film is formed on the substrate. On the resist underlayer film, a silicon-containing resist underlayer film is formed from a silicon-containing resist underlayer 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 resist 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 on the silicon-containing resist lower layer film, and then subjected to heat treatment to form a resist film. In the formula, R 1 R is an organic group having a carboxyl group or an organic group having a carboxyl group substituted by an acid-labile group. 2 R 3 and R 4 These are monovalent organic groups with 1 to 30 carbon atoms, which may be the same or different; 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; but 1 ≤ n3 + n4 ≤ 5; n5 is 1 or 2; n6 is 0, 1, 2, 3, or 4; but 1 ≤ n5 + n6 ≤ 5; n7 is 0, 1, 2, 3, or 4; n8 is 1, 2, 3, or 4. R 11 ~R 18 Each of the following groups is a hydrocarbon group consisting of 1 to 10 carbon atoms, which may be independently composed of halogen atoms or may also contain heteroatoms; furthermore, R 11 and R 12 R 13 and R 14 R 15 and R 16 、or R 17 and R 18 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms; R 21 ~R 24 Each R is an independent hydrocarbon group consisting of halogen atoms, or may contain heteroatoms, with 1 to 40 carbon atoms; when n2 is 2 or more, each R 21 They can be the same or different, and there are multiple Rs. 21 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n4 is 2 or more, each R 22 They can be the same or different, and there are multiple Rs. 22 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n6 is 2 or more, each R 23 They can be the same or different, and there are multiple Rs. 23 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; when n7 is 2 or more, each R 24 They can be the same or different, and there are multiple Rs. 24 They can also bond to each other and form rings together with the carbon atoms of the aromatic rings they are bonded to; R 25 R is a (n8) valence hydrocarbon group with 1 to 40 carbon atoms or a (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R 25 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl bond; furthermore, part or all of the hydrogen atoms of the (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be replaced by a group containing a heteroatom, and part of the -CH2- of the (n8) valence hydrocarbon group can also be replaced by a group containing a heteroatom, R 24 and R 25 They can also bond to each other and form rings together with the carbon atoms they are bonded to and the atoms between those carbon atoms.

6. The method for manufacturing a laminate according to 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 according to claim 5, wherein the resist underlayer film is formed by CVD or ALD.

8. The method of manufacturing a laminate according to any one 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); In the formula, R A It can be a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group; X A It is a single bond, phenylene, naphthylene, or *-C(=O)-OX A1 -;X A1 It is a saturated alkylene group, phenylene group, or naphthylene group with 1 to 10 carbon atoms, and the saturated alkylene group may also contain a hydroxyl group, ether bond, ester bond, or lactone ring; * indicates an atomic bond with a carbon atom in the main chain; p is 1, 2, 3 or 4; R 31 R is a p-valent hydrocarbon group with 1 to 40 carbon atoms or a p-valent heterocyclic group with 2 to 40 carbon atoms; when p is 2, R 31 It can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group or sulfonyl group; furthermore, part or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group can be replaced by a group containing heteroatoms, and part of the -CH2- of the p-valent hydrocarbon group can also be replaced by a group containing heteroatoms. R 32 It is a single bond or a hydrocarbon group with 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbon group can be replaced by a group containing heteroatoms, and part of the -CH2- of the hydrocarbon group can also be replaced by a group containing heteroatoms; when p is 2 to 4, each R 32 They can be the same or different.

9. A method for forming a pattern, comprising the following steps: Expose the resist film of the laminate according to any one of claims 1 to 4 to i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet light. The exposed resist film was developed using a developer.

10. The pattern forming method according to claim 9, wherein, The developer is an organic solvent.

Images