Composition for forming silicon-containing resist film, and patterning process

Abstract

COMPOSITION FOR FORMING SILICON-CONTAINING RESIST FILM CAPABLE OF FORMING ULTRAFINE RESIST PATTERN EXCELLENT IN LWR AND CDU, HAVING HIGH ETCHING SELECTIVITY BETWEEN FORMED RESIST FILM AND ORGANIC MATERIAL, AND CAPABLE OF FORMING PATTERN WITHOUT DEFECTS DUE TO RESIDUE REMAINING AFTER COMPLETION OF PATTERNING, AND PATTERNING PROCESS USING THE SAME SOLUTION: The composition for forming a silicon-containing resist film contains a polysiloxane having a specific structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition for forming a silicon-containing resist film and a pattern forming method using the composition. [Background technology]

[0002] As large-scale integrated circuits (LSIs) become increasingly integrated and faster, pattern dimensions are becoming increasingly fine. Lithography technology has achieved this by shortening the wavelength of light sources and selecting appropriate resist compositions to accommodate this. Single-layer positive photoresist compositions have become the key to this. These single-layer positive photoresist compositions incorporate a backbone that provides etching resistance to dry etching with chlorine- or fluorine-based gas plasmas, and also incorporate a switching mechanism that dissolves exposed areas. This allows the exposed areas to be dissolved to form a pattern, and the remaining resist pattern is then used as an etching mask to dry etch the substrate.

[0003] However, if the thickness of the photoresist film used is made finer, i.e., the pattern width is made smaller, the resolution of the photoresist film decreases, and when an attempt is made to develop the photoresist film into a pattern using a developer, the aspect ratio becomes too large, resulting in pattern collapse. For this reason, photoresist films have been made thinner as patterns become finer.

[0004] On the other hand, substrate processing typically involves dry etching using a patterned photoresist film as an etching mask. However, in reality, no dry etching method exists that can achieve perfect etching selectivity between the photoresist film and the substrate. As a result, the resist film is also damaged and disintegrated during substrate processing, resulting in the inability to accurately transfer the resist pattern to the substrate. Therefore, as patterns become finer, photoresist compositions are required to have higher dry etching resistance. However, to improve resolution, resins with low light absorption at the exposure wavelength have been required for use in photoresist compositions. Therefore, as exposure light wavelengths have become shorter (i-line, KrF, and ArF), the resins used in photoresist compositions have shifted to novolac resins, polyhydroxystyrenes, and resins with aliphatic polycyclic skeletons. However, in reality, the etching rates under dry etching conditions during substrate processing have become faster, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] This means that substrates to be processed must be dry etched using thinner photoresist films with weaker etching resistance, and there is an urgent need to secure the materials and processes required for this processing step.

[0006] One method for solving these problems is the multilayer resist method, in which a resist intermediate film having etching selectivity different from that of a photoresist film (i.e., a resist top layer film) is interposed between the resist top layer film and the substrate to be processed, a pattern is formed on the resist top layer film, and then the pattern is transferred to the resist intermediate film by dry etching using the resist top layer film pattern as a dry etching mask, and the pattern is then transferred to the substrate to be processed by dry etching using the resist intermediate film as a dry etching mask.

[0007] One type of multilayer resist method is the three-layer resist method, which can be performed using a typical resist composition used in the single-layer resist method. In this three-layer resist method, for example, an organic film made of a novolac resin or the like is formed on a substrate to be processed, a silicon-containing resist intermediate film is formed thereon, and a conventional organic photoresist film is formed on top of that as a resist top layer. When dry etching is performed using a fluorine-based gas plasma, the organic resist top layer has a good etching selectivity relative to the silicon-containing resist intermediate film, so the resist top layer pattern can be transferred to the silicon-containing resist intermediate film by dry etching with a fluorine-based gas plasma. This method allows for pattern transfer to the silicon-containing resist intermediate film even when using a resist composition that is difficult to directly form a pattern with a sufficient thickness for processing the substrate to be processed or that does not have sufficient dry etching resistance for substrate processing. Subsequent pattern transfer by dry etching with an oxygen- or hydrogen-based gas plasma can result in an organic film pattern made of a novolac resin or the like that has sufficient dry etching resistance for substrate processing. The silicon-containing resist interlayer remaining after forming the organic film pattern is generally removed by dry etching using a fluorine-based gas plasma or wet etching using an alkaline or fluorine-based etching solution, so as not to leave residues that could cause defects. If the etching rate is insufficient, residues from the silicon-containing resist interlayer may remain and cause defects, or a long etching process may be required, potentially damaging the substrate to be processed. Thus, for accurate patterning and smooth removal, the silicon-containing resist interlayer needs to have an appropriate etching rate.

[0008] On the other hand, in recent years, the advent of ArF immersion lithography, EUV lithography, etc. has made it possible to form finer patterns, but this has also led to the further thinning of photoresist films. This thinning of photoresist films leads to deterioration of line edge roughness (LWR) and hole dimension uniformity (CDU) in ultra-fine patterns, so improving LWR and CDU has become a serious problem.

[0009] Compositions for forming silicon-containing resist films for ArF or EUV lithography containing curing catalysts have been proposed (Patent Documents 1 and 2). These curing catalysts have a structure suitable for catalyzing the silanol condensation reaction and promoting the formation of siloxane bonds, which form the main backbone of silicon-containing resist films. It has also become clear that the selection of curing catalysts has various effects on the properties of silicon-containing resist films. Examples include acidity / basicity, hydrophilicity / hydrophobicity, hardness, film density, and etching rate. These curing catalysts have a structure similar to that of sensitivity adjusters in the top-layer resist. Therefore, diffusion into the top-layer resist due to heating or exposure significantly impacts the pattern formation ability of the photoresist. Because of the impact on LWR and CDU performance, in particular, the development of curing catalysts with reduced diffusion into the top-layer resist is needed.

[0010] On the other hand, photosensitive upper layer resist materials containing compounds containing cations and anions in the molecule are known to improve LWR and CDU (Patent Document 3). However, recent ultra-fine patterns require higher accuracy in LWR and CDU, and improvements in the performance of resist films are also required. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Patent Publication No. 2007-302873 [Patent Document 2] WO2013 / 161372 issue [Patent Document 3] Patent Publication No. 2011-016746 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made to solve the above problems, and an object of the present invention is to provide a composition for forming a silicon-containing resist film that can form a silicon-containing resist film in a multilayer resist method, which has an appropriate etching rate and can improve LWR and CDU in ultrafine patterns, and a pattern formation method using the composition. [Means for solving the problem]

[0013] In order to solve the above problems, the present invention provides a composition for forming a silicon-containing resist film, characterized by containing a polysiloxane containing at least one of a repeating unit represented by the following formula (A-1), a repeating unit represented by the following formula (A-2), and a partial structure represented by the following formula (A-3): [ka] (In the formula, R 1 is a monovalent organic group having 1 to 30 carbon atoms, which may have a substituent, a halogen atom, a hydroxy group, a sulfo group, a nitro group, or a carboxyl group, which acts as a leaving group when exposed to heat, an acid, or a base, and R 2 , R 3 each independently represents a monovalent organic group having 1 to 30 carbon atoms which may have a substituent.)

[0014] The side chains of polysiloxane structures with these repeating units and partial structures undergo elimination reactions when affected by heat, acid, or base, allowing the formation of silicon-containing resist films with a high silicon atom ratio and good LWR and CDU properties. Furthermore, the effect of silicon atoms allows the formation of resist films with good etching rates.

[0015] In the present invention, R in the formulas (A-1), (A-2), and (A-3) 1 is preferably a monovalent group represented by the following formula (B-1) that acts as a leaving group when exposed to heat, acid or base, a halogen atom, a hydroxy group, a sulfo group, a nitro group or a carboxyl group. [ka] (In the formula, R4's are substituents bonded to the aromatic ring, and each R4 independently represents a hydrogen atom or an alkyl group of 1 to 20 carbon atoms which may have a substituent, an aryl group of 6 to 20 carbon atoms which may have a substituent, a halogenated alkyl group of 1 to 20 carbon atoms which may have a substituent, a halogenated aryl group of 6 to 20 carbon atoms which may have a substituent, an alkoxyalkyl group of 1 to 20 carbon atoms which may have a substituent, an alkoxyaryl group of 6 to 20 carbon atoms which may have a substituent, an acyl group of 6 to 20 carbon atoms which may have a substituent, a halogen atom, a hydroxyl group, a sulfo group, a nitro group, or a carboxyl group; a=0 or 1; n=2a+5; and * represents a bond to another atom.)

[0016] The side chains of polysiloxane structures with such repeating units or partial structures are more susceptible to elimination reactions under the influence of heat, acid, or base, allowing for the formation of silicon-containing resist films with a high silicon atom ratio, resulting in better LWR and CDU characteristics. Furthermore, the effect of silicon atoms allows for the formation of resist films with even better etching rates.

[0017] In the present invention, it is preferable that the polysiloxane further contains a thermally crosslinkable polysiloxane containing at least one of a repeating unit represented by the following formula (Sx-1), a repeating unit represented by the following formula (Sx-2), and a partial structure represented by the following formula (Sx-3). [ka] (In the formula, R 5 , R 6 , R 7are each independently a monovalent organic group having 1 to 30 carbon atoms which may have a substituent.)

[0018] If the thermally crosslinkable polysiloxane contains the above-mentioned specific structure, the adhesion to the resist is high, and the effects of the present invention are more fully exhibited.

[0019] It is preferable that the silicon-containing resist film-forming composition of the present invention further contains a crosslinking catalyst.

[0020] In such a silicon-containing resist film-forming composition, the crosslinking reaction proceeds sufficiently, and the resist film derived from the silicon-containing resist film-forming composition of the present invention exhibits good etching resistance.

[0021] In the silicon-containing resist film-forming composition of the present invention, the crosslinking catalyst is preferably an ammonium salt or a sulfonium salt.

[0022] When such a composition for forming a silicon-containing resist film is used, the etching resistance of the resist film derived from the composition for forming a silicon-containing resist film of the present invention is even better.

[0023] It is preferable that the composition for forming a silicon-containing resist film of the present invention further contains an acid generator.

[0024] If necessary, an acid generator may be added to finely adjust the pattern shape, exposure sensitivity, and the like.

[0025] In the silicon-containing resist film-forming composition of the present invention, the crosslinking catalyst is preferably a sulfonium salt.

[0026] Such a silicon-containing composition for forming a resist film can appropriately adjust the pattern shape, exposure sensitivity, etc. of the resist film while minimizing deterioration of other performance properties, and is also effective in reducing residues derived from the resist film.

[0027] The present invention also provides a pattern formation method including the steps of: forming an organic film on a workpiece using a coating-type organic film material; forming a silicon-containing resist intermediate film on the organic film using the silicon-containing resist film-forming composition described above; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film composition consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern by etching onto the silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching onto the organic film using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0028] The present invention also provides a pattern formation method including the steps of: forming a hard mask containing carbon as a main component on a workpiece by a CVD method; forming a silicon-containing resist intermediate film on the hard mask using the silicon-containing resist film-forming composition described above; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film composition consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the hard mask by dry etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and transferring the pattern to the workpiece by dry etching using the hard mask on which the pattern has been transferred as a mask.

[0029] The above-described pattern formation method is particularly practical for forming fine patterns, because it suppresses pattern collapse of the resist upper layer film, provides excellent pattern transfer to the silicon-containing resist intermediate film by dry etching, and is easy to remove the silicon-containing resist intermediate film remaining after patterning is completed, making it unlikely to cause defects due to residues.

[0030] The present invention also provides a pattern formation method, in which the pattern formation in the step of forming a circuit pattern on the resist upper layer film is performed by photolithography, direct writing with an electron beam, nanoimprinting, or a combination thereof, with a wavelength of 10 nm or more and 300 nm or less.

[0031] Such a method for forming a circuit pattern on a resist upper layer film allows the effects of the present invention to be more fully exhibited.

[0032] In the present invention, the workpiece is preferably any one of a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, and a metal oxynitride film.

[0033] When the above-mentioned specific workpiece is used, the effects of the present invention are more fully exhibited.

[0034] In the present invention, the metal constituting the workpiece is preferably silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

[0035] If the metal constituting the workpiece is the specific metal, the effects of the present invention are more fully exhibited. [Effects of the Invention]

[0036] As described above, the polysiloxanes having the repeating units and partial structures of the present invention exhibit high solubility and stability in organic solvents. Furthermore, elimination reactions induced by heat or acid during curing can provide films with a high silicon content. This not only enables the formation of ultrafine upper resist patterns with good LWR and CDU, but also provides excellent dry etching selectivity between the resist film and an organic film or hard mask, enabling semiconductor device patterns to be formed on substrates with high yields. Furthermore, since the formed silicon-containing resist interlayer film exhibits high etching selectivity with respect to organic materials, the formed photoresist pattern can be transferred sequentially to the silicon-containing resist interlayer, an organic film, or a hard mask using a dry etching process. Furthermore, since the formed silicon-containing resist interlayer film has a sufficient etching rate, the remaining silicon-containing resist interlayer film after patterning is easily removed, and defects due to residues are unlikely to occur, making it particularly useful for forming fine patterns. DETAILED DESCRIPTION OF THE INVENTION

[0037] As described above, there has been a need for a composition for forming a silicon-containing resist film that can form a silicon-containing resist film that has an appropriate etching rate and can improve LWR and CDU in ultrafine patterns in a multilayer resist method, and for a pattern formation method using the composition.

[0038] As a result of extensive research into achieving the above-mentioned object, the present inventors have discovered that by incorporating a polysiloxane containing a specific repeating unit or partial structure into a composition for forming a silicon-containing resist film, it is possible to improve the LWR and CDU of ultrafine patterns in a multilayer resist method and provide a silicon-containing resist film having an etching rate appropriate for processing, thereby completing the present invention.

[0039] That is, the present invention provides a composition for forming a silicon-containing resist film, characterized by containing a polysiloxane containing at least one of a repeating unit represented by the following formula (A-1), a repeating unit represented by the following formula (A-2), and a partial structure represented by the following formula (A-3): [ka] (In the formula, R 1 is a monovalent organic group having 1 to 30 carbon atoms, which may have a substituent, a halogen atom, a hydroxy group, a sulfo group, a nitro group, or a carboxyl group, which acts as a leaving group when exposed to heat, an acid, or a base, and R 2 , R 3 each independently represents a monovalent organic group having 1 to 30 carbon atoms which may have a substituent.)

[0040] The present invention will be described in detail below, but the present invention is not limited thereto.

[0041] <Silicon-containing resist film-forming composition> The silicon-containing resist film-forming composition of the present invention is characterized by containing at least one of the repeating units represented by the general formula (A-1), (A-2), and the partial structure represented by the general formula (A-3). In addition, it may contain any other optional components. Hereinafter, each component contained in the composition for forming a silicon-containing resist film of the present invention will be described in detail.

[0042] [Thermal crosslinkable polysiloxane (Sx)] The composition for forming a silicon-containing resist film of the present invention can contain a thermally crosslinkable polysiloxane (Sx) containing at least one of the repeating units represented by the general formula (A-1), (A-2), and the partial structure represented by the general formula (A-3).

[0043] In the repeating units and partial structures represented by the formulae (A-1), (A-2) and (A-3), R 1The following structures can be exemplified for the above, but the present invention is not limited thereto.

[0044] R 1 Specific examples of the alkyl group include a methyl group, an ethyl group, a vinyl group, a propyl group, an isopropyl group, an allyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a t-pentyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group, an ethylphenyl group, a propylphenyl group, an isopropylphenyl group, a fluorophenyl group, a chlorophenyl group, and a bromophenyl group. , iodophenyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, isopropoxyphenyl group, butoxyphenyl group, isobutoxyphenyl group, sec-butoxyphenyl group, t-butoxyphenyl group, pentoxyphenyl group, isopentoxyphenyl group, sec-pentoxyphenyl group, 3-pentoxyphenyl group, t-pentoxyphenyl group, neopentoxyphenyl group, acetylphenyl group, hydroxyphenyl group, sulfophenyl group, nitrophenyl group, naphthyl group, a methyl naphthyl group, an ethyl naphthyl group, a propyl naphthyl group, an isopropyl naphthyl group, a fluoronaphthyl group, a chloronaphthyl group, a bromonaphthyl group, an iodonaphthyl group, a methoxynaphthyl group, an ethoxynaphthyl group, a propoxynaphthyl group, an isopropoxynaphthyl group, a butoxynaphthyl group, an isobutoxynaphthyl group, a sec-butoxynaphthyl group, a t-butoxynaphthyl group, a pentoxynaphthyl group, an isopentoxynaphthyl group, a sec-pentoxynaphthyl group, a 3-pentoxynaphthyl group, Examples include t-pentoxynaphthyl group, neopentoxynaphthyl group, acetylnaphthyl group, hydroxynaphthyl group, sulfonaphthyl group, nitronaphthyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, isopentoxy group, sec-pentoxy group, 3-pentoxy group, t-pentoxy group, neopentoxy group, fluorine, chlorine, bromine, iodine, hydroxy group, sulfo group, nitro group, and carboxy group.

[0045] R 2 , R 3 R each independently represents a monovalent organic group having 1 to 30 carbon atoms which may have a substituent. 2 , R 3 is preferably a saturated or unsaturated organic group having 1 to 20 carbon atoms, which may have a substituent. Examples of the organic group include a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted linear, branched, or cyclic alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a vinyl group, an allyl group, a propenyl group, a phenyl group, and a tolyl group.

[0046] The silicon-containing resist film-forming composition of the present invention is a silicon-containing resist film-forming composition in which R 1 is preferably a monovalent group represented by the following formula (B-1) that acts as a leaving group by heat, acid or base, a halogen atom, a hydroxy group, a sulfo group, a nitro group or a carboxyl group. [ka] (In the formula, R4's are substituents bonded to the aromatic ring, and each R4 independently represents a hydrogen atom or an alkyl group of 1 to 20 carbon atoms which may have a substituent, an aryl group of 6 to 20 carbon atoms which may have a substituent, a halogenated alkyl group of 1 to 20 carbon atoms which may have a substituent, a halogenated aryl group of 6 to 20 carbon atoms which may have a substituent, an alkoxyalkyl group of 1 to 20 carbon atoms which may have a substituent, an alkoxyaryl group of 6 to 20 carbon atoms which may have a substituent, an acyl group of 6 to 20 carbon atoms which may have a substituent, a halogen atom, a hydroxyl group, a sulfo group, a nitro group, or a carboxyl group; a=0 or 1; n=2a+5; and * represents a bond to another atom.)

[0047] The side chains of polysiloxane structures with such partial structures are more susceptible to elimination reactions due to the effects of heat, acid, or base, making it possible to form silicon-containing resist films with a high silicon atom ratio, which have better LWR and CDU characteristics, and also enable the formation of resist films with even better etching rates.

[0048] Specific examples of R4 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group; a vinyl group, an allyl group, a propenyl group; a phenyl group, a tolyl group; a trifluoromethyl group, a trichloromethyl group; a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group; a methoxymethyl group, an ethoxymethyl group; an m-chlorophenyl group; an acetyl group; a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, a sulfo group, a nitro group, and a carboxy group.

[0049] In (B-1), a is preferably 0 or 1, and R4 is preferably a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom.

[0050] The polysiloxane preferably contains a thermally crosslinkable polysiloxane containing at least one of a repeating unit represented by the following formula (Sx-1), a repeating unit represented by the following formula (Sx-2), and a partial structure represented by the following formula (Sx-3).

[0051] [ka] (In the formula, R 5 , R 6 , R 7 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different.

[0052] Above R 5 , R 6 , R 7 is a monovalent organic group having 1 to 30 carbon atoms which may have a substituent. R 5 , R 6 , R 7 Specific examples of the group represented by include a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, which may have a substituent, an alkenyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0053] R 5 , R 6 , R 7 Examples of the organic group include an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds, specifically an organic group having one or more groups selected from the group consisting of an ether bond, an ester bond, an alkoxy group, a hydroxy group, and the like.

[0054] A specific example of the above is one represented by the formula (Sm-R). (P-Q1-(S1) v1 -Q2-)u-(T) v2 -Q3-(S2) v3 -Q4- (Sm-R) (In formula (Sm-R), P represents a hydrogen atom, a cyclic ether group, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or an alkylcarbonyl group having 1 to 6 carbon atoms; Q1, Q2, Q3, and Q4 each independently represent -CqH(2q-p)Pp- (wherein P is as defined above, p is an integer of 0 to 3, and q is an integer of 0 to 10 (wherein q=0 represents a single bond)); u represents an integer of 0 to 3; S1 and S2 each independently represent represents -O-, -CO-, -OCO-, -COO-, or -OCOO-. v1, v2, and v3 each independently represent 0 or 1. T is a divalent group consisting of a divalent atom other than carbon, an alicyclic ring, an aromatic ring, or a heterocyclic ring. Examples of T as an alicyclic ring, an aromatic ring, or a heterocyclic ring that may contain a heteroatom such as an oxygen atom are shown below. The positions at which Q2 and Q3 are bonded in T are not particularly limited, but can be appropriately selected taking into consideration reactivity due to steric factors, the availability of commercially available reagents used in the reaction, and the like.

[0055] [ka]

[0056] Preferred examples of the organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in formula (Sm-R) include the following: In the following formula, (Si) is written to indicate the bonding site with Si.

[0057] [ka]

[0058] [ka]

[0059] Also, R 5 , R 6 , R 7 As examples of the organic group, an organic group containing a silicon-silicon bond can also be used. Specific examples include the following: [ka]

[0060] Also, R 5 , R 6 , and R 7 Examples of the organic group include organic groups having a protecting group that is decomposed by an acid. Specific examples include the organic groups listed in paragraphs (0043) to (0048) of JP-A No. 2013-167669 and the organic groups obtained from silicon compounds listed in paragraph (0056) of JP-A No. 2013-224279.

[0061] Furthermore, R 5 , R 6 , and R 7As an example of the organic group, an organic group having a fluorine atom can also be used. Specific examples include organic groups obtained from silicon compounds described in paragraphs (0059) to (0065) of JP-A No. 2012-53253.

[0062] (Method for synthesizing thermally crosslinkable polysiloxane (Sx)) The thermally crosslinkable polysiloxane of the present invention can be produced by hydrolyzing and condensing the following hydrolyzable monomer (Sm).

[0063] (Hydrolyzable Monomer (Sm))

[0064] The hydrolyzable monomer (Sm) has one, two or three hydrolyzable groups such as chlorine, bromine, iodine, acetoxy, methoxy, ethoxy, propoxy or butoxy groups bonded to the silicon atom represented by (Si) in the partial structure. The hydrolyzable monomer (Sm) is a raw material for synthesizing the thermally crosslinkable polysiloxane (Sx) of the present invention, and specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrippropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrippropoxysilane, and ethyltriisopropoxysilane. Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrippropoxysilane, vinyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrippropoxysilane, propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltrippropoxysilane, isopropyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrippropoxysilane, butyltriisopropoxysilane, isobutyl t-butyltrimethoxysilane, isobutyltriethoxysilane, isobutyltrippropoxysilane, isobutyltriisopropoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltrippropoxysilane, sec-butyltriisopropoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltrippropoxysilane, t-butyltriisopropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrippropoxysilane, allyltriisopropoxy Silane, cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane, cyclopropyltripropoxysilane, cyclopropyltriisopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyltrippropoxysilane, cyclobutyltriisopropoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltrippropoxysilane, cyclopentyltriisopropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,Cyclohexyl tripropoxysilane, cyclohexyl triisopropoxysilane, cyclohexenyl trimethoxysilane, cyclohexenyl triethoxysilane, cyclohexenyl tripropoxysilane, cyclohexenyl triisopropoxysilane, cyclohexenyl ethyl trimethoxysilane, cyclohexenyl ethyl triethoxysilane, cyclohexenyl ethyl tripropoxysilane, cyclohexenyl ethyl triisopropoxysilane, cyclooctyl trimethoxysilane, cyclooctyl triethoxysilane, cyclooctyl tripro cyclooctyltriisopropoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltripropoxysilane, bicycloheptenyltriisopropoxysilane, bicycloheptyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltripropoxysilane, bicycloheptenyltriisopropoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptenyltriisopropoxysilane butyltripropoxysilane, bicycloheptyltriisopropoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyltripropoxysilane, adamantyltriisopropoxysilane, cyclopropylmethyltrimethoxysilane, cyclopropylmethyltriethoxysilane, cyclopropylmethyltripropoxysilane, cyclopropylmethyltriisopropoxysilane, cyclobutylmethyltrimethoxysilane, cyclobutylmethyltriethoxysilane, cyclobutylmethyltripropoxysilane, cyclo butylmethyltriisopropoxysilane, cyclopentylmethyltrimethoxysilane, cyclopentylmethyltriethoxysilane, cyclopentylmethyltripropoxysilane, cyclopentylmethyltriisopropoxysilane, cyclohexylmethyltrimethoxysilane, cyclohexylmethyltriethoxysilane, cyclohexylmethyltripropoxysilane, cyclohexylmethyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrippropoxysilane, phenyltriisopropoxysilane,Benzyltrimethoxysilane, benzyltriethoxysilane, benzyltripropoxysilane, benzyltriisopropoxysilane, methylbenzyltrimethoxysilane, methylbenzyltriethoxysilane, methylbenzyltrippropoxysilane, methylbenzyltriisopropoxysilane, ethylbenzyltrimethoxysilane, ethylbenzyltriethoxysilane, ethylbenzyltrippropoxysilane, ethylbenzyltriisopropoxysilane, propylbenzyltrimethoxysilane, propylbenzyltriethoxysilane, propylbenzyltrippropoxysilane Lan, propylbenzyl triisopropoxysilane, isopropylbenzyl trimethoxysilane, isopropylbenzyl triethoxysilane, isopropylbenzyl tripropoxysilane, isopropylbenzyl triisopropoxysilane, fluorobenzyl trimethoxysilane, fluorobenzyl triethoxysilane, fluorobenzyl tripropoxysilane, fluorobenzyl triisopropoxysilane, chlorobenzyl trimethoxysilane, chlorobenzyl triethoxysilane, chlorobenzyl tripropoxysilane, chlorobenzyl triisopropoxysilane,

[0065] Bromobenzyltrimethoxysilane, Bromobenzyltriethoxysilane, Bromobenzyltripropoxysilane, Bromobenzyltriisopropoxysilane, Iodobenzyltrimethoxysilane, Iodobenzyltriethoxysilane, Iodobenzyltrippropoxysilane, Iodobenzyltriisopropoxysilane, Methoxybenzyltrimethoxysilane, Methoxybenzyltriethoxysilane, Methoxybenzyltrippropoxysilane, Methoxybenzyltriisopropoxysilane, Ethoxybenzyltrimethoxysilane, Ethoxybenzyltriisopropoxysilane Isopropyltriethoxysilane, Ethoxybenzyl tripropoxysilane, Ethoxybenzyl triisopropoxysilane, Propoxybenzyl trimethoxysilane, Propoxybenzyl triethoxysilane, Propoxybenzyl tripropoxysilane, Propoxybenzyl triisopropoxysilane, Isopropoxybenzyl trimethoxysilane, Isopropoxybenzyl triethoxysilane, Isopropoxybenzyl tripropoxysilane, Isopropoxybenzyl triisopropoxysilane, Butoxybenzyl trimethoxysilane, Butoxybenzyl triethoxysilane Silane, butoxybenzyl tripropoxysilane, butoxybenzyl triisopropoxysilane, isobutoxybenzyl trimethoxysilane, isobutoxybenzyl triethoxysilane, isobutoxybenzyl tripropoxysilane, isobutoxybenzyl triisopropoxysilane, sec-butoxybenzyl trimethoxysilane, sec-butoxybenzyl triethoxysilane, sec-butoxybenzyl tripropoxysilane, sec-butoxybenzyl triisopropoxysilane, t-butoxybenzyl trimethoxysilane, t-butoxy Benzyl triethoxysilane, t-butoxybenzyl tripropoxysilane, t-butoxybenzyl triisopropoxysilane, acetylbenzyl trimethoxysilane, acetylbenzyl triethoxysilane, acetylbenzyl tripropoxysilane, acetylbenzyl triisopropoxysilane, hydroxybenzyl trimethoxysilane, hydroxybenzyl triethoxysilane, hydroxybenzyl tripropoxysilane, hydroxybenzyl triisopropoxysilane, sulfobenzyl trimethoxysilane, sulfobenzyl triethoxysilane,Sulfobenzyl tripropoxysilane, sulfobenzyl triisopropoxysilane, nitrobenzyl trimethoxysilane, nitrobenzyl triethoxysilane, nitrobenzyl tripropoxysilane, nitrobenzyl triisopropoxysilane, anisyl trimethoxysilane, anisyl triethoxysilane, anisyl tripropoxysilane, anisyl triisopropoxysilane, tolyl trimethoxysilane, tolyl triethoxysilane, tolyl tripropoxysilane, tolyl triisopropoxysilane, phenethyl trimethoxysilane, Phenethyltriethoxysilane, phenethyltripropoxysilane, phenethyltriisopropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltrippropoxysilane, naphthyltriisopropoxysilane, naphthylmethyltrimethoxysilane, naphthylmethyltriethoxysilane, naphthylmethyltrippropoxysilane, naphthylmethyltriisopropoxysilane, methylnaphthylmethyltrimethoxysilane, methylnaphthylmethyltriethoxysilane, methylnaphthylmethyltrippropoxysilane, Methyl naphthyl methyl triisopropoxysilane, ethyl naphthyl methyl trimethoxysilane, ethyl naphthyl methyl triethoxysilane, ethyl naphthyl methyl tripropoxysilane, ethyl naphthyl methyl triisopropoxysilane, propyl naphthyl methyl trimethoxysilane, propyl naphthyl methyl triethoxysilane, propyl naphthyl methyl tripropoxysilane, propyl naphthyl methyl triisopropoxysilane, isopropyl naphthyl methyl trimethoxysilane, isopropyl naphthyl methyl triethoxysilane, Isopropyl naphthyl methyl tripropoxysilane, isopropyl naphthyl methyl triisopropoxysilane, fluoronaphthyl methyl trimethoxysilane, fluoronaphthyl methyl triethoxysilane, fluoronaphthyl methyl tripropoxysilane, fluoronaphthyl methyl triisopropoxysilane, chloronaphthyl methyl trimethoxysilane, chloronaphthyl methyl triethoxysilane, chloronaphthyl methyl tripropoxysilane, chloronaphthyl methyl triisopropoxysilane, bromonaphthyl methyl trimethoxysilane,

[0066] Bromonaphthyl methyltriethoxysilane, Bromonaphthyl methyltripropoxysilane, Bromonaphthyl methyltriisopropoxysilane, Iodonaphthyl methyltrimethoxysilane, Iodonaphthyl methyltriethoxysilane, Iodonaphthyl methyltripropoxysilane, Iodonaphthyl methyltriisopropoxysilane, Methoxynaphthyl methyltrimethoxysilane, Methoxynaphthyl methyltriethoxysilane, Methoxynaphthyl methyltripropoxysilane, Methoxynaphthyl methyltriisopropoxysilane, Ethoxynaphthyl methyl Trimethoxysilane, Ethoxynaphthylmethyltriethoxysilane, Ethoxynaphthylmethyltripropoxysilane, Ethoxynaphthylmethyltriisopropoxysilane, Propoxynaphthylmethyltrimethoxysilane, Propoxynaphthylmethyltriethoxysilane, Propoxynaphthylmethyltripropoxysilane, Propoxynaphthylmethyltriisopropoxysilane, Isopropoxynaphthylmethyltrimethoxysilane, Isopropoxynaphthylmethyltriethoxysilane, Isopropoxynaphthylmethyltripropoxysilane, Isopropoxynaphthylmethyltripropoxysilane sec-Butoxynaphthylmethyltriisopropoxysilane, Butoxynaphthylmethyltrimethoxysilane, Butoxynaphthylmethyltriethoxysilane, Butoxynaphthylmethyltripropoxysilane, Butoxynaphthylmethyltriisopropoxysilane, Isobutoxynaphthylmethyltrimethoxysilane, Isobutoxynaphthylmethyltriethoxysilane, Isobutoxynaphthylmethyltripropoxysilane, Isobutoxynaphthylmethyltriisopropoxysilane, sec-Butoxynaphthylmethyltrimethoxysilane, sec-Butoxynaphthylmethyltriisopropoxysilane Iethoxysilane, sec-butoxynaphthylmethyltripropoxysilane, sec-butoxynaphthylmethyltriisopropoxysilane, t-butoxynaphthylmethyltrimethoxysilane, t-butoxynaphthylmethyltriethoxysilane, t-butoxynaphthylmethyltripropoxysilane, t-butoxynaphthylmethyltriisopropoxysilane, acetylnaphthylmethyltrimethoxysilane, acetylnaphthylmethyltriethoxysilane, acetylnaphthylmethyltripropoxysilane, acetylnaphthylmethyltriisopropoxysilane,Hydroxynaphthylmethyltrimethoxysilane, Hydroxynaphthylmethyltriethoxysilane, Hydroxynaphthylmethyltripropoxysilane, Hydroxynaphthylmethyltriisopropoxysilane, Sulfonaphthylmethyltrimethoxysilane, Sulfonaphthylmethyltriethoxysilane, Sulfonaphthylmethyltripropoxysilane, Sulfonaphthylmethyltriisopropoxysilane, Nitronaphthylmethyltrimethoxysilane, Nitronaphthylmethyltriethoxysilane, Nitronaphthylmethyltrippropoxysilane, Nitronaphthylmethyl Triisopropoxysilane, Methoxymethyltrimethoxysilane, Methoxymethyltriethoxysilane, Methoxymethyltripropoxysilane, Methoxymethyltriisopropoxysilane, Ethoxymethyltrimethoxysilane, Ethoxymethyltriethoxysilane, Ethoxymethyltripropoxysilane, Ethoxymethyltriisopropoxysilane, Propoxymethyltrimethoxysilane, Propoxymethyltriethoxysilane, Propoxymethyltripropoxysilane, Propoxymethyltriisopropoxysilane, Isopropoxymethyl Trimethoxysilane, Isopropoxymethyltriethoxysilane, Isopropoxymethyltripropoxysilane, Isopropoxymethyltriisopropoxysilane, Butoxymethyltrimethoxysilane, Butoxymethyltriethoxysilane, Butoxymethyltripropoxysilane, Butoxymethyltriisopropoxysilane, Isobutoxymethyltrimethoxysilane, Isobutoxymethyltriethoxysilane, Isobutoxymethyltripropoxysilane, Isobutoxymethyltriisopropoxysilane, Sec-Butoxymethyltrimethoxysilane silane, sec-butoxymethyltriethoxysilane, sec-butoxymethyltripropoxysilane, sec-butoxymethyltriisopropoxysilane, t-butoxymethyltrimethoxysilane, t-butoxymethyltriethoxysilane, t-butoxymethyltripropoxysilane, t-butoxymethyltriisopropoxysilane, pentoxymethyltrimethoxysilane, pentoxymethyltriethoxysilane, pentoxymethyltripropoxysilane, pentoxymethyltriisopropoxysilane, isopentoxymethyltrimethoxysilane,

[0067] Isopentoxymethyltriethoxysilane, isopentoxymethyltripropoxysilane, isopentoxymethyltriisopropoxysilane, sec-pentoxymethyltrimethoxysilane, sec-pentoxymethyltriethoxysilane, sec-pentoxymethyltripropoxysilane, sec-pentoxymethyltriisopropoxysilane, 3-pentoxymethyltrimethoxysilane, 3-pentoxymethyltriethoxysilane, 3-pentoxymethyltripropoxysilane, 3-pentoxymethyltriisopropoxysilane, t-pentoxy Methyltrimethoxysilane, t-pentoxymethyltriethoxysilane, t-pentoxymethyltripropoxysilane, t-pentoxymethyltriisopropoxysilane, neopentoxymethyltrimethoxysilane, neopentoxymethyltriethoxysilane, neopentoxymethyltrippropoxysilane, neopentoxymethyltriisopropoxysilane, fluoromethyltrimethoxysilane, fluoromethyltriethoxysilane, fluoromethyltrippropoxysilane, fluoromethyltriisopropoxysilane, chloromethyltrimethoxysilane , Chloromethyltriethoxysilane, Chloromethyltripropoxysilane, Chloromethyltriisopropoxysilane, Bromomethyltrimethoxysilane, Bromomethyltriethoxysilane, Bromomethyltrippropoxysilane, Bromomethyltriisopropoxysilane, Iodomethyltrimethoxysilane, Iodomethyltriethoxysilane, Iodomethyltrippropoxysilane, Iodomethyltriisopropoxysilane, Hydroxymethyltrimethoxysilane, Hydroxymethyltriethoxysilane, Hydroxymethyltrippropoxysilane, Hydroxymethyltripropoxysilane hydroxymethyltriisopropoxysilane, sulfomethyltrimethoxysilane, sulfohydroxymethyltriethoxysilane, sulfomethyltripropoxysilane, sulfomethyltriisopropoxysilane, nitromethyltrimethoxysilane, nitromethyltriethoxysilane, nitromethyltrippropoxysilane, nitromethyltriisopropoxysilane, carboxymethyltrimethoxysilane, carboxymethyltriethoxysilane, carboxymethyltrippropoxysilane, carboxymethyltriisopropoxysilane, dimethyldimethoxysilane,Dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, dipropyldiisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropyl Propoxysilane, Dibutyldimethoxysilane, Dibutyldiethoxysilane, Dibutyldipropoxysilane, Dibutyldiisopropoxysilane, Di-sec-butyldimethoxysilane, Di-sec-butyldiethoxysilane, Di-sec-butyldipropoxysilane, Di-sec-butyldiisopropoxysilane, Di-t-butyldimethoxysilane, Di-t-butyldiethoxysilane, Di-t-butyldipropoxysilane, Di-t-butyldiisopropoxysilane, Dicyclopropyldimethoxysilane, Dicyclopropyldiethoxysilane, Dicyclopropyldipropoxy Silane, dicyclopropyl diisopropoxysilane, dicyclobutyl dimethoxysilane, dicyclobutyl diethoxysilane, dicyclobutyl dipropoxysilane, dicyclobutyl diisopropoxysilane, dicyclopentyl dimethoxysilane, dicyclopentyl diethoxysilane, dicyclopentyl dipropoxysilane, dicyclopentyl diisopropoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, dicyclohexyl dipropoxysilane, dicyclohexyl diisopropoxysilane, dicyclohexenyl dimethicone dicyclohexenyldiethoxysilane, dicyclohexenyldipropoxysilane, dicyclohexenyldiisopropoxysilane, dicyclohexenylethyldimethoxysilane, dicyclohexenylethyldiethoxysilane, dicyclohexenylethyldipropoxysilane, dicyclohexenylethyldiisopropoxysilane, dicyclooctyldimethoxysilane, dicyclooctyldiethoxysilane, dicyclooctyldipropoxysilane, dicyclooctyldiisopropoxysilane, dicyclopentadienylpropyldimethoxysilane,Dicyclopentadienylpropyldiethoxysilane, dicyclopentadienylpropyldipropoxysilane, dicyclopentadienylpropyldiisopropoxysilane, bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis(bicycloheptenyl)dipropoxysilane, bis(bicycloheptenyl)diisopropoxysilane, bis(bicycloheptyl)dimethoxysilane, bis(bicycloheptyl)diethoxysilane, bis(bicycloheptyl)dipropoxysilane, bis(bicycloheptyl)diisopropoxysilane, diadamantyldimethoxysilane, diadamantyldiethoxysilane, diadamantyldimethoxysilane Examples of such silane include manthyldipropoxysilane, diadamantyldiisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethylnaphthylmethylmethoxysilane, dimethylnaphthylmethylethoxysilane, dimethylphenethylmethoxysilane, and dimethylphenethylethoxysilane.

[0068] Preferred examples of the above compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, and cyclohexenyltriethoxysilane. Examples of such silanes include methoxysilane, cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, and dimethylphenethylmethoxysilane.

[0069] The synthesis of the thermally crosslinkable polysiloxane (Sx) will be explained in more detail below. (Synthesis method 1: acid catalyst) The thermally crosslinkable polysiloxane (Sx) used in the present invention can be produced by hydrolyzing and condensing one or a mixture of two or more hydrolyzable monomers (Sm) in the presence of an acid catalyst.

[0070] Examples of the acid catalyst used in this case include organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid, as well as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid. The amount of the catalyst used is preferably 1×10 to 10 mol, more preferably 1×10 to 5 mol, and even more preferably 1×10 to 1 mol, per mol of the monomer.

[0071] When obtaining a thermally crosslinkable polysiloxane (Sx) from these monomers by hydrolysis and condensation, the amount of water added is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, and even more preferably 0.1 to 30 mol per mol of hydrolyzable substituent bonded to the monomer. If the amount is 100 mol or less, the apparatus used for the reaction can be made smaller and more economical. If the amount is 0.01 mol or more, the reaction proceeds sufficiently.

[0072] The operation method involves adding a monomer to an aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. A preferred method is to maintain the temperature at 5 to 80°C during the dropwise addition of the monomer, and then mature the mixture at 20 to 80°C.

[0073] Examples of organic solvents that can be added to the aqueous catalyst solution or that can be used to dilute the monomer include 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 amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and butanediol monoethyl ether. Preferred are 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, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, and mixtures thereof.

[0074] Among these organic solvents, water-soluble ones are preferred. Examples include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; polyhydric alcohols such as ethylene glycol and propylene glycol; polyhydric alcohol 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. Among these, those having a boiling point of 100° C. or less are particularly preferred.

[0075] The amount of organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per mole of monomer. A smaller amount of organic solvent used allows for a smaller reaction vessel, which is more economical.

[0076] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture. At this time, the amount of alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used in the catalyst. This alkaline substance may be any substance that exhibits alkaline properties in water.

[0077] Subsequently, by-products such as alcohol produced in the hydrolysis-condensation reaction are preferably removed from the aqueous reaction mixture by vacuum removal or the like. The temperature to which the aqueous reaction mixture is heated depends on the types of organic solvent added and alcohol produced in the reaction, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum used here varies depending on the types of organic solvent and alcohol to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure. While it is difficult to accurately determine the amount of alcohol removed, it is desirable to remove approximately 80 mass% or more of the produced alcohol.

[0078] Next, the acid catalyst used in the hydrolysis and condensation may be removed from the aqueous reaction mixture. To remove the acid catalyst, water and the thermally crosslinkable polysiloxane solution are mixed, and the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used here is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl 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, t-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0079] Furthermore, a mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent can also be used. For example, a methanol-ethyl acetate mixture, an ethanol-ethyl acetate mixture, a 1-propanol-ethyl acetate mixture, a 2-propanol-ethyl acetate mixture, a butanediol monomethyl ether-ethyl acetate mixture, a propylene glycol monomethyl ether-ethyl acetate mixture, an ethylene glycol monomethyl ether-ethyl acetate mixture, a butanediol monoethyl ether-ethyl acetate mixture, a propylene glycol monoethyl ether-ethyl acetate mixture, an ethylene glycol monoethyl ether-ethyl acetate mixture, a butanediol monopropyl ether-ethyl acetate mixture, a propylene glycol monopropyl ether-ethyl acetate mixture, an ethylene glycol monopropyl ether-ethyl acetate mixture, a methanol-methyl isobutyl ketone mixture, an ethanol-methyl isobutyl ketone mixture, a 1-propanol-methyl isobutyl ketone mixture, a 2-propanol-methyl isobutyl ketone mixture, a propylene glycol monomethyl ether-methyl isobutyl ketone mixture, an ethylene glycol monomethyl ether-methyl isobutyl ketone mixture, ton mixture, propylene glycol monoethyl ether-methyl isobutyl ketone mixture, ethylene glycol monoethyl ether-methyl isobutyl ketone mixture, propylene glycol monopropyl ether-methyl isobutyl ketone mixture, ethylene glycol monopropyl ether-methyl isobutyl ketone mixture, methanol-cyclopentyl methyl ether mixture, ethanol-cyclopentyl methyl ether mixture, 1-propanol-cyclopentyl methyl ether mixture, 2-propanol-cyclopentyl methyl ether mixture, propylene glycol monomethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monomethyl ether-cyclopentyl methyl ether mixture, propylene glycol monoethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monoethyl ether-cyclopentyl methyl ether mixture, propylene glycol monopropyl ether-cyclopentyl methyl ether mixture, ethylene glycol monopropyl ether-cyclopentyl methyl ether mixture,Preferred combinations include, but are not limited to, a methanol-propylene glycol methyl ether acetate mixture, an ethanol-propylene glycol methyl ether acetate mixture, a 1-propanol-propylene glycol methyl ether acetate mixture, a 2-propanol-propylene glycol methyl ether acetate mixture, a propylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, an ethylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, a propylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, an ethylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, a propylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, and an ethylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture.

[0080] The mixing ratio of the water-soluble organic solvent to the poorly water-soluble organic solvent is selected as appropriate, but is preferably 0.1 to 1,000 parts by mass of the water-soluble organic solvent per 100 parts by mass of the poorly water-soluble organic solvent, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0081] Subsequently, the solution may be washed with neutral water. This water may be what is commonly called deionized water or ultrapure water. The amount of water used is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and even more preferably 0.1 to 5 L per 1 L of the thermally crosslinkable polysiloxane solution. This washing method involves placing both solutions in the same container, stirring them together, and then leaving the solution to stand to separate the aqueous layer. The number of washes may be one or more times, but washing more than 10 times will not provide the desired effect, so the number of washes is preferably about 1 to 5 times.

[0082] Other methods for removing the acid catalyst include a method using an ion exchange resin and a method in which the acid catalyst is neutralized with an epoxy compound such as ethylene oxide or propylene oxide and then removed. These methods can be appropriately selected depending on the acid catalyst used in the reaction.

[0083] This water washing operation may cause a portion of the thermally crosslinkable polysiloxane to escape into the aqueous layer, thereby providing an effect substantially equivalent to that of the fractionation operation. Therefore, the number of water washes and the amount of washing water may be appropriately selected in consideration of the catalyst removal effect and the fractionation effect.

[0084] In both the thermally crosslinkable polysiloxane solution containing a residual acid catalyst and the thermally crosslinkable polysiloxane solution from which the acid catalyst has been removed, the desired thermally crosslinkable polysiloxane solution is obtained by adding a final solvent and performing solvent exchange under reduced pressure. The temperature for solvent exchange depends on the types of reaction solvent and extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum varies depending on the type of extraction solvent to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure.

[0085] In this case, the change in solvent may cause the thermally crosslinkable polysiloxane to become unstable. This occurs due to the compatibility between the final solvent and the thermally crosslinkable polysiloxane. To prevent this, a monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent, as described in paragraphs (0181) and (0182) of JP 2009-126940 A, may 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, per 100 parts by mass of the thermally crosslinkable polysiloxane in the solution before the solvent exchange. However, if added, 0.5 parts by mass or more is preferred. If necessary, the solvent exchange operation may be performed by adding a monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent to the solution before the solvent exchange.

[0086] The thermally crosslinkable polysiloxane is preferably kept in a solution state of an appropriate concentration. The concentration at this time is preferably 0.1 to 20% by mass. At such a concentration, further condensation reaction does not proceed, and the polysiloxane does not change to a state in which it cannot be redissolved in an organic solvent. Furthermore, the amount of solvent required is reduced, which is economical and preferable.

[0087] The final solvent to be added to the thermally crosslinkable polysiloxane solution is preferably an alcohol-based solvent, and particularly preferably a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, or butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, or diacetone alcohol is preferred.

[0088] If these solvents are the main component, it is also possible to add a non-alcoholic solvent as an auxiliary solvent, such as acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl 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, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, or cyclopentyl methyl ether.

[0089] Another reaction procedure using an acid catalyst is to add water or a water-containing organic solvent to a monomer or an organic solution of the monomer to initiate the hydrolysis reaction. The catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. A preferred method involves heating the mixture to 10 to 50°C during the dropwise addition of water, and then raising the temperature to 20 to 80°C for aging.

[0090] When an organic solvent is used, it is preferably a water-soluble one, and examples thereof include polyhydric alcohol condensate derivatives such as 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, and propylene glycol monopropyl ether acetate, and mixtures thereof.

[0091] The amount of organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per mole of monomer. A smaller amount of organic solvent used allows for a smaller reaction vessel, which is more economical. The aqueous reaction mixture obtained can be post-treated in the same manner as described above to obtain a thermally crosslinkable polysiloxane.

[0092] (Synthesis method 2: Alkaline catalyst) The thermally crosslinkable polysiloxane (Sx) can be produced by hydrolyzing and condensing one or a mixture of two or more hydrolyzable monomers (Sm) in the presence of an alkali catalyst. Examples of the alkali catalyst used in this case include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclocyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. The amount of the catalyst used is preferably 1×10 −6 mol to 10 mol, more preferably 1×10 −5 mol to 5 mol, and even more preferably 1×10 −4 mol to 1 mol, per mol of the monomer.

[0093] When obtaining a thermally crosslinkable polysiloxane from the above monomers by hydrolysis and condensation, the amount of water added is preferably 0.1 to 50 moles per mole of hydrolyzable substituent bonded to the monomer. If the amount is 50 moles or less, the equipment used for the reaction can be small and economical. If the amount is 0.1 mole or more, the reaction proceeds sufficiently.

[0094] The operation method involves adding a monomer to an aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. A preferred method is to maintain the temperature at 5 to 80°C during the dropwise addition of the monomer, and then mature the mixture at 20 to 80°C.

[0095] As the organic solvent that can be added to the aqueous alkali catalyst solution or that can dilute the monomer, the same organic solvents as those exemplified as those that can be added to the aqueous acid catalyst solution are preferably used. The amount of organic solvent used is preferably 0 to 1,000 ml per mole of monomer, in order to carry out the reaction economically.

[0096] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture. At this time, the amount of the acidic substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the alkaline substance used in the catalyst. This acidic substance may be any substance that is acidic in water.

[0097] Subsequently, by-products such as alcohol produced in the hydrolysis-condensation reaction are preferably removed from the aqueous reaction mixture by vacuum removal or the like. The temperature to which the aqueous reaction mixture is heated depends on the type of organic solvent added and the type of alcohol produced in the reaction, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum used here varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure. While it is difficult to accurately determine the amount of alcohol removed, it is desirable to remove approximately 80 mass% or more of the produced alcohol.

[0098] Next, to remove the catalyst used in the hydrolysis and condensation, the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used here is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl 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, t-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0099] Furthermore, it is also possible to use a mixture of a water-soluble organic solvent and a slightly water-soluble organic solvent.

[0100] Specific examples of the organic solvent used when removing the alkali catalyst include the organic solvents specifically exemplified above as those used when removing the acid catalyst, and mixtures of water-soluble organic solvents and poorly water-soluble organic solvents.

[0101] The mixing ratio of the water-soluble organic solvent to the poorly water-soluble organic solvent is appropriately selected, but is preferably 0.1 to 1,000 parts by mass of the water-soluble organic solvent per 100 parts by mass of the poorly water-soluble organic solvent, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0102] The mixture is then washed with neutral water. This water may be what is commonly called deionized water or ultrapure water. The amount of water used is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and even more preferably 0.1 to 5 L per 1 L of the thermally crosslinkable polysiloxane solution. This washing method involves placing both in the same container, stirring, and then leaving the mixture to stand to separate the aqueous layer. The number of washes may be one or more times, but washing more than 10 times will not provide the desired effect, so the number of washes is preferably about 1 to 5 times.

[0103] The final solvent is added to the washed thermally crosslinkable polysiloxane solution, and solvent exchange is performed under reduced pressure to obtain the desired thermally crosslinkable polysiloxane solution. The temperature for solvent exchange depends on the type of extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum varies depending on the type of extraction solvent to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure.

[0104] The final solvent to be added to the thermally crosslinkable polysiloxane solution is preferably an alcohol-based solvent, and particularly preferably a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, or dipropylene glycol.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, or diacetone alcohol is preferred.

[0105] Another reaction procedure using an alkali catalyst involves adding water or a water-containing organic solvent to a monomer or an organic solution of the monomer to initiate the hydrolysis reaction. The catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. A preferred method involves heating the mixture to 10 to 50°C during the dropwise addition of water, and then raising the temperature to 20 to 80°C for aging.

[0106] The organic solvent that can be used as the organic solution of the monomer or the aqueous organic solvent is preferably a water-soluble one, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, polyhydric alcohol condensate derivatives such as 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, and propylene glycol monopropyl ether acetate, and mixtures thereof.

[0107] The molecular weight of the thermally crosslinkable polysiloxane obtained by synthesis method 1 or 2 can be adjusted not only by the selection of monomers but also by controlling the reaction conditions during polymerization, but a weight-average molecular weight of 100,000 or less prevents the generation of foreign matter or coating spots, so it is preferable to use one of 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. Note that the data on the weight-average molecular weight above was measured by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an eluent, and expressed as a molecular weight converted into polystyrene using polystyrene as a standard substance.

[0108] The physical properties of the thermally crosslinkable polysiloxane used in the present invention vary depending on the type of acid or alkali catalyst used during hydrolysis and condensation and the reaction conditions, and therefore can be appropriately selected according to the desired performance of the resist film.

[0109] Furthermore, a polysiloxane derivative produced by using a mixture of one or more hydrolyzable monomers (Sm) and a hydrolyzable metal compound represented by the following formula (Mm) under the conditions using the acid or alkali catalyst can be used as a component of a composition for forming a resist film. U(OR 7 ) m7 (OR 8 ) m8 (Mm) (In the formula, R 7 , R 8 is an organic group having 1 to 30 carbon atoms, m7 + m8 is the same as the valence determined by the type of U, m7 and m8 are integers of 0 or more, and U is an element of Group III, IV, or V of the periodic table, excluding carbon and silicon.

[0110] Examples of the hydrolyzable metal compound represented by the above formula (Mm) used in this case include the following: When U is boron, examples of the hydrolyzable metal compound represented by formula (Mm) include boron methoxide, boron ethoxide, boron propoxide, boron butoxide, boron amyloxide, boron hexyloxide, boron cyclopentoxide, boron cyclohexyloxide, boron allyloxide, boron phenoxide, boron methoxyethoxide, boric acid, and boron oxide.

[0111] When U is aluminum, examples of the hydrolyzable metal compound represented by the formula (Mm) include aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, aluminum amyloxide, aluminum hexyloxide, aluminum cyclopentoxide, aluminum cyclohexyloxide, aluminum allyloxide, aluminum phenoxide, aluminum methoxyethoxide, aluminum ethoxyethoxide, aluminum dipropoxyethyl acetoacetate, aluminum dibutoxyethyl acetoacetate, aluminum propoxybisethyl acetoacetate, aluminum butoxybisethyl acetoacetate, aluminum 2,4-pentanedionate, and aluminum 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0112] When U is gallium, examples of the hydrolyzable metal compound represented by the formula (Mm) include gallium methoxide, gallium ethoxide, gallium propoxide, gallium butoxide, gallium amyloxide, gallium hexyloxide, gallium cyclopentoxide, gallium cyclohexyloxide, gallium allyloxide, gallium phenoxide, gallium methoxyethoxide, gallium ethoxyethoxide, gallium dipropoxyethyl acetoacetate, gallium dibutoxyethyl acetoacetate, gallium propoxybisethyl acetoacetate, gallium butoxybisethyl acetoacetate, gallium 2,4-pentanedionate, and gallium 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0113] When U is yttrium, examples of the hydrolyzable metal compound represented by the formula (Mm) include yttrium methoxide, yttrium ethoxide, yttrium propoxide, yttrium butoxide, yttrium amyloxide, yttrium hexyloxide, yttrium cyclopentoxide, yttrium cyclohexyloxide, yttrium allyloxide, yttrium phenoxide, yttrium methoxyethoxide, yttrium ethoxyethoxide, yttrium dipropoxyethyl acetoacetate, yttrium dibutoxyethyl acetoacetate, yttrium propoxybisethyl acetoacetate, yttrium butoxybisethyl acetoacetate, yttrium 2,4-pentanedionate, and yttrium 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0114] When U is germanium, examples of the hydrolyzable metal compound represented by formula (Mm) include germanium methoxide, germanium ethoxide, germanium propoxide, germanium butoxide, germanium amyloxide, germanium hexyloxide, germanium cyclopentoxide, germanium cyclohexyloxide, germanium allyloxide, germanium phenoxide, germanium methoxyethoxide, and germanium ethoxyethoxide.

[0115] When U is titanium, examples of the hydrolyzable metal compound represented by the formula (Mm) include titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, titanium amyloxide, titanium hexyloxide, titanium cyclopentoxide, titanium cyclohexyloxide, titanium allyloxide, titanium phenoxide, titanium methoxyethoxide, titanium ethoxyethoxide, titanium dipropoxybisethylacetoacetate, titanium dibutoxybisethylacetoacetate, titanium dipropoxybis2,4-pentanedionate, and titanium dibutoxybis2,4-pentanedionate.

[0116] When U is hafnium, examples of the hydrolyzable metal compound represented by the formula (Mm) include hafnium methoxide, hafnium ethoxide, hafnium propoxide, hafnium butoxide, hafnium amyloxide, hafnium hexyloxide, hafnium cyclopentoxide, hafnium cyclohexyloxide, hafnium allyloxide, hafnium phenoxide, hafnium methoxyethoxide, hafnium ethoxyethoxide, hafnium dipropoxybisethylacetoacetate, hafnium dibutoxybisethylacetoacetate, hafnium dipropoxybis2,4-pentanedionate, and hafnium dibutoxybis2,4-pentanedionate.

[0117] When U is tin, examples of the hydrolyzable metal compound represented by formula (Mm) include methoxytin, ethoxytin, propoxytin, butoxytin, phenoxytin, methoxyethoxytin, ethoxyethoxytin, tin 2,4-pentanedionate, and tin 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0118] When U is arsenic, examples of the hydrolyzable metal compound represented by formula (Mm) include methoxy arsenic, ethoxy arsenic, propoxy arsenic, butoxy arsenic, and phenoxy arsenic.

[0119] When U is antimony, examples of the hydrolyzable metal compound represented by formula (Mm) include methoxyantimony, ethoxyantimony, propoxyantimony, butoxyantimony, phenoxyantimony, antimony acetate, and antimony propionate.

[0120] When U is niobium, examples of the hydrolyzable metal compound represented by formula (Mm) include methoxy niobium, ethoxy niobium, propoxy niobium, butoxy niobium, and phenoxy niobium.

[0121] When U is tantalum, examples of the hydrolyzable metal compound represented by the formula (Mm) include methoxytantalum, ethoxytantalum, propoxytantalum, butoxytantalum, and phenoxytantalum.

[0122] When U is bismuth, examples of the hydrolyzable metal compound represented by the formula (Mm) include methoxybismuth, ethoxybismuth, propoxybismuth, butoxybismuth, and phenoxybismuth.

[0123] When U is phosphorus, examples of the hydrolyzable metal compound represented by formula (Mm) include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, and diphosphorus pentoxide.

[0124] When U is vanadium, examples of the hydrolyzable metal compound represented by formula (Mm) include vanadium oxide bis(2,4-pentanedionate), vanadium 2,4-pentanedionate, vanadium tributoxide oxide, and vanadium tripropoxide oxide.

[0125] When U is zirconium, examples of the hydrolyzable metal compound represented by formula (Mm) include methoxyzirconium, ethoxyzirconium, propoxyzirconium, butoxyzirconium, phenoxyzirconium, zirconium dibutoxide bis(2,4-pentanedionate), and zirconium dipropoxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate).

[0126] In the composition for forming a silicon-containing resist film of the present invention, the blending amount of the thermally crosslinkable polysiloxane (Sx) is preferably, for example, 0.1 to 10% by mass relative to the solvent.

[0127] [Other ingredients] [Acid generator] The silicon-containing resist film-forming composition of the present invention preferably further contains an acid generator. One or more types of acid generators can be blended. The acid generator may be any substance that acts as an acid precursor, such as a thermal acid generator, a photoacid generator, or an acid multiplier.

[0128] In the present invention, the acid generator is preferably a photoacid generator that generates an acid upon the action of high-energy rays, and the acid generator is preferably a sulfonium salt. Furthermore, a photoacid generator that generates an acid upon the action of high-energy rays is more preferable. More specifically, examples of the photoacid generator include, but are not limited to, the materials described in paragraphs

[0160] to

[0179] of JP 2009-126940 A. The amount of the acid generator to be added is preferably 0 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane (Sx). If necessary, an acid generator may be added to finely adjust the pattern shape, exposure sensitivity, and the like.

[0129] (Crosslinking catalyst) The silicon-containing resist film-forming composition of the present invention can contain a crosslinking catalyst. Such a silicon-containing resist film-forming composition can appropriately adjust the pattern shape, exposure sensitivity, etc. of the resist film while minimizing deterioration of other performance properties, and is also effective in reducing residues derived from the resist film.

[0130] Examples of the crosslinking catalyst (Xc) that can be added include compounds represented by the following formula (Xc0). LaHbA (Xc0) (In formula (Xc0), L represents lithium, sodium, potassium, rubidium, cesium, sulfonium, iodonium, phosphonium, or ammonium; A represents a non-nucleophilic counter ion; a represents an integer of 1 or greater; b represents 0 or an integer of 1 or greater; and a+b represents the valence of the non-nucleophilic counter ion.)

[0131] Specific examples of the crosslinking catalyst (Xc) used in the present invention as a compound represented by formula (Xc0) include sulfonium salts of the following formula (Xc-1), iodonium salts of (Xc-2), phosphonium salts of (Xc-3), and ammonium salts and alkali metal salts of (Xc-4).

[0132] The crosslinking catalyst (Xc) used in the present invention is preferably a sulfonium salt of the following formula (Xc-1) or an ammonium salt of the following formula (Xc-4).

[0133] The sulfonium salts (Xc-1), iodonium salts (Xc-2), phosphonium salts (Xc-3), and ammonium salts (Xc-4) will be explained.

[0134] [ka] (In the formula, R 204 , R 205 , R 206 , and R 207 represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group or the like. 205 and R 206 may form a ring, and when a ring is formed, R 205 , R 206 Each represents an alkylene group having 1 to 6 carbon atoms. A- represents a non-nucleophilic counter ion. R 208 , R 209 , R 210 , and R 211 is R 204 , R 205 , R 206 , and R 207 R is the same as R, but may also be a hydrogen atom. 208 and R 209 , or R 208 and R 209 and R 210may form a ring, and when a ring is formed, R 208 and R 209 , and R 208 and R 209 and R 210 represents an alkylene group having 3 to 10 carbon atoms.

[0135] Above R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , and R 211may be the same or different, and specific 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, norbornyl, and adamantyl. Examples of alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Examples of oxoalkyl groups include 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl. Examples of the oxoalkenyl group include a 2-oxopropenyl group, a 2-oxobutenyl group, a 2-oxohexenyl group, a 2-oxocyclopentenyl group, and a 2-oxocyclohexenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, etc., alkoxyphenyl groups such as p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, and m-tert-butoxyphenyl group, alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group, alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group, alkoxynaphthyl groups such as methoxynaphthyl group and ethoxynaphthyl group, dialkylnaphthyl groups such as dimethylnaphthyl group and diethylnaphthyl group, and dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group, etc. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. Examples of the aryloxoalkyl group include 2-aryl-2-oxoethyl groups such as a 2-phenyl-2-oxoethyl group, a 2-(1-naphthyl)-2-oxoethyl group, and a 2-(2-naphthyl)-2-oxoethyl group.

[0136] Examples of the non-nucleophilic counter ion of A- in the above (Xc-1) to (Xc-4) include hydroxide ion, formate ion, acetate ion, propionate ion, butanoate ion, pentanoate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleate ion, linolenate ion, benzoate ion, phthalate ion, isophthalate ion, terephthalate ion, salicylate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, trichloroacetate ion, fluorine ion, chloride ion, bromide ion, and iodide. Examples of monovalent ions include monobasic ions, nitrate ions, nitrite ions, chlorate ions, bromate ions, methanesulfonate ions, paratoluenesulfonate ions, and monomethylsulfate ions; monovalent or divalent oxalate ions; malonate ions, methylmalonate ions, ethylmalonate ions, propylmalonate ions, butylmalonate ions, dimethylmalonate ions, diethylmalonate ions, succinate ions, methylsuccinate ions, glutarate ions, adipate ions, itaconate ions, maleate ions, fumarate ions, citraconic acid ions, citrate ions, carbonate ions, and sulfate ions.

[0137] Examples of alkali metal salts include monovalent salts such as hydroxide, formate, acetate, propionate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, oleate, stearate, linoleate, linolenate, benzoate, phthalate, isophthalate, terephthalate, salicylate, trifluoroacetate, monochloroacetate, dichloroacetate, and trichloroacetate; monovalent or divalent oxalate; malonate, methylmalonate, ethylmalonate, propylmalonate, butylmalonate, dimethylmalonate, diethylmalonate, succinate, methylsuccinate, glutarate, adipate, itaconate, maleate, fumarate, citraconate, citrate, and carbonate of lithium, sodium, potassium, cesium, magnesium, and calcium.

[0138] Specifically, examples of the sulfonium salt (Xc-1) include triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionate, triphenylsulfonium butanoate, 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, triphenylsulfonium methylmalonate, ethylenediamine, ethylenediamine, ethylenediamine, ethylenediamine, ethylenediamine, ethylenediamine Examples of the alkyl esters include triphenylsulfonium ethylmalonate, triphenylsulfonium propylmalonate, triphenylsulfonium butylmalonate, triphenylsulfonium dimethylmalonate, triphenylsulfonium diethylmalonate, triphenylsulfonium succinate, triphenylsulfonium methylsuccinate, triphenylsulfonium glutarate, triphenylsulfonium adipate, triphenylsulfonium itaconate, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylsulfonium citraconic acid, triphenylsulfonium citrate, triphenylsulfonium carbonate, bistriphenylsulfonium oxalate, bistriphenylsulfonium maleate, bistriphenylsulfonium fumarate, bistriphenylsulfonium citraconic acid, bistriphenylsulfonium citrate, and bistriphenylsulfonium carbonate.

[0139] Specific examples of the iodonium salt (Xc-2) include diphenyliodonium formate, diphenyliodonium acetate, diphenyliodonium propionate, diphenyliodonium butanoate, diphenyliodonium benzoate, diphenyliodonium phthalate, diphenyliodonium isophthalate, diphenyliodonium terephthalate, diphenyliodonium salicylate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium monochloroacetate, diphenyliodonium dichloroacetate, diphenyliodonium trichloroacetate, diphenyliodonium hydroxide, Examples of the diphenyliodonium carbonate include bisdiphenyliodonium oxalate, bisdiphenyliodonium maleate, bisdiphenyliodonium fumarate, bisdiphenyliodonium citraconic acid, bisdiphenyliodonium citrate, and bisdiphenyliodonium carbonate.

[0140] Specific examples of the phosphonium salt (Xc-3) include tetraethylphosphonium formate, tetraethylphosphonium acetate, tetraethylphosphonium propionate, tetraethylphosphonium butanoate, tetraethylphosphonium benzoate, tetraethylphosphonium phthalate, tetraethylphosphonium isophthalate, tetraethylphosphonium terephthalate, tetraethylphosphonium salicylate, tetraethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoroacetate, tetraethylphosphonium monochloroacetate, tetraethylphosphonium dichloroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium hydroxide, tetraethylphosphonium nitrate, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetraethylphosphonium oxalate, tetraethylphosphonium maleate, tetraethylphosphonium fumarate, tetraethylphosphonium citraconic acid, tetraethylphosphonium citrate, tetraethylphosphonium carbonate, bistetraethylphosphonium oxalate, bistetraethylphosphonium maleate, thiaminyl phosphonium, bistetraethylphosphonium fumarate, bistetraethylphosphonium citraconic acid, bistetraethylphosphonium citrate, bistetraethylphosphonium carbonate, tetraphenylphosphonium formate, tetraphenylphosphonium acetate, tetraphenylphosphonium propionate, tetraphenylphosphonium butanoate, tetraphenylphosphonium benzoate, tetraphenylphosphonium phthalate, tetraphenylphosphonium isophthalate, tetraphenylphosphonium terephthalate, tetraphenylphosphonium salicylate, tetraphenylphosphonium trifluoromethanesulfonate, tetraphenylphosphonium trifluoroacetate, tetraphenylphosphonium monochloroacetate, tetraphenylphosphonium dichloroacetate, tetraphenylphosphonium trichloroacetate, tetraphenylphosphonium hydroxide, tetraphenylphosphonium nitrate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium oxalate, tetraphenylphosphonium maleate, tetraphenylphosphonium fumarate,Examples of such tetraphenylphosphonium compounds include tetraphenylphosphonium citrate, tetraphenylphosphonium carbonate, bistetraphenylphosphonium oxalate, bistetraphenylphosphonium maleate, bistetraphenylphosphonium fumarate, bistetraphenylphosphonium citraconic acid, bistetraphenylphosphonium citrate, and bistetraphenylphosphonium carbonate.

[0141] On the other hand, specific examples of the ammonium salt (Xc-4) include tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butanoate, 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 citraconate, tetramethylammonium citrate, and tetramethylammonium carbonate. ammonium, bistetramethylammonium oxalate, bistetramethylammonium malonate, bistetramethylammonium maleate, bistetramethylammonium fumarate, bistetramethylammonium citraconate, bistetramethylammonium citrate, bistetramethylammonium carbonate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butanoate, 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 citraconate, tetraethylammonium citrate, tetraethylammonium carbonate, bistetraethylammonium oxalate, bistetraethylammonium malonate, bistetraethylammonium maleate, bistetraethylammonium fumarate, bistetraethylammonium citraconate, bistetraethylammonium citrate, bistetraethylammonium carbonate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butanoate, tetrapropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dipropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dipropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dipropylammonium benzoate, tetra ...benzoate, Tetrapropylammonium dichloroacetate, tetrapropylammonium trichloroacetate, tetrapropylammonium hydroxide, tetrapropylammonium nitrate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrapropylammonium monomethylsulfate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium maleate, tetrapropylammonium fumarate, tetrapropylammonium citraconate, tetrapropylammonium citrate, tetrapropylammonium carbonate, bistetrapropylammonium oxalate, bistetrapropylammonium malonate, bistetrapropylammonium maleate, bistetrapropylammonium fumarate, bistetrapropylammonium citraconate, bistetrapropylammonium citrate, bistetrapropylammonium carbonate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butanoate, tetrabutylammonium benzoate,Examples of the ammonium nitrate include 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 monomethylsulfate, tetrabutylammonium oxalate, tetrabutylammonium malonate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citraconate, tetrabutylammonium citrate, tetrabutylammonium carbonate, bistetrabutylammonium oxalate, bistetrabutylammonium malonate, bistetrabutylammonium maleate, bistetrabutylammonium fumarate, bistetrabutylammonium citraconate, bistetrabutylammonium citrate, and bistetrabutylammonium carbonate.

[0142] Examples of alkali metal salts include lithium formate, lithium acetate, lithium propionate, lithium butanoate, 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 hydrogen oxalate, lithium hydrogen malonate, lithium hydrogen maleate, Lithium hydrogen fumarate, lithium hydrogen citraconic acid, lithium hydrogen citrate, lithium hydrogen carbonate, lithium oxalate, lithium malonate, lithium maleate, lithium fumarate, lithium citraconic acid, lithium citrate, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butanoate, sodium benzoate, sodium phthalate, sodium isophthalate, sodium terephthalate, sodium salicylate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, Sodium dichloroacetate, sodium trichloroacetate, sodium hydroxide, sodium nitrate, sodium chloride, sodium bromide, sodium iodide, sodium methanesulfonate, sodium hydrogen oxalate, sodium hydrogen malonate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium hydrogen citraconate, sodium hydrogen citrate, sodium bicarbonate, sodium oxalate, sodium malonate, sodium maleate, sodium fumarate, sodium citraconate, sodium citrate, sodium carbonate, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium benzoate, potassium phthalate, potassium isophthalate, potassium terephthalate, 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 citraconate,Examples include potassium hydrogen citrate, potassium hydrogen carbonate, potassium oxalate, potassium malonate, potassium maleate, potassium fumarate, potassium citraconate, potassium citrate, and potassium carbonate.

[0143] (Polysiloxane (Xc-10) having a crosslinking catalyst as part of the molecule structure) In the present invention, a polysiloxane (Xc-10) having an ammonium salt, a sulfonium salt, a phosphonium salt, or an iodonium salt as part of its structure may be blended into the composition for forming a resist film as the crosslinking catalyst (Xc).

[0144] As a raw material used to produce (Xc-10) used here, a compound represented by the following formula (Xm) can be used. R 1A A1 R 2A A2 R 3A A3 Si(OR 0A ) (4-A1-A2-A3) (Xm) (In formula (Xm), R 0A is a hydrocarbon group having 1 to 6 carbon atoms, and R 1A , R 2A , and R 3A At least one of these is an organic group having an ammonium salt, a sulfonium salt, a phosphonium salt, or an iodonium salt, and the other is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. A1, A2, and A3 are 0 or 1, and 1≦A1+A2+A3≦3.

[0145] where R 0A Examples of such alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and a phenyl group.

[0146] Examples of Xm include compounds represented by the following formula (Xm-1), which are hydrolyzable silicon compounds having a sulfonium salt as part of their structure. [ka]

[0147] (In formula (Xm-1), R SA1 , and R SA2 represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, or the like. SA1 and R SA2 may form a ring together with the sulfur atom to which they are attached, and when they form a ring, R SA1 , and R SA2 R represents an alkylene group having 1 to 6 carbon atoms. SA3 represents a linear, branched, or cyclic alkylene or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like.

[0148] In the above formula (Xm-1), (Si) is written to indicate the bonding site with Si.

[0149] X- can be hydroxide ion, fluorine ion, chloride ion, bromide ion, iodide ion, formate ion, acetate ion, propionate ion, butanoate ion, pentanoate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleate ion, linolenate ion, benzoate ion, p-methylbenzoate ion, pt-butylbenzoate ion, phthalate ion, isophthalate ion, terephthalate ion, salicylate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, or trichloroacetate ion. , nitrate ion, chlorate ion, perchlorate ion, bromate ion, iodate ion, methanesulfonate ion, benzenesulfonate ion, toluenesulfonate ion, monomethylsulfate ion, hydrogen sulfate ion, oxalate ion, malonate ion, methylmalonate ion, ethylmalonate ion, propylmalonate ion, butylmalonate ion, dimethylmalonate ion, diethylmalonate ion, succinate ion, methylsuccinate ion, glutarate ion, adipate ion, itaconate ion, maleate ion, fumarate ion, citraconic acid ion, citrate ion, and carbonate ion.

[0150] Specific examples of the cation moiety of the compound represented by the above formula (Xm-1) include the following ions. [ka]

[0151] As Xm, for example, a compound represented by the following formula (Xm-2) can be exemplified as a hydrolyzable silicon compound having an iodonium salt as part of its structure. [ka] (In formula (Xm-2), R IA1R represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, or the like. IA2 represents a linear, branched, or cyclic alkylene or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like.

[0152] In the above formula (Xm-2), (Si) is written to indicate the bonding site with Si. X- is as defined above.

[0153] Specific examples of the cation moiety of the compound represented by the above formula (Xm-2) include the following ions.

[0154] [ka]

[0155] As Xm, for example, a compound represented by the following formula (Xm-3) can be exemplified as a hydrolyzable silicon compound having a phosphonium salt as part of its structure. [ka] (In formula (Xm-3), R PA1 , R PA2 , and R PA3represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, or the like. PA1 and R PA2 may form a ring together with the phosphorus atom to which they are attached, and when they form a ring, R PA1 , and R PA2 R represents an alkylene group having 1 to 6 carbon atoms. PA4 is a linear, branched, or cyclic alkylene or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like.

[0156] In the above formula (Xm-3), (Si) is written to indicate the bonding site with Si. X- is as defined above.

[0157] Specific examples of the cation moiety of the compound represented by the above formula (Xm-3) include the following ions.

[0158] [ka]

[0159] [ka]

[0160] As Xm, for example, a compound represented by the following formula (Xm-4) can be exemplified as a hydrolyzable silicon compound having an ammonium salt as part of its structure. [ka] (In formula (Xm-4), RNA1 , R NA2 , and R NA3 each represents a hydrogen atom, a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like. NA1 and R NA2 may form a ring together with the nitrogen atom to which they are attached, and when they form a ring, R NA1 , and R NA2 R represents an alkylene group having 1 to 6 carbon atoms, or a nitrogen-containing heterocyclic ring, or a heteroaromatic ring. NA4 R represents a linear, branched, or cyclic alkylene or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like. NA1 and R NA2 , or R NA1 and R NA4 If the ring structure is formed and contains an unsaturated nitrogen atom, nN3 = 0, otherwise nN3 = 1.)

[0161] In the above formula (Xm-4), (Si) is written to indicate the bonding site with Si. - is as described above.

[0162] Specific examples of the cation moiety of the compound represented by the above formula (Xm-4) include the following ions.

[0163] [ka]

[0164] [ka]

[0165]

change

[0166]

change

[0167]

change

[0168]

change

[0169]

change

[0170]

change

[0171]

change

[0172]

change

[0173]

change

[0174]

change

[0175]

change

[0176] To produce (Xc-10), the hydrolyzable silicon compound used together with (Xm-1), (Xm-2), (Xm-3), and (Xm-4) can be, for example, the hydrolyzable monomer (Sm). A hydrolyzable metal compound (Mm) represented by the formula (Mm) may also be added.

[0177] One or more of the monomers (Xm-1), (Xm-2), (Xm-3), and (Xm-4) shown above, one or more of (Sm), and if necessary, one or more of (Mm), can be selected and mixed before or during the reaction to form (Xc-10). The reaction conditions may be the same as those for the synthesis of the thermally crosslinkable polysiloxane (Sx).

[0178] The molecular weight of the resulting crosslinking catalyst (Xc-10) can be adjusted not only by selecting the monomer but also by controlling the reaction conditions during polymerization, but a weight-average molecular weight of 100,000 or less prevents the generation of foreign matter or coating spots, so it is preferable to use one of 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. Note that the data regarding the weight-average molecular weight above was measured by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an eluent, and expressed as a molecular weight converted into polystyrene using polystyrene as a standard substance.

[0179] The crosslinking catalysts (Xc-1), (Xc-2), (Xc-3), (Xc-4), and (Xc-10) can be used alone or in combination of two or more. The amount of the crosslinking catalyst added is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, per 100 parts by mass of the base polymer (the thermally crosslinkable polysiloxane (Sx) obtained by the above method).

[0180] (organic acid) To improve the stability of the silicon-containing resist film-forming composition of the present invention, it is preferable to add a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms. Examples of the acid to be added include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and citric acid. Oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, and citric acid are particularly preferred. To maintain stability, two or more acids may be mixed and used. The amount of organic acid added is preferably 0.001 to 25 parts by mass, more preferably 0.01 to 15 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of silicon contained in the composition for forming a silicon-containing resist film of the present invention.

[0181] Alternatively, the organic acid may be added so that the pH of the composition for forming a silicon-containing resist film of the present invention is preferably 0≦pH≦7, more preferably 0.3≦pH≦6.5, and even more preferably 0.5≦pH≦6.

[0182] (water) In the present invention, water may be added to the silicon-containing resist film-forming composition. Adding water hydrates the polysiloxane compound in the silicon-containing resist film-forming composition of the present invention, thereby improving lithography performance. The water content in the solvent component of the silicon-containing resist film-forming composition of the present invention is preferably greater than 0% by mass and less than 50% by mass, particularly preferably 0.3 to 30% by mass, and even more preferably 0.5 to 20% by mass. When the amount of water added is less than 50% by mass, the uniformity of the silicon-containing resist film is improved and repellency does not occur. On the other hand, when the amount of water added is greater than 0% by mass, the lithography performance is improved.

[0183] The amount of the total solvent including water used is preferably 100 to 100,000 parts by mass, and particularly preferably 200 to 50,000 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane that is the base polymer.

[0184] (stabilizer) Furthermore, in the present invention, a stabilizer can be added to the silicon-containing resist film-forming composition. A monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent can be added as a stabilizer. In particular, the addition of a stabilizer described in paragraphs

[0181] and

[0182] of JP 2009-126940 A can improve the stability of the silicon-containing resist film-forming composition. The amount of stabilizer added is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane (Sx) that is the base polymer.

[0185] (surfactant) Furthermore, in the present invention, a surfactant can be added to the silicon-containing resist film-forming composition as needed. Specifically, the materials described in paragraph

[0185] of JP 2009-126940 A can be added. The amount of surfactant added is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane (Sx) that is the base polymer.

[0186] (High boiling point solvent) Furthermore, in the present invention, a high boiling point solvent having a boiling point of 180° C. or higher can be added to the composition as needed. Examples of such high boiling point solvents include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 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, glycerin, gamma butyrolactone, tripropylene glycol monomethyl ether, and diacetone alcohol. Examples of the high-boiling point solvent include ethanol, n-nonyl acetate, ethylene glycol monoethyl ether acetate, 1,2-diacetoxyethane, 1-acetoxy-2-methoxyethane, 1,2-diacetoxypropane, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, etc. The amount of the high-boiling point solvent to be blended is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, based on the solvent components.

[0187] [Pattern formation method] One pattern formation method of the present invention is a pattern formation method comprising the steps of: forming an organic film on a workpiece using a coating-type organic film material; forming a silicon-containing resist intermediate film on the organic film using the silicon-containing resist film-forming composition described above; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film composition consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern by etching onto the silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching onto the organic film using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask (a so-called "multilayer resist method").

[0188] One pattern formation method of the present invention is a pattern formation method comprising the steps of: forming a hard mask containing carbon as a main component on a workpiece by a CVD method; forming a silicon-containing resist intermediate film on the hard mask using the silicon-containing resist film-forming composition described above; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film composition consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the hard mask by dry etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and transferring the pattern to the workpiece by dry etching using the hard mask on which the pattern has been transferred as a mask.

[0189] The above-described pattern formation method is particularly practical for forming fine patterns, because it suppresses pattern collapse of the resist upper layer film, provides excellent pattern transfer to the silicon-containing resist intermediate film by dry etching, and is easy to remove the silicon-containing resist intermediate film remaining after patterning is completed, making it unlikely to cause defects due to residues.

[0190] One of the pattern formation methods of the present invention is a method for forming a pattern on a workpiece, and includes the steps of: forming a silicon-containing resist intermediate film on the workpiece using the silicon-containing resist film-forming composition described above; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film composition consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; and transferring the pattern to the workpiece by dry etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask.

[0191] In the positive pattern formation method, a photoresist film (resist upper layer film) is formed, heat-treated, exposed to light, and then typically developed with an alkaline developer to obtain a positive resist pattern. It is also preferable to perform post-exposure baking (PEB) after exposure.

[0192] As the alkaline developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) or the like can be used.

[0193] The method for forming a circuit pattern on the resist upper layer film is preferably a pattern formation method using photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0194] Such a method for forming a circuit pattern on a resist upper layer film allows the effects of the present invention to be more fully exhibited.

[0195] The workpiece is preferably a semiconductor device substrate, or a semiconductor device substrate having any of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, and a metal oxynitride film formed thereon.

[0196] When the above-mentioned specific workpiece is used, the effects of the present invention are more fully exhibited.

[0197] The metal preferably used is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

[0198] If the metal constituting the workpiece is the specific metal, the effects of the present invention are more fully exhibited. [Example]

[0199] The present invention will be specifically explained below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these descriptions. In the following examples, % indicates mass %, and the molecular weight Mw is the weight average molecular weight converted into polystyrene by GPC measurement using tetrahydrofuran as an elution solvent. Furthermore, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0200] [Synthesis Example 1 (Synthesis of Compound 1)] A mixture of 16.4 g of compound (101), 22.8 g of compound (102), and 5.1 g of compound (110) (molar ratio: 40 / 50 / 10) was added to a mixture of 75.6 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol ethyl ether (PGEE) and 1.0 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 240 g of a PGEE solution of thermally crosslinkable polysiloxane compound 1 (compound concentration: 10%). The polystyrene-equivalent molecular weight of thermally crosslinkable polysiloxane compound 1 was measured to be Mw = 2,600.

[0201] Compounds 2 to 18 were synthesized using the monomers shown in Table 1 under the same conditions as in Synthesis Example 1 (Synthesis Examples 2 to 18).

[0202] [Table 1]

[0203] [Comparative synthesis example] Comparative polysiloxane compounds R1 and R2 were synthesized using the monomers shown in Table 2 under the same conditions as in Synthesis Example 1 (Comparative Synthesis Examples 1 and 2). [Table 2]

[0204] PhSi(OCH3)3...Compound (100) CH3Si(OCH3)3...Compound (101) Si(OCH3)4...Compound (102) [ka]

[0205] [Examples and Comparative Examples] The thermally crosslinkable polysiloxane compounds 1 to 18 of the present invention synthesized in the above Synthesis Examples, the comparative polysiloxane compounds R1 and R2 synthesized in the above Comparative Synthesis Examples, a crosslinking catalyst, an acid, a photoacid generator, a solvent, and water were mixed in the proportions shown in Tables 3 and 4, and filtered through a 0.1 μm fluororesin filter to prepare silicon-containing film-forming composition solutions, designated Sol. 1 to 30, respectively.

[0206] [Table 3]

[0207] [Table 4]

[0208] The crosslinking catalysts used were as follows: XL-1 Triphenylsulfonium nitrate XL-2 Tetramethylammonium Nitrate XL-3 Tetraoctylammonium Nitrate

[0209] The solvents used were as follows: PGEE: Propylene glycol monoethyl ether PGME: Propylene glycol monomethyl ether GBL: Gamma Butyrolactone DAA: Diacetone alcohol

[0210] [Table 5]

[0211] [Examples 1-1 to 1-28, Comparative Examples 1-1 to 1-2] (EUV patterning test) Sol. 1 to 30, which are compositions for forming silicon-containing resist films, were spin-coated onto silicon wafers and heated at 220° C. for 60 seconds to prepare Films 1 to 30, which are silicon-containing resist films with a thickness of 25 nm.

[0212] Next, a resist material containing the following components dissolved in the proportions shown in Table 6 was spin-coated onto Films 1 to 30 and pre-baked for 60 seconds at 105°C using a hot plate to produce a 60nm thick resist top layer film. This was then exposed using an ASML EUV scanner NXE3300 (NA 0.33, σ 0.9 / 0.6, quadruple-pole illumination, wafer dimensions 46nm pitch, +20% bias hole pattern mask), subjected to PEB on a hot plate at 100°C for 60 seconds, and developed for 30 seconds in a 2.38% by mass TMAH aqueous solution to obtain a hole pattern with a dimension of 23nm. Using a critical dimension SEM (CG5000) manufactured by Hitachi High-Technologies Corporation, the exposure dose when holes were formed with a dimension of 23 nm was measured and used as the sensitivity. The dimensions of 50 holes were also measured and the dimension variation (CDU, 3σ) was calculated. The results are shown in Table 7.

[0213] The polymer, quencher, sensitizer, surfactant and organic solvent used as the resist material are as follows:

[0214] [ka]

[0215] [ka]

[0216] [ka]

[0217] Surfactant: 3M FC-4430 PGMEA: Propylene glycol monomethyl ether acetate CyHO: Cyclohexanone PGME: Propylene glycol monomethyl ether

[0218] [Table 6]

[0219] (Silicon-containing resist film etching test) Sol. 1 to 30, which are compositions for forming silicon-containing resist films, were spin-coated onto silicon wafers and heated at 220° C. for 60 seconds to prepare Films 1 to 30, which are silicon-containing resist intermediate films with a thickness of 25 nm. These silicon-containing resist intermediate films were subjected to an etching test under the following etching conditions.

[0220] Etching test using CHF3 / CF4 gas Equipment: Tokyo Electron Ltd. dry etching equipment Telius SP Etching test: Chamber pressure 10Pa Upper / Lower RF Power 200W / 100W CHF3 gas flow rate 50ml / min CF4 gas flow rate 50ml / min N2 gas flow rate 100ml / min Processing time: 20 seconds

[0221] [Table 7]

[0222] As shown in Comparative Examples 1-1 and 1-2 in Table 7, Films 29 to 30, which do not use polysiloxanes containing the specific partial structure of the present invention, were found to have poor CDU values ​​or insufficient etching rates. On the other hand, as shown in Examples 1-1 to 1-28, Films 1 to 28, which use polysiloxanes containing the specific partial structure of the present invention, were found to have improved CDU and sufficient etching rates. This is likely due to the elimination reaction of specific substituents caused by heat treatment, resulting in the formation of a strong film with a high Si content. Furthermore, Films 19 to 25, which contain a photoacid generator, are found to have higher sensitivity than the corresponding Films 1 to 7, which do not contain a photoacid generator.

[0223] [Examples 2-1 to 2-28 and Comparative Examples 2-1 to 2-2] (ArF patterning test) A 200 nm thick spin-on carbon film ODL-102 (carbon content: 89% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was formed on a silicon wafer. Silicon-containing resist film-forming compositions Sol. 1 to 30 were applied onto the spin-on carbon film and heated at 220°C for 60 seconds to produce 20 nm thick silicon-containing resist intermediate films Films 1 to 30.

[0224] Next, a positive development ArF resist solution (PR-1) shown in Table 8 was applied onto the silicon-containing resist film and baked at 110°C for 60 seconds to form a photoresist film with a thickness of 100 nm. Further, an immersion protective film material (TC-1) shown in Table 9 was applied onto the photoresist film and baked at 90°C for 60 seconds to form a protective film with a thickness of 50 nm. These were then exposed using an ArF immersion exposure system (ASML XT-1900i, NA 1.35, σ 0.97 / 0.77, 35-degree dipole polarized illumination), baked at 100°C for 60 seconds (PEB), and developed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, yielding a 40 nm 1:1 positive line-and-space pattern. LWR was observed for this dimension using a Hitachi High-Technologies Corporation CG5000 electron microscope. The results are shown in Table 10.

[0225] [Table 8]

[0226] ArF resist polymer 1 [molecular weight (Mw) = 7,800, dispersity (Mw / Mn) = 1.78]:

[0227] [ka]

[0228] Acid generator: PAG-A [ka]

[0229] Base: Quencher [ka]

[0230] Surfactant: 3M FC-4430

[0231] [Table 9]

[0232] Protective film polymer [molecular weight (Mw) = 8,800, dispersity (Mw / Mn) = 1.69]

[0233] [ka]

[0234] [Table 10]

[0235] As shown in Examples 2-1 to 2-28 in Table 10, it was confirmed that Films 1 to 28, which used polysiloxanes containing the specific partial structure of the present invention, exhibited an LWR improvement effect. On the other hand, as shown in Comparative Examples 2-1 to 2-2, Films 29 to 30, which did not use polysiloxanes containing the specific partial structure, exhibited inferior LWR. This is thought to be because in Examples 2-1 to 2-28, the heat treatment caused an elimination reaction of the specific substituent, forming a strong film with a high Si ratio, which suppressed diffusion into the upper layer resist.

[0236] The present specification includes the following aspects.

[0237] [1]: A composition for forming a silicon-containing resist film, characterized by containing a polysiloxane containing at least one of a repeating unit represented by the following formula (A-1), a repeating unit represented by the following formula (A-2), and a partial structure represented by the following formula (A-3): [ka] (In the formula, R 1 is a monovalent organic group having 1 to 30 carbon atoms, which may have a substituent, a halogen atom, a hydroxy group, a sulfo group, a nitro group, or a carboxyl group, which acts as a leaving group when exposed to heat, an acid, or a base, and R 2 , R 3 each independently represents a monovalent organic group having 1 to 30 carbon atoms which may have a substituent.) [2]: R in the formulas (A-1), (A-2), and (A-3) 1 is a monovalent group represented by the following formula (B-1) that functions as a leaving group in the presence of heat, an acid, or a base, a halogen atom, a hydroxy group, a sulfo group, a nitro group, or a carboxyl group: [ka] (In the formula, R4's are substituents bonded to the aromatic ring, and each R4 independently represents a hydrogen atom or an alkyl group of 1 to 20 carbon atoms which may have a substituent, an aryl group of 6 to 20 carbon atoms which may have a substituent, a halogenated alkyl group of 1 to 20 carbon atoms which may have a substituent, a halogenated aryl group of 6 to 20 carbon atoms which may have a substituent, an alkoxyalkyl group of 1 to 20 carbon atoms which may have a substituent, an alkoxyaryl group of 6 to 20 carbon atoms which may have a substituent, an acyl group of 6 to 20 carbon atoms which may have a substituent, a halogen atom, a hydroxyl group, a sulfo group, a nitro group, or a carboxyl group; a=0 or 1; n=2a+5; and * represents a bond to another atom.) [3]: The composition for forming a silicon-containing resist film according to either [1] or [2], wherein the polysiloxane contains a thermally crosslinkable polysiloxane containing at least one of a repeating unit represented by the following formula (Sx-1), a repeating unit represented by the following formula (Sx-2), and a partial structure represented by the following formula (Sx-3): [ka] (In the formula, R 5 , R 6 , R 7 are each independently a monovalent organic group having 1 to 30 carbon atoms which may have a substituent.) [4]: The composition for forming a silicon-containing resist film according to any one of [1] to [3], further comprising a crosslinking catalyst. [5]: The composition for forming a silicon-containing resist film according to [4], wherein the crosslinking catalyst is an ammonium salt or a sulfonium salt. [6]: The composition for forming a silicon-containing resist film according to any one of [1] to [5], further comprising an acid generator. [7]: The composition for forming a silicon-containing resist film according to [6], wherein the acid generator is a sulfonium salt. [8]: A pattern formation method comprising the steps of: forming an organic film on a workpiece using a coating-type organic film material; forming a silicon-containing resist intermediate film on the organic film using the silicon-containing resist film-forming composition according to any one of [1] to [7]; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film composition comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern by etching to the silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching to the organic film using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask. [9]: A pattern formation method comprising the steps of: forming a hard mask mainly composed of carbon on a workpiece by a CVD method; forming a silicon-containing resist intermediate film on the hard mask using the silicon-containing resist film-forming composition according to any one of [1] to [7]; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film composition comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the hard mask by dry etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and transferring the pattern to the workpiece by dry etching using the hard mask on which the pattern has been transferred as a mask.

[10] : The pattern forming method according to [8], characterized in that the pattern formation in the step of forming a circuit pattern on the resist upper layer film is performed by photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[11] : The pattern forming method according to [8], characterized in that the workpiece is any one of a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film.

[12] : The pattern forming method according to

[11] , characterized in that the metal constituting the workpiece is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

[0238] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A composition for forming a silicon-containing resist film, characterized by containing a polysiloxane containing at least one of a repeating unit represented by the following formula (A-1), a repeating unit represented by the following formula (A-2), and a partial structure represented by the following formula (A-3): 【Chemistry 1】 (In the formula, R １ is a monovalent organic group having 1 to 30 carbon atoms, which may have a substituent, a halogen atom, a hydroxy group, a sulfo group, a nitro group, or a carboxyl group, which acts as a leaving group when exposed to heat, an acid, or a base, and R ２ , R ３ each independently represents a monovalent organic group having 1 to 30 carbon atoms which may have a substituent.

2. R in the formulae (A-1), (A-2), and (A-3) １ is a monovalent group represented by the following formula (B-1) that acts as a leaving group in the presence of heat, an acid, or a base, a halogen atom, a hydroxy group, a sulfo group, a nitro group, or a carboxyl group: 【Chemistry 2】 (R in the formula ４ are substituents bonded to the aromatic ring, each independently representing a hydrogen atom or an alkyl group of 1 to 20 carbon atoms which may have a substituent, an aryl group of 6 to 20 carbon atoms which may have a substituent, a halogenated alkyl group of 1 to 20 carbon atoms which may have a substituent, a halogenated aryl group of 6 to 20 carbon atoms which may have a substituent, an alkoxyalkyl group of 1 to 20 carbon atoms which may have a substituent, an alkoxyaryl group of 6 to 20 carbon atoms which may have a substituent, an acyl group of 6 to 20 carbon atoms which may have a substituent, a halogen atom, a hydroxy group, a sulfo group, a nitro group, or a carboxyl group, a = 0 or 1, n = 2a + 5, and * represents a bond to another atom.

3. 2. The composition for forming a silicon-containing resist film according to claim 1, wherein the polysiloxane contains a thermally crosslinkable polysiloxane containing at least one of a repeating unit represented by the following formula (Sx-1), a repeating unit represented by the following formula (Sx-2), and a partial structure represented by the following formula (Sx-3): 【Transformation 3】 (In the formula, R ５ , R ６ , R ７ are each independently a monovalent organic group having 1 to 30 carbon atoms which may have a substituent.

4. 2. The composition for forming a silicon-containing resist film according to claim 1, further comprising a crosslinking catalyst.

5. 5. The composition for forming a silicon-containing resist film according to claim 4, wherein the crosslinking catalyst is an ammonium salt or a sulfonium salt.

6. 2. The composition for forming a silicon-containing resist film according to claim 1, further comprising an acid generator.

7. 7. The composition for forming a silicon-containing resist film according to claim 6, wherein the acid generator is a sulfonium salt.

8. a step of forming a resist upper layer film on the silicon-containing resist intermediate film using a composition for a resist upper layer film comprising a photoresist composition; a step of forming a circuit pattern on the resist upper layer film; a step of transferring the pattern by etching onto the silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; a step of transferring the pattern by etching onto the organic film using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and a step of transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

9. a step of forming a silicon-containing resist intermediate film on the hard mask by a CVD method using the silicon-containing resist film-forming composition according to any one of claims 1 to 7; a step of forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film composition comprising a photoresist composition; a step of forming a circuit pattern on the resist upper layer film; a step of transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; a step of transferring the pattern to the hard mask by dry etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and a step of transferring the pattern to the workpiece by dry etching using the hard mask on which the pattern has been transferred as a mask.

10. 9. The pattern forming method according to claim 8, wherein the pattern formation in the step of forming a circuit pattern on the resist upper layer film is performed by photolithography, direct writing using an electron beam, nanoimprinting, or a combination thereof, with a wavelength of 10 nm or more and 300 nm or less.

11. 9. The pattern forming method according to claim 8, wherein the workpiece is any one of a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film.

12. 12. The pattern formation method according to claim 11, wherein the metal constituting the workpiece is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

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