Silicon-containing sulfonium salt compound, composition for forming a silicon-containing resist underlayer film, and patterning process

Abstract

[Problem] In a multilayer resist method, a silicon-containing resist sublayer forming composition capable of forming a silicon-containing resist sublayer capable of improving LWR or CDU in ultrafine patterns having an appropriate etching rate, a silicon-containing sulfonium salt compound included in the composition, and a pattern forming method using the composition are provided. [Solution] A silicon-containing sulfonium salt compound characterized by being represented by the following general formula (A-1).

Description

Technology Field

[0001] The present invention relates to a silicon-containing sulfonium salt compound, a composition for forming a silicon-containing resist underlayer film containing said compound, and a method for forming a pattern using said composition. Background Technology

[0002] With the increasing integration and speed of large-scale integrated circuits (LSIs), the miniaturization of pattern dimensions is progressing rapidly. Along with this miniaturization, lithography technology has achieved the formation of fine patterns by shortening the wavelength of the light source and appropriately selecting the corresponding resist composition. At the center of this is the single-layer positive photoresist composition. This single-layer positive photoresist composition has a framework within the resist resin that has etching resistance against dry etching by chlorine-based or fluorine-based gas plasma, and also has a switching mechanism such as dissolving the exposed area, thereby dissolving the exposed area to form a pattern, and then dry etching the substrate to be processed using the remaining resist pattern as an etching mask.

[0003] However, when the thickness of the photoresist film used is reduced while keeping the pattern width smaller, the resolution performance of the photoresist film deteriorates, and when the photoresist film is patterned using a developer, the so-called aspect ratio increases, resulting in pattern collapse. For this reason, photoresist films have been made thinner as the pattern is reduced.

[0004] Meanwhile, for processing a substrate to be processed, a method is typically used in which the substrate is processed by dry etching using a patterned photoresist film as an etching mask; however, in reality, there is no dry etching method capable of achieving complete etching selectivity between the photoresist film and the substrate to be processed. Consequently, there was a problem in that the resist film was damaged and collapsed during the processing of the substrate, making it impossible to accurately transfer the resist pattern to the substrate to be processed. Therefore, as patterns became more miniaturized, higher dry etching resistance was required for photoresist compositions. However, on the other hand, to improve resolution, resins with low light absorption at the exposure wavelength were required for the resins used in photoresist compositions. For this reason, as the exposure light has become shorter wavelengths such as i-line, KrF, and ArF, the resins used in photoresist compositions have also changed to novolak resins, polyhydroxystyrene, and resins with aliphatic polycyclic backbones; however, in reality, the etching rate under dry etching conditions during substrate processing has become fast, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] As a result, the substrate to be processed must be dry-etched with a thinner photoresist film that has lower etching resistance, and securing materials and processes for this processing process has become an urgent task.

[0006] One method to solve these problems is the multilayer resist method. This method involves interposing a photoresist film (i.e., an upper resist film) and a lower resist film having different etching selectivity between the upper resist film and the substrate to be processed, obtaining a pattern on the upper resist film, using the pattern on the upper resist film as a dry etching mask to transfer the pattern to the lower resist film by dry etching, and also using the lower resist film as a dry etching mask to transfer the pattern to the substrate to be processed by dry etching.

[0007] As one of the multilayer resist methods, there is a three-layer resist method that can be performed using a general resist composition used in the single-layer resist method. In this three-layer resist method, for example, an organic film made of novolak resin, etc., is formed as a resist lower layer on a substrate to be processed, a silicon-containing resist intermediate film is formed thereon, and a conventional organic photoresist film is formed thereon as a resist upper layer. When performing dry etching with a fluorine-based gas plasma, the organic resist upper layer can have a good etching selectivity ratio with respect to the silicon-containing resist intermediate film, so the resist upper layer pattern can be transferred to the silicon-containing resist intermediate film by dry etching with a fluorine-based gas plasma. According to this method, even if a resist composition that is difficult to form a pattern with a sufficient film thickness for directly processing a substrate to be processed, or a resist composition that does not have sufficient dry etching resistance for processing the substrate is used, a pattern can be transferred to a silicon-containing resist intermediate film. Subsequently, if pattern transfer is performed by dry etching with an oxygen-based or hydrogen-based gas plasma, an organic film pattern made of a novolak resin, etc., that has sufficient dry etching resistance for processing the substrate can be obtained. The silicon-containing resist intermediate film remaining after forming the organic film pattern is generally removed by dry etching with a fluorine-based gas plasma or by wet etching with an etching solution such as an alkaline or fluorine-based one, so as not to become a residue that causes defects. If the etching rate is insufficient, there is a high possibility of problems such as residues originating from the silicon-containing resist intermediate film remaining and becoming defects, or requiring a long etching process and causing damage to the substrate to be processed. As such, for accurate patterning and smooth removal, an appropriate etching rate is required for the silicon-containing resist intermediate film.

[0008] Meanwhile, with the recent emergence of ArF immersion lithography and EUV lithography, it has become possible to form finer patterns, but consequently, the thinning of photoresist films has progressed further. Since this thinning of photoresist films leads to the deterioration of edge roughness (LWR) and hole pattern dimensional uniformity (CDU) in ultrafine patterns, improving LWR and CDU has become a serious problem.

[0009] Here, a composition for forming a silicon-containing resist intermediate film for ArF or EUV lithography containing a curing catalyst has been proposed (Patent Documents 1 and 2). This curing catalyst has a structure suitable for promoting the formation of siloxane bonds that form the main framework of the silicon-containing resist intermediate film by catalyzing the condensation reaction of silanol. Furthermore, it is becoming known that the selection of the curing catalyst imparts various effects to the properties of the silicon-containing resist intermediate film. Examples include acidity / basicity, hydrophilicity / hydrophobicity, hardness, film density, and etching rate. Such curing catalysts have a structure similar to that of sensitivity modifiers in the upper layer resist. Consequently, if diffusion into the upper layer resist occurs due to heating or exposure, it becomes a problem that it significantly affects the pattern-forming ability of the photoresist. In particular, since it affects the performance of the LWR or CDU, there is a need to develop a curing catalyst in which diffusion into the upper layer resist is suppressed.

[0010] On the other hand, photosensitive upper layer resist materials are known to have compounds containing cations and anions within the molecule added to improve LWR or CDU (Patent Document 3). However, for recent ultrafine patterns, higher precision LWR or CDU is required, and performance improvement of silicon-containing resist intermediate films is also required. Prior art literature

[0011] Patent Document 1: Japanese Patent Publication No. 2007-302873 Patent Document 2: International Publication No. 2013 / 161372 Patent Document 3: Japanese Patent Publication No. 2011-016746 The problem to be solved

[0012] The present invention aims to provide a composition for forming a silicon-containing resist underlayer capable of forming a silicon-containing resist underlayer capable of improving LWR or CDU in ultrafine patterns having an appropriate etching rate in a multilayer resist method, a silicon-containing sulfonium salt compound included in the composition, and a method for forming a pattern using the composition. means of solving the problem

[0013] To solve the above problem, the present invention provides a silicon-containing sulfonium salt compound represented by the following general formula (A-1).

[0014]

[0015] (during food, Ar 1 , Ar 2 , and Ar 3 Each is independently an aromatic group having 6 to 20 carbon atoms that may have substituents, or a heteroaromatic group having 4 to 20 carbon atoms that may have substituents. Also, Ar 1 , Ar 2 , and Ar 3 Any two or more selected from may combine with each other to form a ring together with the sulfur atom in the formula. a, b, and c are each independently integers from 0 to 3, and 1 ≤ a + b + c ≤ 9. X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, and may be identical or different from each other. A - represents an organic or inorganic anion that serves as the counterion for a sulfonium cation.

[0016] If such a silicon-containing sulfonium salt compound is added to a composition for forming a silicon-containing resist sublayer, it functions as a curing catalyst and can promote the thermal curing thereof. In addition, since the silicon-containing sulfonium salt compound of the present invention has high affinity with silicon polymers, by adding it to a composition for forming a silicon-containing resist sublayer, diffusion into the upper resist is suppressed, thereby enabling the formation of a silicon-containing resist sublayer having good LWR or CDU characteristics. Furthermore, due to the effect of silicon atoms, a silicon-containing resist sublayer having a good etching rate can be formed.

[0017] In addition, the present invention provides a composition for forming a silicon-containing resist underlayer, comprising the silicon-containing sulfonium salt compound described above and a thermally crosslinkable polysiloxane.

[0018] With such a silicon-containing resist underlayer forming composition, in a multilayer resist method, a silicon-containing resist underlayer can be formed that has an appropriate etching rate and can improve LWR or CDU in ultrafine patterns.

[0019] It is preferable that the above-mentioned thermally crosslinkable polysiloxane comprises one or more of the repeating unit represented by the following general formula (Sx-1), the repeating unit represented by the following general formula (Sx-2), and the substructure represented by the following general formula (Sx-3).

[0020]

[0021]

[0022]

[0023] (during food, R 1 , R 2 , and R 3 Each is a monovalent organic group having 1 to 30 carbon atoms, which may be identical or different.

[0024] When the above-mentioned thermally crosslinkable polysiloxane includes the above-mentioned specific structure, the effects of the present invention are more fully exhibited.

[0025] The silicon-containing resist underlayer forming composition of the present invention preferably further contains an acid generating agent.

[0026] By adding an acid generator as needed, the pattern shape, exposure sensitivity, etc., can be finely adjusted.

[0027] It is preferable that the above acid generator is a photo-generating agent that generates acid through the action of high-energy rays.

[0028] In this case, the pattern shape and exposure sensitivity of the resist upper layer can be appropriately adjusted while minimizing the degradation of other performance, and additionally, it may be effective in reducing residue originating from the resist upper layer.

[0029] In addition, the present invention provides a method for forming a pattern on a workpiece, wherein

[0030] A process of forming an organic film on a workpiece using a coating-type organic film material, and

[0031] A process of forming a silicon-containing resist underlayer on the above organic film using the silicon-containing resist underlayer forming composition described above, and

[0032] A process for forming a resist upper layer using a composition for a resist upper layer comprising a photoresist composition on the silicon-containing resist lower layer, and

[0033] A process of forming a circuit pattern on the upper layer of the above-mentioned resist, and

[0034] A process of transferring a pattern to a silicon-containing resist lower film by etching using the resist upper film having the circuit pattern formed thereon as a mask, and

[0035] A process of transferring a pattern to an organic film by etching using the silicon-containing resist lower layer film on which the above pattern has been transferred as a mask, and

[0036] A process of transferring a pattern to a workpiece by etching using the organic film having the above pattern transferred thereon as a mask.

[0037] A pattern forming method including is provided.

[0038] In addition, the present invention provides a method for forming a pattern on a workpiece, wherein

[0039] A process of forming a hard mask on a workpiece using the CVD method, and

[0040] A process of forming a silicon-containing resist underlayer on the hard mask using the silicon-containing resist underlayer forming composition described above, and

[0041] A process for forming a resist upper layer using a composition for a resist upper layer comprising a photoresist composition on the silicon-containing resist lower layer, and

[0042] A process of forming a circuit pattern on the upper layer of the above-mentioned resist, and

[0043] A process of transferring a pattern to a silicon-containing resist lower film by etching using the resist upper film having the circuit pattern formed thereon as a mask, and

[0044] A process of transferring a pattern onto a hard mask by dry etching using the silicon-containing resist lower layer film having the above pattern transferred thereon as a mask, and

[0045] A process of transferring a pattern to a workpiece by dry etching using the hard mask having the above pattern transferred thereon as a mask.

[0046] A pattern forming method including is provided.

[0047] The above pattern forming method is a pattern forming method that is particularly practical for forming fine patterns because the pattern collapse of the upper resist film is suppressed, the pattern transfer to the lower silicon-containing resist film by dry etching is excellent, and the removal of the remaining lower silicon-containing resist film after the patterning is finished is easy, making it difficult for defects caused by residue to occur.

[0048] As a method for forming a circuit pattern on the upper layer of the above-mentioned resist, it is preferable to use photolithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof.

[0049] If the method of forming a circuit pattern on the upper layer of the resist is the specific method described above, the effects of the present invention are more fully exhibited.

[0050] As the above-mentioned workpiece, a semiconductor device substrate, or any one of 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 formed on the semiconductor device substrate may be used.

[0051] When the above-mentioned specific material is used as the above-mentioned workpiece, the effects of the present invention are more fully exhibited.

[0052] In addition, as the metal, it is preferable to use silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

[0053] When the metal constituting the above-mentioned workpiece is the specific metal mentioned above, the effect of the present invention is more fully manifested. Effects of the invention

[0054] As described above, by adding the silicon-containing sulfonium salt compound of the present invention to a composition for forming a silicon-containing resist sublayer containing a thermally crosslinkable polysiloxane as a curing catalyst, it is possible to form an ultrafine upper layer resist pattern having good LWR or CDU. Furthermore, since the dry etching selectivity between the resist upper layer and the organic film or hard mask is excellent, a pattern for a semiconductor device can be formed on a substrate with high yield. In addition, since high etching selectivity between the formed silicon-containing resist sublayer and the organic material is obtained, the formed upper layer resist pattern can be transferred sequentially to the silicon-containing resist sublayer and the organic film or hard mask using a dry etching process. Moreover, since the formed silicon-containing resist sublayer has a sufficient etching rate, the silicon-containing resist sublayer remaining after the patterning is completed is easy to remove, and since it is difficult for defects caused by residue to occur, it is particularly useful for forming fine patterns. Specific details for implementing the invention

[0055] As previously mentioned, in a multilayer resist method, there was a need for the development of a silicon-containing resist underlayer forming composition capable of forming a silicon-containing resist underlayer capable of improving LWR or CDU in ultrafine patterns with an appropriate etching rate, a silicon-containing sulfonium salt compound included in the composition, and a pattern forming method using the composition.

[0056] The inventors, having conducted repeated examinations to achieve the above objective, discovered that by incorporating a silicon-containing sulfonium salt compound of a specific structure into a composition for forming a silicon-containing resist underlayer, it is possible to improve the LWR or CDU of an ultrafine pattern in a multilayer resist method and also provide a silicon-containing resist underlayer having an etching rate suitable for processing, thereby completing the present invention.

[0057] That is, the present invention is a silicon-containing sulfonium salt compound, represented by the following general formula (A-1).

[0058]

[0059] (during food, Ar 1 , Ar 2 , and Ar 3 Each is independently an aromatic group having 6 to 20 carbon atoms that may have substituents, or a heteroaromatic group having 4 to 20 carbon atoms that may have substituents. Also, Ar 1 , Ar 2 , and Ar 3 Any two or more selected from may combine with each other to form a ring together with the sulfur atom in the formula. a, b, and c are each independently integers from 0 to 3, and 1 ≤ a + b + c ≤ 9. X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, and may be identical or different from each other. A - represents an organic or inorganic anion that serves as the counterion for a sulfonium cation.

[0060] The present invention will be described in detail below, but the invention is not limited to these.

[0061] Composition for forming a silicon-containing resist underlayer

[0062] The silicon-containing resist underlayer forming composition of the present invention comprises a silicon-containing sulfonium salt compound represented by the following general formula (A-1) and a thermally crosslinkable polysiloxane. In addition, it may include any other components.

[0063] Hereinafter, each component included in the silicon-containing resist underlayer forming composition of the present invention will be described in detail.

[0064] Silicon-containing sulfonium salt compounds

[0065] The silicon-containing sulfonium salt compound of the present invention is a silicon-containing sulfonium salt compound represented by the following general formula (A-1) and can be used as a curing catalyst.

[0066]

[0067] (during food, Ar 1 , Ar 2 , and Ar 3 Each is independently an aromatic group having 6 to 20 carbon atoms that may have substituents, or a heteroaromatic group having 4 to 20 carbon atoms that may have substituents. Also, Ar 1 , Ar 2 , and Ar 3 Any two or more selected from may combine with each other to form a ring together with the sulfur atom in the formula. a, b, and c are each independently integers from 0 to 3, and 1 ≤ a + b + c ≤ 9. X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, and may be identical or different from each other. A - represents an organic or inorganic anion that serves as the counterion for a sulfonium cation.

[0068] The silicon-containing sulfonium salt compound of the present invention functions as a curing catalyst by being added to a composition for forming a silicon-containing resist underlayer film, thereby promoting thermal curing. During curing, since the compound has high affinity with silicon polymers, diffusion into the upper resist is suppressed, contributing to the improvement of LWR or CDU. In addition, the formed silicon-containing resist underlayer film is thought to have a sufficient etching rate for processing because it contains an appropriate composition and structure.

[0069] In addition, in this specification, a layer formed below the upper resist layer is referred to as a lower layer, and includes a resist lower layer or a silicon-containing resist intermediate layer.

[0070] Among the above general formula (A-1), Ar 1 , Ar 2 , and Ar3 Each represents, independently, an aromatic group having 6 to 20 carbon atoms that may have substituents, or a heteroaromatic group having 4 to 20 carbon atoms that may have substituents. Specifically, examples of aromatic groups having 6 to 20 carbon atoms include phenyl groups, naphthyl groups, anthracenyl groups, phenanthrenyl groups, and pyrenyl groups. Specifically, examples of heteroaromatic groups having 4 to 20 carbon atoms include furanyl groups, thiophenyl groups, pyrrolyl groups, benzofuranyl groups, pyridinyl groups, indolyl groups, oxazolyl groups, imidazolyl groups, and benzimidazolyl groups. Possible substituents include straight-chain, branched, or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups, heteroaromatic groups, alkoxy groups, hydroxyl groups, ester groups, carbonyl groups, amino groups, halogen groups, sulfide groups, carboxyl groups, sulfo groups, amide groups, imide groups, cyano groups, aldehyde groups, imino groups, urea groups, carbamate groups, carbonate groups, nitro groups, sulfonyl groups, and groups formed by combinations thereof. To more effectively exhibit the effects of the present invention, phenyl groups, naphthyl groups, furanyl groups, thiophenyl groups, pyrrolyl groups, and pyridinyl groups are preferred, and more preferably, phenyl groups and naphthyl groups. In addition, Ar 1 , Ar 2 , and Ar 3 Any two or more selected from may combine with each other to form a ring with a sulfur atom in the formula, but from the perspective of solubility and stability, it is more desirable not to form a ring.

[0071] In the above general formula (A-1), X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, and may be the same or different from each other. Specifically, examples of monovalent organic groups having 1 to 14 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, alkenyl group, oxoalkyl group, aryl group, aryl alkyl group, aryl oxoalkyl group, etc.

[0072] Examples of alkenyl groups include vinyl groups, allyl groups, propenyl groups, butenyl groups, hexenyl groups, cyclohexanyl groups, etc.

[0073] Examples of oxoalkyl groups include 2-oxocyclopentyl groups, 2-oxocyclohexyl groups, etc., and 2-oxopropyl groups, 2-cyclopentyl-2-oxoethyl groups, 2-cyclohexyl-2-oxoethyl groups, 2-(4-methylcyclohexyl)-2-oxoethyl groups, etc.

[0074] Examples of aryl groups include phenyl groups, naphthyl groups, alkoxyphenyl groups such as p-methoxyphenyl groups, m-methoxyphenyl groups, o-methoxyphenyl groups, ethoxyphenyl groups, p-tert-butoxyphenyl groups, m-tert-butoxyphenyl groups, alkylphenyl groups such as 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, alkylnaphthyl groups such as methylnaphthyl groups and ethylnaphthyl groups, alkoxynaphthyl groups such as methoxynaphthyl groups and ethoxynaphthyl groups, dialkylnaphthyl groups such as dimethylnaphthyl groups and diethylnaphthyl groups, and diallkoxynaphthyl groups such as dimethoxynaphthyl groups and diethoxynaphthyl groups.

[0075] Examples of aralkyl groups include benzyl groups, phenylethyl groups, and phenethyl groups.

[0076] Examples of aryl-oxoalkyl groups include 2-aryl-2-oxoethyl groups, 2-(1-naphthyl)-2-oxoethyl groups, 2-(2-naphthyl)-2-oxoethyl groups, and 2-aryl-2-oxoethyl groups.

[0077] To more effectively demonstrate the effects of the present invention, methyl groups, ethyl groups, and isopropyl groups are preferred, and methyl groups and ethyl groups are more preferred.

[0078] Among the above general formula (A-1), A - represents an organic or inorganic anion that serves as the counterpart ion to a sulfonium cation. Specifically, examples of organic anions include formate, acetate, propionate, butyrate, hexanoate, benzoate, t-butylbenzoate, trichloroacetate, trifluoroacetate, 2-hydroxy-2,2-bis(trifluoromethyl)acetate, trimethylacetate, pentafluoropropionate, methanesulfonate, butanesulfonate, benzenesulfonate, toluenesulfonate, trifluoromethanesulfonate, methyl sulfate ion, etc. Specifically, examples of inorganic anions include chloride ions, bromide ions, iodide ions, fluoride ions, cyanide ions, nitrate ions, nitrite ions, hydroxide ions, etc. Among these anions, chloride ions, iodide ions, fluoride ions, nitrate ions, nitrite ions, and hydroxide ions are preferred, and chloride ions and nitrate ions are more preferred.

[0079] In the present invention, the silicon-containing sulfonium salt compound represented by the general formula (A-1) may be used alone or in a mixture of two or more types. The amount of the silicon-containing sulfonium salt compound represented by the general formula (A-1) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, with respect to 100 parts by mass of the thermocrosslinkable polysiloxane (Sx) described later.

[0080] As silicon-containing sulfonium salt compounds represented by the above general formula (A-1), more specifically, the following compounds may be exemplified, but are not limited thereto. In the following formulas, Me represents a methyl group, and the same applies hereinafter.

[0081]

[0082]

[0083]

[0084] [Thermocrosslinkable polysiloxane]

[0085] The composition for forming a silicon-containing resist underlayer of the present invention comprises, in addition to one or more silicon-containing sulfonium salt compounds represented by the general formula (A-1), a thermally crosslinkable polysiloxane.

[0086] The thermally crosslinkable polysiloxane (Sx) used in the present invention preferably contains one or more of the following general formula (Sx-1), the following general formula (Sx-2), and the following substructure (Sx-3).

[0087]

[0088]

[0089]

[0090] (during food, R 1 , R 2 , and R 3 Each is a monovalent organic group having 1 to 30 carbon atoms, which may be identical or different.

[0091] The above thermally crosslinkable polysiloxane (Sx) can be prepared, for example, by hydrolyzing and condensing the following hydrolyzable monomer (Sm).

[0092] Specifically as a hydrolyzable monomer (Sm), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltriethoxysilane, Isopropyltripropoxysilane, Isopropyltriisopropoxysilane, Butyltrimethoxysilane, Butyltriethoxysilane, Butyltripropoxysilane, Butyltripropoxysilane, Butyltriisopropoxysilane, Isobutyltrimethoxysilane, Isobutyltriethoxysilane, Isobutyltripropoxysilane, Isobutyltriisopropoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltripropoxysilane, sec-butyltriisopropoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltripropoxysilane, t-butyltriisopropoxysilane, Allyltrimethoxysilane, Allyltriethoxysilane, Allyltripropoxysilane, Allyltriisopropoxysilane, Cyclopropyltrimethoxysilane, Cyclopropyltriethoxysilane, Cyclopropyltripropoxysilane, Cyclopropyltriisopropoxysilane, Cyclobutyltrimethoxysilane, Cyclobutyltriethoxysilane, Cyclobutyltripropoxysilane, Cyclobutyltriisopropoxysilane, Cyclopentyltrimethoxysilane, Cyclopentyltriethoxysilane, Cyclopentyltripropoxysilane, Cyclopentyltriisopropoxysilane, Cyclohexyltrimethoxysilane, Cyclohexyltriethoxysilane, Cyclohexyltripropoxysilane, Cyclohexyltriisopropoxysilane, Cyclohexyltrimethoxysilane, Cyclohexyltripropoxysilane, Cyclohexyltriisopropoxysilane, Cyclohexenyltrimethoxysilane, Cyclohexenyltripropoxysilane, Cyclohexenyltriisopropoxysilane, Cyclohexenylethyltrimethoxysilane, Cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane,Cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltriethoxysilane, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltripropoxysilane, bicycloheptenyltriisopropoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyltripropoxysilane, bicycloheptyltriisopropoxysilane, adamantyltrimethoxysilane, Adamantyltriethoxysilane, Adamantyltripropoxysilane, Adamantyltriisopropoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, Phenyltripropoxysilane, Phenyltripropoxysilane, Phenyltriisopropoxysilane, Benzyltrimethoxysilane, Benzyltriethoxysilane, Benzyltripropoxysilane, Benzyltriisopropoxysilane, Anisyltrimethoxysilane, Anisyltriethoxysilane, Anisyltripropoxysilane, Anisyltriisopropoxysilane, Tolyltrimethoxysilane, Tolyltriethoxysilane, Tolyltripropoxysilane, Tolyltriisopropoxysilane, Phenethyltrimethoxysilane, Phenethyltriethoxysilane, Phenethyltripropoxysilane, Phenethyltriisopropoxysilane, Naphthyltrimethoxysilane, Naphthyltriethoxysilane, Naphthyltripropoxysilane, Naphthyltriisopropoxysilane, Dimethyldimethoxysilane, Dimethyldiethoxysilane, Methylethyldimethoxysilane, Methylethyldiethoxysilane, Dimethyldipropoxysilane, Dimethyldiisopropoxysilane, Diethyldimethoxysilane, Diethyldiethoxysilane, Diethyldipropoxysilane, Diethyldiisopropoxysilane, Dipropyldimethoxysilane, Dipropyldiethoxysilane, Dipropyldipropoxysilane, Dipropyldiisopropoxysilane, Diisopropyldimethoxysilane, Diisopropyldiethoxysilane, Diisopropyldipropoxysilane, Diisopropyldiisopropoxysilane, Dibutyldimethoxysilane, Dibutyldiethoxysilane, Dibutyldipropoxysilane, Dibutyl diisopropoxysilane, disec-butyl dimethoxysilane, disec-butyl diethoxysilane, disec-butyl dipropoxysilane, disec-butyl diisopropoxysilane,Dit-butyl dimethoxysilane, Dit-butyl diethoxysilane, Dit-butyl dipropoxysilane, Dit-butyl diisopropoxysilane, Dicyclopropyl dimethoxysilane, Dicyclopropyl diethoxysilane, Dicyclopropyl dipropoxysilane, 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 dimethoxysilane, Dicyclohexenyl diethoxysilane, Dicyclohexenyl dipropoxysilane, Dicyclohexenyl diisopropoxysilane, Dicyclohexenyl ethyl dimethoxysilane, Dicyclohexenyl ethyl diethoxysilane, Dicyclohexenyl ethyl dipropoxysilane, Dicyclohexenyl ethyl diisopropoxysilane, Dicyclohexenyl ethyl diisopropoxysilane, Dicyclooctyl dimethoxysilane, Dicyclooctyl diethoxysilane, Dicyclooctyl dipropoxysilane, Dicyclooctyl diisopropoxysilane, Dicyclopentadienyl propyl dimethoxysilane, Dicyclopentadienyl propyl diethoxysilane, Dicyclopentadienyl propyl dipropoxysilane, Dicyclopentadienyl propyl diisopropoxysilane, 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, Diadamantyldipropoxysilane, Diadamantyldiisopropoxysilane, Diphenyldimethoxysilane, Diphenyldiethoxysilane, Methylphenyldimethoxysilane, Methylphenyldiethoxysilane, Diphenyldipropoxysilane, Diphenyldiisopropoxysilane, Trimethylmethoxysilane, Trimethylethoxysilane, Examples include dimethyl ethyl methoxysilane, dimethyl ethyl ethoxysilane, dimethyl phenyl methoxysilane, dimethyl phenyl ethoxysilane, dimethyl benzyl methoxysilane, dimethyl benzyl ethoxysilane, dimethyl phenethyl methoxysilane, dimethyl phenethyl ethoxysilane, etc.

[0093] Preferably as the above compound, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, phenyltrimethoxysilane, Examples include phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane, etc.

[0094] The above R 1 , R 2 , and R 3 As a separate example of an organic group represented by, an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds may be cited. Specifically, it is an organic group having one or more groups selected from the group consisting of ether bonds, ester bonds, alkoxy groups, hydroxyl groups, etc. An example of this is represented by the following general formula (Sm-R).

[0095] (P-Q1-(S1) v1 -Q2-) u -(T) v2 -Q3-(S2) v3 -Q4- (Sm-R)

[0096] (in the general formula (Sm-R), P is a hydrogen atom, a cyclic ether group, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkyl carbonyloxy group having 2 to 6 carbon atoms, or an alkyl carbonyl group having 2 to 6 carbon atoms, and Q1, Q2, Q3, and Q4 are each independently -C q H (2q-p) P p -(In the formula, P is the same as above, p is an integer from 0 to 3, and q is an integer from 0 to 10 (where q=0 indicates a single bond).), u is an integer from 0 to 3, and S1 and S2 each independently represent -O-, -CO-, -OCO-, -COO-, or -OCOO-. v1, v2, and v3 each independently represent 0 or 1. T is a divalent group including a divalent atom other than carbon, an alicyclic ring, an aromatic ring, or a heterocyclic ring.)

[0097] Examples of alicyclic, aromatic, or heterocyclic rings that may include heteroatoms such as oxygen atoms as T are shown below. The bonding positions of T with Q2 and Q3 are not particularly limited, but can be appropriately selected by considering reactivity due to steric factors or the availability of commercially available reagents used in the reaction.

[0098]

[0099] Preferred examples of organic groups having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (Sm-R) include the following. In addition, in the following formula, (Si) is described to indicate the bonding location with Si.

[0100]

[0101]

[0102] Also, R 1 , R 2 , and R 3 As an example of an organic group, an organic group containing silicon-silicon bonds may be used. Specifically, the following may be cited.

[0103]

[0104] Also, R 1 , R 2 , and R 3 As an example of an organic group, an organic group having a protecting group that decomposes with acid may be used. Specifically, examples include the organic group mentioned in paragraphs

[0043] through

[0048] of Japanese Patent Publication No. 2013-167669, and the organic group obtained from a silicon compound shown in paragraph

[0056] of Japanese Patent Publication No. 2013-224279.

[0105] Also, R 1 , R 2 , and R 3 As an example of an organic group, an organic group having a fluorine atom may be used. Specifically, an organic group obtained from a silicon compound as described in paragraphs

[0059] through

[0065] of Japanese Patent Publication No. 2012-053253 may be used.

[0106] The above 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 represented by (Si) in the above partial structure.

[0107] [Method for Synthesis of Thermally Crosslinkable Polysiloxane (Sx)]

[0108] (Synthesization Method 1: Acid Catalyst)

[0109] The thermally crosslinkable polysiloxane (Sx) used in the present invention can be prepared by performing hydrolysis condensation of one or more hydrolyzable monomers (Sm) in the presence of an acid catalyst.

[0110] The acid catalyst used at this time may 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, hydrobromide, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid. The amount of catalyst used is preferably 1 × 10⁻⁶ per mole of monomer. -6 ~10 moles, more preferably 1×10 -5 ~5 moles, more preferably 1×10⁻⁶ -4 ~1 mole.

[0111] When obtaining a thermally crosslinkable polysiloxane (Sx) from these monomers by hydrolytic condensation, it is preferable to add 0.01 to 100 moles of water per mole of hydrolyzable substituent bonded to the monomer, more preferably 0.05 to 50 moles, and even more preferably 0.1 to 30 moles. If the amount is 100 moles or less, the apparatus used for the reaction becomes smaller and more economical. If the amount is 0.01 moles or more, the reaction proceeds sufficiently.

[0112] As a method of operation, a monomer is added to an aqueous catalyst solution to initiate a hydrolysis-condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, the monomer may be diluted with an organic solvent, or both methods may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. It is preferable to maintain the temperature at 5 to 80°C when adding the monomer dropwise, and then age it at 20 to 80°C.

[0113] As organic solvents that can be added to an aqueous catalyst solution or dilute monomers, 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, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, Butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol monot-butyl ether acetate, γ-butyrolactone, and mixtures thereof are preferred.

[0114] 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 condensation derivatives such as butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, and ethylene glycol monopropyl ether; acetone; acetonitrile; and tetrahydrofuran. Among these, those with a boiling point of 100°C or lower are particularly preferred.

[0115] In addition, the amount of organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per mole of monomer. If the amount of organic solvent used is reduced, the reaction vessel becomes smaller, making it economical.

[0116] Afterwards, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous solution of the 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 as a catalyst. Any substance may be used as long as it exhibits alkalinity in water.

[0117] Furthermore, it is desirable to remove by-products, such as alcohol generated by the hydrolysis condensation reaction from the aqueous solution of the reaction mixture, using methods such as vacuum removal. At this time, the temperature at which the aqueous solution of the reaction mixture is heated depends on the type of alcohol, etc. generated by the reaction with the added organic solvent, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. In addition, the degree of vacuum at this time varies depending on the type of organic solvent and alcohol, etc. to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably at or below atmospheric pressure, more preferably at or below 80 kPa in absolute pressure, and even more preferably at or below 50 kPa in absolute pressure. Although it is difficult to know the exact amount of alcohol removed at this time, it is desirable that approximately 80 mass% or more of the generated alcohol, etc. is removed.

[0118] Next, the acid catalyst used for hydrolysis condensation may be removed from the aqueous solution of the reaction mixture. As a method for removing the acid catalyst, water and a thermally crosslinkable polysiloxane solution are mixed, and the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used at this time is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methylamyl 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 methoxypropionate, ethyl ethoxypropionate, Examples include t-butyl acetate, t-butyl propionate, propylene glycol monot-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0119] In addition, it is also possible to use a mixture of water-soluble organic solvents and water-insoluble organic solvents. 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, Propylene glycol monomethyl ether-methyl isobutyl ketone mixture, ethylene glycol monomethyl ether-methyl isobutyl ketone 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-cyclopentylmethyl ether mixture, ethanol-cyclopentylmethyl ether mixture, 1-propanol-cyclopentylmethyl ether mixture, 2-propanol-cyclopentylmethyl ether mixture, propylene glycol monomethyl ether-cyclopentylmethyl ether mixture, ethylene glycol monomethyl ether-cyclopentylmethyl ether mixture, propylene glycol monoethyl ether-cyclopentylmethyl ether mixture, ethylene glycol monoethyl ether-cyclopentylmethyl ether mixture, Propylene glycol monopropyl ether-cyclopentyl methyl ether mixture, ethylene glycol monopropyl ether-cyclopentyl methyl ether mixture, methanol-propylene glycol methyl ether acetate mixture, ethanol-propylene glycol methyl ether acetate mixture, 1-propanol-propylene glycol methyl ether acetate mixture, 2-propanol-propylene glycol methyl ether acetate mixture,A mixture of propylene glycol monomethyl ether-propylene glycol methyl ether acetate, a mixture of ethylene glycol monomethyl ether-propylene glycol methyl ether acetate, a mixture of propylene glycol monoethyl ether-propylene glycol methyl ether acetate, a mixture of ethylene glycol monoethyl ether-propylene glycol methyl ether acetate, a mixture of propylene glycol monopropyl ether-propylene glycol methyl ether acetate, a mixture of ethylene glycol monopropyl ether-propylene glycol methyl ether acetate, etc. are preferred, but the combination is not limited to these.

[0120] In addition, the mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent is appropriately selected, but for every 100 parts by mass of the water-insoluble organic solvent, 0.1 to 1,000 parts by mass of the water-soluble organic solvent is preferred, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0121] Next, it may be washed with neutral water. This water may be used as what is commonly referred to as deionized water or ultrapure water. The amount of this water 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 thermocrosslinkable polysiloxane solution. For this washing method, both materials may be placed in the same container, mixed, and then allowed to stand to separate the aqueous layer. The number of washes may be at least once, but since the effect of washing is not achieved even if washed more than 10 times, it is preferably about 1 to 5 times.

[0122] Other methods for removing acid catalysts include using ion exchange resins or removing them after neutralization with epoxy compounds such as ethylene oxide or propylene oxide. These methods can be appropriately selected according to the acid catalyst used in the reaction.

[0123] Since the washing operation at this stage causes some of the thermally crosslinkable polysiloxane to escape into the water layer, thereby achieving an effect substantially equivalent to fractionation, it is advisable to appropriately select the number of washes and the amount of washing water, taking into account the catalyst removal effect and the fractionation effect.

[0124] In either the thermocrosslinkable polysiloxane solution in which the acid catalyst remains or the thermocrosslinkable polysiloxane solution from which the acid catalyst has been removed, a final solvent is added, and a desired thermocrosslinkable polysiloxane solution is obtained by solvent exchange under reduced pressure. The temperature of the solvent exchange at this time depends on the type of reaction solvent or 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. In addition, the degree of reduced pressure at this time varies depending on the type of extraction solvent to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably at atmospheric pressure or lower, more preferably at an absolute pressure of 80 kPa or lower, and even more preferably at an absolute pressure of 50 kPa or lower.

[0125] At this time, the thermocrosslinkable polysiloxane may become unstable due to changes in the solvent. This occurs due to the compatibility between the final solvent and the thermocrosslinkable polysiloxane, but to prevent this, as a stabilizer, a monovalent or divalent alcohol having a cyclic ether as a substituent, as described in paragraphs

[0181] to

[0182] of Japanese Patent Publication No. 2009-126940, may be added. The amount added is preferably 0 to 25 parts by mass, more preferably 0 to 15 parts by mass, and even more preferably 0 to 5 parts by mass relative to 100 parts by mass of the thermocrosslinkable polysiloxane in the solution before solvent exchange, but an amount of 0.5 parts by mass or more is preferred when adding. If necessary, the solvent exchange operation may be performed by adding a monovalent or divalent alcohol having a cyclic ether as a substituent to the solution before solvent exchange.

[0126] It is desirable to keep the thermally crosslinkable polysiloxane in a solution state at an appropriate concentration. The concentration is preferably 0.1 to 20 mass%. At this concentration, since additional condensation reactions do not proceed, it does not change into a state that is irresolvable in organic solvents. In addition, since the amount of solvent is reduced, it is economical and desirable.

[0127] As a final solvent to be added to a heat-crosslinkable polysiloxane solution, an alcohol-based solvent is preferred, and particularly preferred are monoalkyl ether derivatives such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, and diacetone alcohol are preferred.

[0128] If these solvents are the main components, it is also possible to add a non-alcoholic solvent as an auxiliary solvent. Examples of such auxiliary solvents include acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methylamyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, 3-methyl methoxypropionate, 3-ethyl ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol monot-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0129] In addition, as a separate reaction operation using an acid catalyst, water or an aqueous organic solvent is added to the monomer or an organic solution of the monomer to initiate a hydrolysis reaction. At this time, the catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the aqueous organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. It is preferable to heat to 10 to 50°C when adding water dropwise, and then raise the temperature to 20 to 80°C to age the mixture.

[0130] When using an organic solvent, it is preferable that it be water-soluble, and examples include polyhydric alcohol condensation 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, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether, as well as mixtures thereof.

[0131] The amount of organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per mole of monomer. Using less organic solvent is more economical as it allows for a smaller reaction vessel. The resulting aqueous reaction mixture can be post-treated in the same manner as above to obtain a thermally crosslinkable polysiloxane.

[0132] (Synthesization Method 2: Alkali Catalyst)

[0133] In addition, the thermally crosslinkable polysiloxane (Sx) can be produced by performing hydrolysis condensation of one or more hydrolyzable monomers (Sm) in the presence of an alkali catalyst. The alkali catalyst used at this time is 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, picolin, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, Examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. The amount of catalyst used is preferably 1 × 10⁻⁶ per 1 mole of monomer. -6 moles to 10 moles, more preferably 1×10 -5 moles to 5 moles, more preferably 1×10⁻⁶ -4 It is 1 mole.

[0134] When obtaining a thermally crosslinkable polysiloxane from the above monomer by hydrolytic condensation, it is preferable to add 0.1 to 50 moles of water per mole of hydrolyzable substituent bonded to the monomer. If the amount is 50 moles or less, the apparatus used for the reaction becomes smaller and more economical. If the amount is 0.1 moles or more, the reaction proceeds sufficiently.

[0135] As a method of operation, a monomer is added to an aqueous catalyst solution to initiate a hydrolysis-condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, the monomer may be diluted with an organic solvent, or both methods may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. It is preferable to maintain the temperature at 5 to 80°C when adding the monomer dropwise, and then age it at 20 to 80°C.

[0136] As an organic solvent that can be added to an aqueous alkali catalyst solution or dilute the monomer, it is preferable to use the same organic solvent exemplified as one that can be added to an aqueous acid catalyst solution. In addition, the amount of organic solvent used is preferably 0 to 1,000 ml per mole of monomer, as this allows the reaction to be carried out economically.

[0137] Afterwards, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous solution of the reaction mixture. At this time, the amount of acidic substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the alkaline substance used as a catalyst. Any substance may be used as long as it exhibits acidity in water.

[0138] Furthermore, it is desirable to remove by-products, such as alcohol generated by the hydrolysis condensation reaction from the aqueous solution of the reaction mixture, using methods such as vacuum removal. At this time, the temperature at which the aqueous solution of the reaction mixture is heated depends on the type of alcohol generated by the reaction with the added organic solvent, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. In addition, the degree of vacuum at this time varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably at or below atmospheric pressure, more preferably at or below 80 kPa in absolute pressure, and even more preferably at or below 50 kPa in absolute pressure. Although it is difficult to know the exact amount of alcohol removed at this time, it is desirable that approximately 80 mass% or more of the generated alcohol be removed.

[0139] Next, to remove the catalyst used in the hydrolysis condensation, the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used at this time is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methylamyl 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 methoxypropionate, ethyl ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol monot-butyl ether acetate, Examples include γ-butyrolactone, methylisobutylketone, cyclopentylmethyl ether, and mixtures thereof.

[0140] In addition, it is also possible to use a mixture of water-soluble organic solvents and water-insoluble organic solvents.

[0141] Specific examples of organic solvents used when removing alkali catalysts may be the same as the organic solvents specifically exemplified as those used when removing acid catalysts, or mixtures of water-soluble organic solvents and water-insoluble organic solvents.

[0142] In addition, the mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent is appropriately selected, but for every 100 parts by mass of the water-insoluble organic solvent, preferably 0.1 to 1,000 parts by mass of the water-soluble organic solvent, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0143] Next, the solution is washed with neutral water. It is preferable to use water commonly referred to as deionized water or ultrapure water. The amount of this water is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and preferably 0.1 to 5 L per 1 L of the heat-crosslinkable polysiloxane solution. For this washing method, the two solutions are placed in the same container, mixed, and then allowed to stand to separate the aqueous layer. The number of washes may be at least once, but since the effect of washing is not achieved even if washed more than 10 times, it is preferably about 1 to 5 times.

[0144] A final solvent is added to the thermocrosslinkable polysiloxane solution after washing, and the desired thermocrosslinkable polysiloxane solution is obtained by exchanging the solvent under reduced pressure. The temperature of the solvent exchange at this time 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. In addition, the degree of reduced pressure at this time varies depending on the type of extraction solvent to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably at or below atmospheric pressure, more preferably at or below 80 kPa in absolute pressure, and even more preferably at or below 50 kPa in absolute pressure.

[0145] As a final solvent to be added to a heat-crosslinkable polysiloxane solution, an alcohol-based solvent is preferred, and a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, or dipropylene glycol is particularly preferred. Specifically, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol, etc. are preferred.

[0146] In addition, as a separate reaction operation using an alkali catalyst, water or an aqueous organic solvent is added to the monomer or an organic solution of the monomer to initiate a hydrolysis reaction. At this time, the catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the aqueous organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. It is preferable to heat to 10 to 50°C when adding water dropwise, and then raise the temperature to 20 to 80°C to age the mixture.

[0147] As for organic solvents that can be used as organic solutions or aqueous organic solvents of monomers, water-soluble ones are preferred, and examples include polyhydric alcohol condensation derivatives such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether, and mixtures thereof.

[0148] The molecular weight of the thermally crosslinkable polysiloxane obtained by the above synthesis method 1 or 2 can be adjusted not only by the selection of monomers but also by controlling the reaction conditions during polymerization. However, since the occurrence of foreign substances or coating stains does not occur when the weight average molecular weight is 100,000 or less, it is preferable to use one with a molecular weight of 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. In addition, the data regarding the weight average molecular weight is expressed as the molecular weight in polystyrene equivalent using polystyrene as a standard material by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an elution solvent.

[0149] The properties of the thermally crosslinkable polysiloxane used in the present invention vary depending on the type of acid or alkali catalyst used during hydrolysis condensation or the reaction conditions. Therefore, it can be appropriately selected to match the performance of the desired resist underlayer.

[0150] In addition, a polysiloxane derivative prepared under conditions using the acid or alkali catalyst, comprising a mixture of one or more hydrolyzable monomers (Sm) and a hydrolyzable metal compound represented by the following general formula (Mm), can be used as a component of a composition for forming a resist underlayer.

[0151]

[0152] (of the general formula (Mm), R 7 , and R 8 Each is independently an organic group having 1 to 30 carbon atoms, m7+m8 is equal to the valence determined by the type of U, m7 and m8 are integers greater than or equal to 0, and U is an element of Group III, IV, or V of the periodic table, excluding carbon and silicon.)

[0153] Examples of hydrolyzable metal compounds represented by the general formula (Mm) used at this time include the following. When U is boron, examples of hydrolyzable metal compounds represented by the general 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, boron acid, boron oxide, etc.

[0154] When U is aluminum, examples of hydrolyzable metal compounds represented by the general 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 dipropoxyethylacetoacetate, aluminum dibutoxyethylacetoacetate, aluminum propoxybisethylacetoacetate, aluminum butoxybisethylacetoacetate, aluminum 2,4-pentanedianate, aluminum 2,2,6,6-tetramethyl-3,5-heptanedianate, etc.

[0155] When U is gallium, examples of hydrolyzable metal compounds represented by the general 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 dipropoxyethylacetoacetate, gallium dibutoxyethylacetoacetate, gallium propoxybisethylacetoacetate, gallium butoxybisethylacetoacetate, gallium 2,4-pentanedianate, gallium 2,2,6,6-tetramethyl-3,5-heptanedianate, etc.

[0156] When U is yttrium, examples of hydrolyzable metal compounds represented by the general 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 dipropoxyethylacetoacetate, yttrium dibutoxyethylacetoacetate, yttrium propoxybisethylacetoacetate, yttrium butoxybisethylacetoacetate, yttrium 2,4-pentanedianate, yttrium 2,2,6,6-tetramethyl-3,5-heptanedianate, etc.

[0157] When U is germanium, examples of hydrolyzable metal compounds represented by the general 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, germanium ethoxyethoxide, etc.

[0158] When U is titanium, examples of hydrolyzable metal compounds represented by the general 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 dipropoxybis ethylacetoacetate, titanium dibutoxybis ethylacetoacetate, titanium dipropoxybis 2,4-pentanedianate, titanium dibutoxybis 2,4-pentanedianate, etc.

[0159] When U is hafnium, examples of hydrolyzable metal compounds represented by the general formula (Mm) include hafnium methoxide, hafnium ethoxide, hafnium propoxide, hafnium butoxide, hafnium amyloxide, hafnium hexyloxide, hafnium cyclopentoxide, hafnium cyclohexyloxide, hafnium aryloxide, hafnium phenoxide, hafnium methoxyethoxide, hafnium ethoxyethoxide, hafnium dipropoxybis ethylacetoacetate, hafnium dibutoxybis ethylacetoacetate, hafnium dipropoxybis 2,4-pentanedianate, hafnium dibutoxybis 2,4-pentanedianate, etc.

[0160] When U is tin, examples of hydrolyzable metal compounds represented by the general formula (Mm) include methoxytin, ethoxytin, propoxytin, butoxytin, phenoxytin, methoxyethoxytin, ethoxyethoxytin, tin 2,4-pentanedione, tin 2,2,6,6-tetramethyl-3,5-heptanedione.

[0161] When U is arsenic, examples of hydrolyzable metal compounds represented by the general formula (Mm) include methoxyarsenic, ethoxyarsenic, propoxyarsenic, butoxyarsenic, phenoxyarsenic, etc.

[0162] When U is antimony, examples of hydrolyzable metal compounds represented by the general formula (Mm) include methoxycyantimony, ethoxycyantimony, propoxycyantimony, butoxycyantimony, phenoxycyantimony, antimony acetate, antimony propionate, etc.

[0163] When U is niobium, examples of hydrolyzable metal compounds represented by the general formula (Mm) include methoxyniobium, ethoxyniobium, propoxyniobium, butoxyniobium, phenoxyniobium, etc.

[0164] When U is tantalum, examples of hydrolyzable metal compounds represented by the general formula (Mm) include methoxytantal, ethoxytantal, propoxytantal, butoxytantal, phenoxytantal, etc.

[0165] When U is bismuth, examples of hydrolyzable metal compounds represented by the general formula (Mm) include methoxybismuth, ethoxybismuth, propoxybismuth, butoxybismuth, phenoxybismuth, etc.

[0166] When U is phosphorus, examples of hydrolyzable metal compounds represented by the general formula (Mm) include trimethylphosphate, triethylphosphate, tripropylphosphate, trimethylphosphite, triethylphosphite, tripropylphosphite, and phosphorus pentoxide.

[0167] When U is vanadium, examples of hydrolyzable metal compounds represented by the general formula (Mm) include vanadium oxide bis(2,4-pentanedianate), vanadium 2,4-pentanedianate, vanadium tributoxide oxide, vanadium tripropoxide oxide, etc.

[0168] When U is zirconium, examples of hydrolyzable metal compounds represented by the general formula (Mm) include methoxyzirconium, ethoxyzirconium, propoxyzirconium, butoxyzirconium, phenoxyzirconium, zirconium dibutoxidebis(2,4-pentanedianate), zirconium dipropoxidebis(2,2,6,6-tetramethyl-3,5-heptanedianate).

[0169] In the composition for forming a silicon-containing resist underlayer of the present invention, the amount of thermally crosslinkable polysiloxane (Sx) is preferably 0.1 to 10 mass% with respect to the solvent, for example.

[0170] [Acid generator]

[0171] The composition for forming a silicon-containing resist underlayer according to the present invention preferably further contains an acid generating agent. One or more types of acid generating agents may be incorporated. As for the acid generating agent, any substance acting as an acid precursor, such as a thermal acid generating agent, a photogenerative agent, or an acid proliferator, may be used; however, in the present invention, it is preferable that the acid generating agent is a photogenerative agent that generates acid by the action of high-energy rays, and it is more preferable that the acid generating agent incorporated is a sulfonium salt and a photogenerative agent that generates acid by the action of high-energy rays. More specifically, materials described in paragraphs

[0160] to

[0179] of Japanese Patent Publication No. 2009-126940 may be exemplified, but are not limited thereto. The amount of acid generating agent incorporated is preferably 0 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of thermally crosslinkable polysiloxane (Sx).

[0172] [Other ingredients]

[0173] (Cross-linking catalyst)

[0174] In the composition for forming a silicon-containing resist underlayer of the present invention, in addition to the silicon-containing sulfonium salt compound represented by the general formula (A-1), another crosslinking catalyst (Xc) may be incorporated. As a crosslinking catalyst (Xc) that can be incorporated, a compound represented by the following general formula (Xc0) may be used.

[0175] L a H b A (Xc0)

[0176] (In the general formula (Xc0), L is lithium, sodium, potassium, rubidium, cesium, sulfonium, iodonium, phosphonium, or ammonium; A is a non-nucleophilic counterion; a is an integer greater than or equal to 1; b is an integer greater than or equal to 0 or 1; and a+b is the valence of the non-nucleophilic counterion.)

[0177] Examples of the crosslinking catalyst (Xc) used in the present invention as a compound represented by the specific general formula (Xc0) include the sulfonium salt of the following general formula (Xc-1), the iodonium salt of (Xc-2), the phosphonium salt of (Xc-3), the ammonium salt of (Xc-4), and alkali metal salts.

[0178] The following are examples of sulfonium salts (Xc-1), iodonium salts (Xc-2), phosphonium salts (Xc-3), and ammonium salts (Xc-4).

[0179]

[0180]

[0181] (during food, R 204 , R 205 , R 206 , and R 207 Each represents a straight-chain, 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 of these groups may be substituted by an alkoxy group, etc. Additionally, R 205 and R 206 A ring may be formed, and if a ring is formed, R 205 , R 206 Each represents an alkylene group having 1 to 6 carbon atoms. A - represents a non-nucleophilic counterion. R 208 , R 209 , R 210 , and R 211 silver, R 204 , R 205 , R 206 , and R 207 It is identical to, but may be a hydrogen atom. R 208 and R 209 , or R 208 and R 209 and R 210 A ring may be formed, and if a ring is formed, R208 and R 209 , and R 208 and R 209 and R 210 ...represents an alkylene group having 3 to 10 carbon atoms.

[0182] The above R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , and R 211The groups may be identical or different from each other. Specifically, examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl, etc. Examples of alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl, etc. Examples of oxoalkyl groups include 2-oxocyclopentyl group, 2-oxocyclohexyl group, 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2-(4-methylcyclohexyl)-2-oxoethyl group, etc. Examples of oxoalkenyl groups include 2-oxopropenyl group, 2-oxobutenyl group, 2-oxohexenyl group, 2-oxocyclopentenyl group, 2-oxocyclohexenyl group, etc. Examples of aryl groups include phenyl groups, naphthyl groups, alkoxyphenyl groups such as p-methoxyphenyl groups, m-methoxyphenyl groups, o-methoxyphenyl groups, ethoxyphenyl groups, p-tert-butoxyphenyl groups, m-tert-butoxyphenyl groups, alkylphenyl groups such as 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, alkylnaphthyl groups such as methylnaphthyl groups and ethylnaphthyl groups, alkoxynaphthyl groups such as methoxynaphthyl groups and ethoxynaphthyl groups, dialkylnaphthyl groups such as dimethylnaphthyl groups and diethylnaphthyl groups, and diallkoxynaphthyl groups such as dimethoxynaphthyl groups and diethoxynaphthyl groups. Examples of aralkyl groups include benzyl groups, phenylethyl groups, phenethyl groups, etc. Examples of aryl-oxoalkyl groups include 2-aryl-2-oxoethyl groups, 2-(1-naphthyl)-2-oxoethyl groups, 2-(2-naphthyl)-2-oxoethyl groups, etc.

[0183] A -As non-nucleophilic counterions, hydroxide ions, formate ions, acetate ions, propionic ions, butanoate ions, pentanate ions, hexanoate ions, heptanoate ions, octanoate ions, nonanoate ions, decanoate ions, oleate ions, stearate ions, linoleic ions, linolenic ions, benzoate ions, phthalate ions, isophthalate ions, terephthalate ions, salicylate ions, trifluoroacetate ions, monochloroacetate ions, dichloroacetate ions, trichloroacetate ions, fluoride ions, chloride ions, bromide ions, iodide ions, nitrate ions, nitrite ions, chloride ions, bromate ions, bromic acid ions, methanesulfonate ions, p-toluenesulfonate ions, monomethylsulfate ions, monovalent or divalent oxalate ions, malonicate ions, methylmalonicate ions, ethylmalonicate ions, Examples include propylmalonicate ions, butylmalonicate ions, dimethylmalonicate ions, diethylmalonicate ions, succinate ions, methylsuccinate ions, glutarate ions, adipicate ions, itaconate ions, maleate ions, fumarate ions, citraconicate ions, citrate ions, carbonate ions, sulfate ions, etc.

[0184] Examples of alkali metal salts include hydroxides, formates, acetates, propionates, butanoates, pentanates, hexanoates, heptanoates, octanoates, nonanoates, decanoates, oleates, stearates, linoleates, linolenicates, benzoates, phthalates, isophthalates, terephthalates, salicylates, monovalent salts such as trifluoroacetates, monochloroacetates, dichloroacetates, and trichloroacetates, monovalent or divalent oxalates, malonsates, methylmalonsates, ethylmalonsates, propylmalonsates, butylmalonsates, dimethylmalonsates, diethylmalonsates, succinates, methylsuccinates, glutarates, adipates, itaconates, maleates, fumarates, citraconates, citrates, carbonates, etc.

[0185] Specifically, as a sulfonium salt (Xc-1), triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionic acid, triphenylsulfonium butoxate, triphenylsulfonium benzoate, triphenylsulfonium phthalate, triphenylsulfonium isophthalate, triphenylsulfonium terephthalate, triphenylsulfonium salicylate, triphenylsulfonium trifluoromethanesulfonic acid, triphenylsulfonium trifluoroacetate, triphenylsulfonium monochloroacetate, triphenylsulfonium dichloroacetate, triphenylsulfonium trichloroacetate, triphenylsulfonium hydroxide, triphenylsulfonium nitrate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium oxalate, triphenylsulfonium malonicate, triphenylsulfonium methylmalonicate, triphenylsulfonium ethylmalonicate, triphenylsulfonium propylmalonicate, Examples include triphenylsulfonium butylmalonicate, triphenylsulfonium dimethylmalonicate, triphenylsulfonium diethylmalonicate, triphenylsulfonium succinate, triphenylsulfonium methylsuccinate, triphenylsulfonium glutarate, triphenylsulfonium adipicate, triphenylsulfonium itaconate, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylsulfonium citraconicate, triphenylsulfonium citrate, triphenylsulfonium carbonate, bistriphenylsulfonium oxalate, bistriphenylsulfonium maleate, bistriphenylsulfonium fumarate, bistriphenylsulfonium citraconicate, bistriphenylsulfonium citrate, bistriphenylsulfonium carbonate, etc.

[0186] In addition, specifically as iodium salts (Xc-2), diphenyliodonium formate, diphenyliodonium acetate, diphenyliodonium propionate, diphenyliodonium butanoate, diphenyliodonium benzoate, diphenyliodonium phthalate, diphenyliodonium isophthalate, diphenyliodonium terephthalate, diphenyliodonium salicylate, diphenyliodonium trifluoromethanesulfonicate, diphenyliodonium trifluoroacetate, diphenyliodonium monochloroacetate, diphenyliodonium dichloroacetate, diphenyliodonium trichloroacetate, diphenyliodonium hydroxide, diphenyliodonium nitrate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide, diphenyliodonium oxalate, diphenyliodonium maleate, Examples include diphenyliodonium fumarate, diphenyliodonium citraconic acid, diphenyliodonium citrate, diphenyliodonium carbonate, bisdiphenyliodonium oxalate, bisdiphenyliodonium maleate, bisdiphenyliodonium fumarate, bisdiphenyliodonium citraconic acid, bisdiphenyliodonium citrate, bisdiphenyliodonium carbonate, etc.

[0187] In addition, specifically as phosphonium salts (Xc-3), tetraethylphosphonium formate, tetraethylphosphonium acetate, tetraethylphosphonium propionate, tetraethylphosphonium butoxate, 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 citraconate, Tetraethylphosphonium citrate, Tetraethylphosphonium carbonate, Bistraethylphosphonium oxalate, Bistraethylphosphonium maleate, Bistraethylphosphonium fumarate, Bistraethylphosphonium citraconate, Bistraethylphosphonium citrate, Bistraethylphosphonium 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, Tetraphenylphosphonium citraconate, Tetraphenylphosphonium citrate, Tetraphenylphosphonium carbonate, Bistetraphenylphosphonium oxalate, Bistetraphenylphosphonium maleate, Bistetraphenylphosphonium fumarate, Bistetraphenylphosphonium citraconate, Bistetraphenylphosphonium citrate,Examples include bistetraphenylphosphonium carbonate, etc.

[0188] Meanwhile, specifically as ammonium salts (Xc-4), 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 malonicate, tetramethylammonium maleate, Tetramethylammonium fumarate, Tetramethylammonium citraconate, Tetramethylammonium citrate, Tetramethylammonium carbonate, Bistetramethylammonium oxalate, Bistetramethylammonium malonicate, 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 malonicate, Tetraethylammonium maleate, Tetraethylammonium fumarate, Tetraethylammonium citraconate, Tetraethylammonium citrate, Tetraethylammonium carbonate, Bistetraethylammonium oxalate, Bistetraethylammonium malonicate, 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, Tetrapropylammonium dichloroacetate, Tetrapropylammonium trichloroacetate, Tetrapropylammonium hydroxide, Tetrapropylammonium nitrate, Tetrapropylammonium chloride, Tetrapropylammonium bromide, Tetrapropylammonium iodide, Tetrapropylammonium monomethylsulfate, Tetrapropylammonium oxalate, Tetrapropylammonium malonicate, Tetrapropylammonium maleate, Tetrapropylammonium fumarate, Tetrapropylammonium citraconic acid, Tetrapropylammonium citrate, Tetrapropylammonium carbonate, Bistetrapropylammonium oxalate, Bistetrapropylammonium malonicate, Bistetrapropylammonium maleate, Bistetrapropylammonium fumarate, Bistetrapropylammonium citraconic acid, Bistetrapropylammonium citrate, Bistetrapropylammonium carbonate, Tetrabutylammonium formate, Tetrabutylammonium acetate, Tetrabutylammonium propionate, Tetrabutylammonium butylammonium butylammonium benzoate, Tetrabutylammonium phthalate, Tetrabutylammonium isophthalate, Tetrabutylammonium terephthalate, Tetrabutylammonium salicylate, Tetrabutylammonium trifluoromethanesulfonic acid, 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 malonicate, Tetrabutylammonium maleate, Tetrabutylammonium fumarate, Tetrabutylammonium citraconic acid, Tetrabutylammonium citrate, Tetrabutylammonium carbonate,Examples include bistetrabutylammonium oxalate, bistetrabutylammonium malonicate, bistetrabutylammonium maleate, bistetrabutylammonium fumarate, bistetrabutylammonium citraconic acid, bistetrabutylammonium citrate, bistetrabutylammonium carbonate, etc.

[0189] As alkali metal salts, 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 malonicate, lithium hydrogen maleate, lithium hydrogen fumarate, lithium hydrogen citrate, lithium hydrogen citrate, lithium bicarbonate, lithium oxalate, lithium malonicate, lithium maleate, lithium fumarate, lithium citrate, 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 malonicate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium hydrogen citrate, sodium bicarbonate, sodium oxalate, sodium malonicate, sodium maleate, sodium fumarate, sodium citrate, sodium citrate, sodium carbonate, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium benzoate, potassium phthalate, potassium isophthalate, Examples include 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 malonicate, potassium hydrogen maleate, potassium hydrogen fumarate, potassium hydrogen citrate, potassium hydrogen citrate, potassium bicarbonate, potassium oxalate, potassium malonicate, potassium maleate, potassium fumarate, potassium citrate, potassium citrate, potassium carbonate, etc.

[0190] In the present invention, as a crosslinking catalyst (Xc), 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 incorporated into the composition for forming a resist underlayer.

[0191] As a raw material used to manufacture the (Xc-10) used here, a compound represented by the following general formula (Xm) may be used.

[0192] R 1A A1 R 2A A2 R 3A A3 Si(OR 0A ) (4-A1-A2-A3) (Xm)

[0193] (of the general 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 them 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.)

[0194] Here, R 0A Examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, and phenyl group.

[0195] As Xm, for example, a compound represented by the following general formula (Xm-1), which is a hydrolyzable silicon compound having a sulfonium salt as part of its structure, can be exemplified.

[0196]

[0197] (of the general formula (Xm-1), R SA1 , and R SA2Each represents a straight-chain, 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 of these groups may be substituted by an alkoxy group, an amino group, an alkylamino group, a halogen atom, etc. Additionally, R SA1 and R SA2 They may form a ring together with the sulfur atom to which they bond, and if a ring is formed, R SA1 , and R SA2 Each represents an alkylene group having 1 to 6 carbon atoms. R SA3 ...is represented by a straight-chain, 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 by an alkoxy group, an amino group, an alkylamino group, etc.)

[0198] In addition, in the above general formula (Xm-1), (Si) is described to indicate the bonding location with Si.

[0199] X -As, hydroxide ion, fluoride ion, chloride ion, bromide ion, iodide ion, formate ion, acetate ion, propionic ion, butanoate ion, pentanate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleic ion, linolenic ion, benzoate ion, p-methylbenzoate ion, pt-butylbenzoate ion, phthalate ion, isophthalate ion, terephthalate ion, salicylate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, trichloroacetate ion, nitrate ion, chlorate ion, perchlorate ion, bromate ion, iodate ion, methanesulfonate ion, benzenesulfonate ion, toluenesulfonate ion, monomethylsulfate ion, hydrogen sulfate ion, oxalic acid Examples include ions, malonicate ions, methylmalonicate ions, ethylmalonicate ions, propylmalonicate ions, butylmalonicate ions, dimethylmalonicate ions, diethylmalonicate ions, succinate ions, methylsuccinate ions, glutarate ions, adipicate ions, itaconate ions, maleate ions, fumarate ions, citraconicate ions, citrate ions, carbonate ions, etc.

[0200] As the cation portion of the compound represented by the above general formula (Xm-1), specifically, the following ions are exemplified.

[0201]

[0202] As Xm, for example, a hydrolyzable silicon compound having an iodine salt as part of its structure can be exemplified by a compound represented by the following general formula (Xm-2).

[0203]

[0204] (of the general formula (Xm-2), R IA1R represents a straight-chain, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxo-alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryl-oxoalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, an amino group, an alkylamino group, a halogen atom, etc. IA2 ...represents a straight-chain, 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 by an alkoxy group, an amino group, an alkylamino group, etc.)

[0205] In addition, in the above general formula (Xm-2), (Si) is described to indicate the bonding site with Si. X - It is as stated above.

[0206] As the cation portion of the compound represented by the above general formula (Xm-2), specifically, the following ions are exemplified.

[0207]

[0208] As Xm, for example, a hydrolyzable silicon compound having a phosphonium salt as part of its structure can be exemplified by a compound represented by the following general formula (Xm-3).

[0209]

[0210] (of the general formula (Xm-3), R PA1 , R PA2 , and R PA3Each represents a straight-chain, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxo-alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryl-oxoalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, an amino group, an alkylamino group, a halogen atom, etc. Additionally, R PA1 and R PA2 They may form a ring together with the phosphorus atom to which they bond, and if a ring is formed, R PA1 , and R PA2 Each represents an alkylene group having 1 to 6 carbon atoms. R PA4 is a straight-chain, 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 by an alkoxy group, an amino group, an alkylamino group, etc.)

[0211] In addition, in the above general formula (Xm-3), (Si) is described to indicate the bonding site with Si. X - It is as stated above.

[0212] As the cation portion of the compound represented by the above general formula (Xm-3), specifically, the following ions are exemplified.

[0213]

[0214]

[0215] As Xm, for example, a hydrolyzable silicon compound having an ammonium salt as part of its structure can be exemplified by a compound represented by the following general formula (Xm-4).

[0216]

[0217] (of the general formula (Xm-4), R NA1 , R NA2 , and R NA3Each represents a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group, an oxoalkyl group, or an oxo-alkenyl group, 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 of these groups may be substituted by an alkoxy group, an amino group, an alkylamino group, etc. Additionally, R NA1 and R NA2 They may form a ring with the nitrogen atom to which they bond, and if a ring is formed, R NA1 , and R NA2 represents, respectively, an alkylene group having 1 to 6 carbon atoms, a nitrogen-containing cyclic heterocyclic ring, or a complex aromatic ring. NA4 represents a straight-chain, 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 by an alkoxy group, an amino group, an alkylamino group, etc. R NA1 and R NA2 , or R NA1 and R NA4 In cases where it forms a cyclic structure and contains additional unsaturated nitrogen, it is n N3 =0, otherwise n N3 =1.)

[0218] In addition, in the above general formula (Xm-4), (Si) is described to indicate the bonding site with Si. X - It is as stated above.

[0219] As the cation portion of the compound represented by the above general formula (Xm-4), specifically, the following ions are exemplified.

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233] To manufacture (Xc-10), the hydrolyzable monomer (Sm) may be exemplified as a hydrolyzable silicon compound used simultaneously with (Xm-1), (Xm-2), (Xm-3), and (Xm-4). Additionally, a hydrolyzable metal compound (Mm) represented by the general formula (Mm) may be added.

[0234] One or more of the monomers (Xm-1), (Xm-2), (Xm-3), and (Xm-4) shown as described above, one or more of (Sm), and if additionally necessary, one or more of (Mm) can be selected and mixed before or during the reaction to form (Xc-10) as reaction raw materials. The reaction conditions may be the same as the synthesis method of the thermally crosslinkable polysiloxane (Sx).

[0235] The molecular weight of the obtained crosslinking catalyst (Xc-10) can be adjusted not only by the selection of monomers but also by controlling reaction conditions during polymerization. However, since the occurrence of foreign substances or coating stains does not occur when the weight average molecular weight is 100,000 or less, it is preferable to use one with a molecular weight of 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. In addition, the data regarding the weight average molecular weight is expressed as a polystyrene equivalent by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an elution solvent, using polystyrene as a standard material.

[0236] In addition, the above-mentioned crosslinking catalysts (Xc-1), (Xc-2), (Xc-3), (Xc-4), and (Xc-10) may be used individually or in combination of two or more types. The amount of 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 (thermally crosslinkable polysiloxane (Sx) obtained by the above method).

[0237] (Organic acid)

[0238] To improve the stability of the silicon-containing resist underlayer 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 acids added at this time include formic acid, acetic acid, propionic acid, butanoic acid, pentoic 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, citric acid, etc. In particular, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid, etc. are preferred. In addition, to maintain stability, two or more types of 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, based on 100 parts by mass of silicon included in the silicon-containing resist underlayer forming composition of the present invention.

[0239] Alternatively, the above organic acid is preferably formulated such that the pH of the composition for forming a silicon-containing resist underlayer of the present invention is converted to 0≤pH≤7, more preferably 0.3≤pH≤6.5, and even more preferably 0.5≤pH≤6.

[0240] (water)

[0241] In the present invention, water may be added to the composition for forming a silicon-containing resist sublayer. When water is added, the polysiloxane compound in the composition for forming a silicon-containing resist sublayer of the present invention becomes hydrated, thereby improving lithography performance. The water content in the solvent component of the composition for forming a silicon-containing resist sublayer of the present invention is preferably greater than 0 mass% and less than 50 mass%, particularly preferably 0.3 to 30 mass%, and more preferably 0.5 to 20 mass%. If the amount of water added is less than 50 mass%, the uniformity of the silicon-containing resist sublayer is improved, and splashing does not occur. On the other hand, if the amount of water added exceeds 0 mass%, the lithography performance improves.

[0242] The total amount of solvent including water used is preferably 100 to 100,000 parts by mass, and particularly preferably 200 to 50,000 parts by mass, with respect to 100 parts by mass of the base polymer, which is a thermocrosslinkable polysiloxane.

[0243] (stabilizator)

[0244] In addition, in the present invention, a stabilizer may be added to the composition for forming a silicon-containing resist underlayer. As a stabilizer, a monovalent or divalent or higher alcohol having a cyclic ether as a substituent may be added. In particular, adding the stabilizer described in paragraphs

[0181] to

[0182] of Japanese Patent Publication No. 2009-126940 can improve the stability of the composition for forming a silicon-containing resist underlayer. The amount of the stabilizer is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, with respect to 100 parts by mass of the base polymer, thermocrosslinkable polysiloxane (Sx).

[0245] (Surfactant)

[0246] In addition, in the present invention, it is possible to incorporate a surfactant into the composition for forming a silicon-containing resist underlayer as needed. Specifically, the material described in paragraph

[0185] of Japanese Patent Publication No. 2009-126940 may be added. The amount of surfactant incorporated is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, with respect to 100 parts by mass of the base polymer, thermocrosslinkable polysiloxane (Sx).

[0247] (High boiling point solvent)

[0248] In addition, in the present invention, it is also possible to add a high-boiling point solvent having a boiling point of 180°C or higher to the composition as needed. As this high-boiling point solvent, 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, diacetone alcohol, n-nonyl acetate, ethylene glycol monoethyl ether, 1,2-diacetoxyethane, 1-acetoxy-2-methoxyethane, 1,2-diacetoxypropane, diethylene glycol monomethyl ether, Examples include diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether. The amount of high-boiling point solvent is preferably 0 to 20 mass%, more preferably 0 to 10 mass%, of the solvent component.

[0249] [Pattern Formation Method]

[0250] One of the pattern forming methods of the present invention is a method of forming a pattern on a workpiece, wherein

[0251] A process of forming an organic film on a workpiece using a coating-type organic film material, and

[0252] A process of forming a silicon-containing resist underlayer on the above organic film using the silicon-containing resist underlayer forming composition described above, and

[0253] A process for forming a resist upper layer using a composition for a resist upper layer comprising a photoresist composition on the silicon-containing resist lower layer, and

[0254] A process of forming a circuit pattern on the upper layer of the above-mentioned resist, and

[0255] A process of transferring a pattern to a silicon-containing resist lower film by etching using the resist upper film having the circuit pattern formed thereon as a mask, and

[0256] A process of transferring a pattern to an organic film by etching using the silicon-containing resist lower layer film on which the above pattern has been transferred as a mask, and

[0257] A process of transferring a pattern to a workpiece by etching using the organic film having the above pattern transferred thereon as a mask.

[0258] It is a pattern forming method including (so-called "multilayer resist method").

[0259] One of the pattern forming methods of the present invention is a method of forming a pattern on a workpiece, wherein

[0260] A process of forming a hard mask on a workpiece using the CVD method, and

[0261] A process of forming a silicon-containing resist underlayer on the hard mask using the silicon-containing resist underlayer forming composition described above, and

[0262] A process for forming a resist upper layer using a composition for a resist upper layer comprising a photoresist composition on the silicon-containing resist lower layer, and

[0263] A process of forming a circuit pattern on the upper layer of the above-mentioned resist, and

[0264] A process of transferring a pattern to a silicon-containing resist lower film by etching using the resist upper film having the circuit pattern formed thereon as a mask, and

[0265] A process of transferring a pattern onto a hard mask by dry etching using the silicon-containing resist lower layer film having the above pattern transferred thereon as a mask, and

[0266] A process of transferring a pattern to a workpiece by dry etching using the hard mask having the above pattern transferred thereon as a mask.

[0267] It is a pattern forming method including (so-called "multilayer resist method").

[0268] One of the pattern forming methods of the present invention is a method of forming a pattern on a workpiece, wherein

[0269] A process of forming a silicon-containing resist underlayer on a workpiece using the silicon-containing resist underlayer forming composition described above, and

[0270] A process for forming a resist upper layer using a composition for a resist upper layer comprising a photoresist composition on the silicon-containing resist lower layer, and

[0271] A process of forming a circuit pattern on the upper layer of the above-mentioned resist, and

[0272] A process of transferring a pattern to a silicon-containing resist lower film by etching using the resist upper film having the circuit pattern formed thereon as a mask, and

[0273] A process of transferring a pattern to a workpiece by dry etching using the silicon-containing resist lower layer film having the above pattern transferred thereon as a mask.

[0274] It is a pattern forming method including (so-called "multilayer resist method").

[0275] The pattern obtained by incorporating the silicon-containing sulfonium salt compound of the present invention into a composition for forming a silicon-containing resist sublayer can form a fine pattern on a substrate with excellent LWR or CDU by optimizing the combination of a hard mask or an organic film as described above. In addition, since the silicon-containing resist sublayer remaining after pattern formation is easily removed by etching or the like, residues that cause defects can be suppressed, and substrate damage caused by excessive etching conditions can also be prevented.

[0276] In a method for forming a positive type pattern, after forming a photoresist film (resist upper layer) and performing heat treatment, exposure is performed, and alkaline development is performed using a conventional alkaline developer to obtain a positive type resist pattern. Additionally, it is preferable to perform a post-exposure bake (PEB) after exposure.

[0277] As the above alkaline developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) or the like can be used.

[0278] As a method for forming a circuit pattern on the upper layer of the above-mentioned resist, it is preferable to use a pattern forming method utilizing photolithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof.

[0279] It is preferable to use, as the above-mentioned workpiece, a semiconductor device substrate, or a material on which any one of 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 is formed.

[0280] As the above metal, it is preferable to use silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or alloys thereof.

[0281] Examples

[0282] The present invention will be specifically described below by presenting synthetic examples, comparative synthetic examples, examples, and comparative examples, but the present invention is not limited by these descriptions. In addition, in the following examples, % represents mass %, and molecular weight (Mw) is the weight-average molecular weight converted to polystyrene by GPC measurement.

[0283] [Synthesized Example 1-1]

[0284] A mixture of 30.6 g of compound (101), 38.1 g of compound (102), and 5.9 g of compound (110) was added to a mixture of 120 g of methanol, 0.1 g of 10% nitric acid, and 60 g of deionized water (molar ratio: 40 / 50 / 10), and hydrolytic condensation was carried out by maintaining at 40°C for 12 hours. After the reaction was finished, 600 g of propylene glycol monoethyl ether (PGEE) was added, and the water and byproduct alcohol provided for the hydrolytic condensation were removed by distillation under reduced pressure to obtain 440 g of a PGEE solution of polysiloxane compound 1 (compound concentration 10%). The polystyrene equivalent molecular weight of polysiloxane compound 1 was measured and found to be Mw = 2,900.

[0285] [Synthetic Example 1-1] was performed using the monomers shown in Table 1 under the same conditions as [Synthetic Example 1-1], and [Synthetic Example 1-2] to [Synthetic Example 1-18] were obtained, with polysiloxane compounds 2 to 18 respectively.

[0286]

[0287] PhSi(OCH3)3···compound (100)

[0288] CH3Si(OCH3)3···compound (101)

[0289] Si(OCH3)4···compound (102)

[0290]

[0291] [Example of Synthesis of Crosslinked Catalyst]

[0292] [Synthesization Example 2-1] Synthesis of Compound A (Intermediate 1)

[0293]

[0294] 55 g of trimethylsilyl magnesium bromide was dissolved in 190 g of tetrahydrofuran, and 14 g of thionyl chloride dissolved in 35 g of tetrahydrofuran was added dropwise to this solution at 0°C. After aging at room temperature for 6 hours, 10% hydrochloric acid was added to quench the mixture, the reaction solution was diluted with dichloromethane and washed with water, and water was added to the organic layer three times to perform separation. The resulting organic layer was then concentrated under reduced pressure, the resulting oil phase was decanted with hexane, and the solid obtained after filtration was dried under reduced pressure to obtain 52 g of the target compound A as white crystals (yield 69%).

[0295] [Synthesization Example 2-2] Synthesis of Compound B

[0296]

[0297] 10 g of Compound A prepared in Synthesis Example 2-1 was dissolved in 50 g of dichloromethane, and 9 g of chlorotrimethylsilane was added dropwise under ice cooling. Subsequently, a separately adjusted Grignard reagent was added dropwise under ice cooling. After aging at room temperature for 1.5 hours, an aqueous ammonium chloride solution was added under ice cooling, followed by the addition of dichloromethane to separate the organic layer, and water was added to the organic layer five times to perform separation. The obtained organic layer was then concentrated under reduced pressure, the resulting oil phase was decanted with diisopropyl ether, and the solid obtained after filtration was dried under reduced pressure to obtain 12 g of the target product, Compound B, as white crystals (yield 92%).

[0298] [Synthesization Example 2-3] Synthesis of Compound B'

[0299]

[0300] 7 g of compound B prepared in Synthesis Example 2-2 was dissolved in 100 g of dichloromethane, and 25 g of a 7% aqueous nitric acid solution was added thereto to separate the organic layer. The same operation was repeated twice. Additionally, water was added to the organic layer four times to separate the liquids. The obtained organic layer was then concentrated under reduced pressure, the resulting oil phase was decanted with diisopropyl ether, and the solid obtained after filtration was dried under reduced pressure to obtain 7 g of the target compound B' as a white crystal (yield 94%).

[0301] [Synthetic Examples 2-4] through [Synthetic Examples 2-13] were performed using the raw materials and acids shown in Table 2 under the same conditions as Synthetic Examples 2-2 and 3, and the target products were obtained for each.

[0302]

[0303] [Reaction Material]

[0304]

[0305] [prize]

[0306]

[0307] [Comparative Synthesis Example 1-1] Synthesis of Sulfonium Salt-Containing Polysiloxane Compound R

[0308] A mixture of 61.3 g of compound (101) and 24.4 g of compound (120) was added to a mixture of 120 g of methanol, 0.1 g of 10% nitric acid, and 60 g of deionized water, and hydrolytic condensation was carried out by maintaining the mixture at 40°C for 12 hours. After the reaction was finished, 300 g of propylene glycol monoethyl ether (PGEE) was added, and the water and byproduct alcohol provided for the hydrolytic condensation were removed by distillation under reduced pressure to obtain 250 g of a PGEE solution of polysiloxane compound R containing a sulfonium salt (compound concentration 20%). The polystyrene equivalent molecular weight of polysiloxane compound R was measured and found to be Mw = 2,000.

[0309] [Examples 1-1 to 1-55, and Comparative Examples 1-1 to 1-4]

[0310] Polysiloxane compounds 1 to 18 obtained in the above synthesis examples, a silicon-containing sulfonium salt compound represented by the above general formula (A-1) or a comparative crosslinking catalyst as a crosslinking catalyst, an acid, a photocatalyst (PAG-1 to 7 listed in Table 6), a solvent, and water were mixed in the ratios shown in Tables 3 to 5, and by filtering with a 0.1 μm fluoropolymer filter, a silicon-containing underlayer forming composition solution was prepared and each was designated as Sol. 1 to 59.

[0311]

[0312]

[0313]

[0314] The crosslinking catalysts used are as follows.

[0315] XL-1···Compound (B)

[0316] XL-2···Compound (B')

[0317] XL-3···Compound (C)

[0318] XL-4···Compound (D)

[0319] XL-5···Compound (E)

[0320] XL-6···Compound (F)

[0321] XL-7···Compound (G)

[0322] XL-8···Compound (I)

[0323] XL-9···Compound (K)

[0324] XL-10···Compound (M)

[0325] XL-11···Compound (O)

[0326] XL-12···Compound (Q)

[0327] XL-13···triphenylsulfonium nitrate

[0328] XL-14···Tetramethylammonium nitrate

[0329] XL-15···Tetraoctylammonium nitrate

[0330] XL-16···Sulfonium salt-containing polysiloxane compound (R)

[0331] The solvents used are as follows.

[0332] PGEE···propylene glycol monoethyl ether

[0333] PGME···propylene glycol monomethyl ether

[0334] GBL···Gamma-butyrolactone

[0335] DAA···diacetone alcohol

[0336]

[0337] (EUV Patterning Test)

[0338] Sol. 1 to 59, which is a composition for forming a silicon-containing resist underlayer film on a silicon wafer, was spin-coated onto a Si substrate and heated at 220°C for 60 seconds to produce a silicon-containing resist underlayer film, Film 1 to 59, with a film thickness of 25 nm.

[0339] Next, a resist material prepared by dissolving the following components in the ratios shown in Table 7 was spin-coated onto Films 1 to 59, and a resist upper layer film with a thickness of 60 nm was fabricated by pre-baking at 105°C for 60 seconds using a hot plate. This was then exposed using an ASML EUV scanner NXE3300 (NA 0.33, σ 0.9 / 0.6, quadruple illumination, wafer dimensions pitch 46 nm, +20% bias hole pattern mask), PEB was performed on a hot plate at 100°C for 60 seconds, and development was performed with a 2.38 mass% TMAH aqueous solution for 30 seconds to obtain a hole pattern with dimensions of 23 nm.

[0340] Using a measuring SEM (CG5000) manufactured by Hitachi High Technologies Co., Ltd., the exposure amount at which the hole dimension is formed to 23 nm was measured and used as the sensitivity. Additionally, the dimensions of 50 holes at this time were measured to calculate the dimensional deviation (CDU, 3σ). The results are shown in Tables 8 and 9.

[0341] The polymer, quencher, sensitizer, surfactant, and organic solvent used as resist materials are as follows.

[0342]

[0343]

[0344]

[0345] Surfactant: 3M FC-4430

[0346] PGMEA: Propylene glycol monomethyl ether acetate

[0347] CyHO: Cyclohexanone

[0348] PGME: Propylene glycol monomethyl ether

[0349]

[0350] (Silicon-containing resist underlayer etching test)

[0351] Sol. 1 to 59, which is a composition for forming a silicon-containing resist underlayer film on a silicon wafer, was spin-coated onto a Si substrate and heated at 220°C for 60 seconds to produce a silicon-containing resist underlayer film, Film 1 to 59, with a film thickness of 25 nm.

[0352] These silicon-containing resist underlayer films were subjected to an etching test under the following etching conditions.

[0353] Etching test in CHF3 / CF4 gas

[0354] Device: Telius SP dry etching device manufactured by Tokyo Electron Co., Ltd.

[0355] Etching test:

[0356] Chamber pressure 10 Pa

[0357] Upper / Lower RF power 200 W / 100 W

[0358] CHF3 gas flow rate 50 ml / min

[0359] CF4 gas flow rate 50 ml / min

[0360] N2 gas flow rate 100 ml / min

[0361] Processing time 20 sec

[0362]

[0363]

[0364] As shown in Comparative Examples 1-1 to 1-4 of Tables 8 and 9, it was confirmed that in Films 56 to 59, which do not use the silicon-containing sulfonium salt compound represented by the general formula (A-1) of the present invention as a crosslinking catalyst, there is deterioration of the CDU or a lack of sufficient etching speed. On the other hand, as shown in Examples 1-1 to 1-55, it was found that in Films 1 to 55, which use the silicon-containing sulfonium salt compound represented by the general formula (A-1) of the present invention as a crosslinking catalyst, diffusion into the upper resist is suppressed due to high affinity with the silicon polymer, thereby providing a CDU improvement effect and a sufficient etching speed.

[0365] [Examples 2-1 to 2-14, and Comparative Examples 2-1 to 2-4]

[0366] (ArF patterning test)

[0367] On a silicon wafer, a spin-on carbon film ODL-102 (carbon content 89 mass%) manufactured by Shin-Etsu Chemical Co., Ltd. was formed with a film thickness of 200 nm. On the above, Sol. 1-4, 10-12, 26-29, 50-52, 56-59, which is a composition for forming a silicon-containing resist underlayer film, was applied onto the spin-on carbon film and heated at 220°C for 60 seconds to produce a silicon-containing resist underlayer film, Film 1-4, 10-12, 26-29, 50-52, 56-59, with a film thickness of 20 nm.

[0368] Next, an ArF resist solution for positive development (PR-1) described in Table 10 was applied onto the silicon-containing resist sublayer film and baked at 110°C for 60 seconds to form a photoresist film with a thickness of 100 nm. In addition, an immersion protective film material (TC-1) described in Table 11 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.

[0369] Next, these were exposed to an ArF immersion lithography system (manufactured by ASML; XT-1900i, NA 1.35, σ 0.97 / 0.77, 35-degree dipole polarized illumination), baked (PEB) at 100°C for 60 seconds, and developed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to obtain a 40 nm 1:1 positive line and space pattern. For this dimension, LWR was observed using an electron microscope (CG5000) manufactured by Hitachi High Technologies Co., Ltd. The results are shown in Table 12.

[0370]

[0371] ArF Resist Polymer 1 [Molecular Weight (Mw) = 7,800, Dispersion (Mw / Mn) = 1.78]:

[0372]

[0373] Acid-generating agent: PAG-A

[0374]

[0375] Base: Quencher

[0376]

[0377] Surfactant: 3M FC-4430

[0378]

[0379] Protective polymer [Molecular weight (Mw) = 8,800, Dispersion (Mw / Mn) = 1.69]

[0380]

[0381]

[0382] As shown in Examples 2-1 to 2-14 of Table 12, it was confirmed that Films 1 to 4, 10 to 12, 26 to 29, and 50 to 52, which used a silicon-containing sulfonium salt compound represented by the general formula (A-1) of the present invention as a crosslinking catalyst, showed an LWR improvement effect because diffusion into the upper layer resist was suppressed due to high affinity with the silicon polymer.

[0383] Meanwhile, as shown in Comparative Examples 2-1 to 2-4, in Films 56 to 59 in which the silicon-containing sulfonium salt compound represented by the general formula (A-1) of the present invention is not used as a crosslinking catalyst, the LWR deteriorated.

[0384] The present specification includes the following aspects.

[0385] [1]: A silicon-containing sulfonium salt compound characterized by being represented by the following general formula (A-1).

[0386]

[0387] (during food, Ar 1 , Ar 2 , and Ar 3Each is independently an aromatic group having 6 to 20 carbon atoms that may have substituents, or a heteroaromatic group having 4 to 20 carbon atoms that may have substituents. Also, Ar 1 , Ar 2 , and Ar 3 Any two or more selected from may combine with each other to form a ring together with the sulfur atom in the formula. a, b, and c are each independently integers from 0 to 3, and 1 ≤ a + b + c ≤ 9. X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, and may be identical or different from each other. A - represents an organic or inorganic anion that serves as the counterion for a sulfonium cation.

[0388] [2]: A composition for forming a silicon-containing resist underlayer, characterized by containing the silicon-containing sulfonium salt compound of [1] and a thermally crosslinkable polysiloxane.

[0389] [3]: A composition for forming a silicon-containing resist underlayer of [2], characterized in that the above-mentioned thermally crosslinkable polysiloxane comprises one or more of the following general formula (Sx-1), the following general formula (Sx-2), and the following substructure (Sx-3).

[0390]

[0391]

[0392]

[0393] (during food, R 1 , R 2 , and R 3 Each is a monovalent organic group having 1 to 30 carbon atoms, which may be identical or different.

[0394] [4]: A composition for forming a silicon-containing resist underlayer of [2] or [3], characterized by further containing an acid-generating agent.

[0395] [5]: A composition for forming a silicon-containing resist underlayer according to [4], characterized in that the above acid generator is a photo-generating agent that generates acid by the action of high-energy rays.

[0396] [6]: A method of forming a pattern on a workpiece,

[0397] A process of forming an organic film on a workpiece using a coating-type organic film material, and

[0398] A process of forming a silicon-containing resist underlayer on the above organic film using any one of the silicon-containing resist underlayer forming compositions [2] to [5], and

[0399] A process for forming a resist upper layer using a composition for a resist upper layer comprising a photoresist composition on the silicon-containing resist lower layer, and

[0400] A process of forming a circuit pattern on the upper layer of the above-mentioned resist, and

[0401] A process of transferring a pattern to a silicon-containing resist lower film by etching using the resist upper film having the circuit pattern formed thereon as a mask, and

[0402] A process of transferring a pattern to an organic film by etching using the silicon-containing resist lower layer film on which the above pattern has been transferred as a mask, and

[0403] A process of transferring a pattern to a workpiece by etching using the organic film having the above pattern transferred thereon as a mask.

[0404] A pattern forming method characterized by including

[0405] [7]: A method of forming a pattern on a workpiece,

[0406] A process of forming a hard mask on a workpiece using the CVD method, and

[0407] A process of forming a silicon-containing resist underlayer on the hard mask using any one of the silicon-containing resist underlayer forming compositions [2] to [5], and

[0408] A process for forming a resist upper layer using a composition for a resist upper layer comprising a photoresist composition on the silicon-containing resist lower layer, and

[0409] A process of forming a circuit pattern on the upper layer of the above-mentioned resist, and

[0410] A process of transferring a pattern to a silicon-containing resist lower film by etching using the resist upper film having the circuit pattern formed thereon as a mask, and

[0411] A process of transferring a pattern onto a hard mask by dry etching using the silicon-containing resist lower layer film having the above pattern transferred thereon as a mask, and

[0412] A process of transferring a pattern to a workpiece by dry etching using the hard mask having the above pattern transferred thereon as a mask.

[0413] A pattern forming method characterized by including

[0414] [8]: A method for forming a circuit pattern on the upper layer of the resist, characterized by using photolithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof. [6] or [7] pattern formation method.

[0415] [9]: A method for forming a pattern of any one of [6] to [8], characterized by using a semiconductor device substrate, or a semiconductor device substrate on which 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 are formed.

[0416]

[10] : The pattern forming method of [9] is characterized by using silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof as the metal.

[0417] Furthermore, the present invention is not limited to the above embodiments. The above embodiments are merely examples, and any configuration substantially identical to the technical concept described in the claims of the present invention and any function that exhibits the same effect are included within the technical scope of the present invention.

Claims

Claim 1 A silicon-containing sulfonium salt compound characterized by being represented by the following general formula (A-1). (during food, Ar 1 , Ar 2 , and Ar 3 Each is independently an aromatic group having 6 to 20 carbon atoms, which may have substituents, or a heteroaromatic group having 4 to 20 carbon atoms, which may have substituents. The above substituents are straight-chain, branched, or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups, heteroaromatic groups, alkoxy groups, hydroxyl groups, ester groups, carbonyl groups, amino groups, halogen groups, carboxyl groups, sulfonyl groups, amide groups, imide groups, cyano groups, aldehyde groups, imino groups, urea groups, carbamate groups, carbonate groups, nitro groups, sulfonyl groups, and groups formed by combinations of these groups. Additionally, Ar 1 , Ar 2 , and Ar 3 Any two or more selected from may combine with each other to form a ring together with the sulfur atom in the formula. a, b, and c are each independently integers from 0 to 3, and 1 ≤ a + b + c ≤ 9. X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, and may be identical or different from each other. A - represents an organic or inorganic anion that serves as the counterion for a sulfonium cation. Claim 2 A composition for forming a silicon-containing resist underlayer, characterized by containing the silicon-containing sulfonium salt compound described in claim 1 and a thermally crosslinkable polysiloxane. Claim 3 A composition for forming a silicon-containing resist underlayer according to claim 2, characterized in that the thermally crosslinkable polysiloxane comprises one or more of the following general formula (Sx-1), the following general formula (Sx-2), and the following substructure (Sx-3). (during food, R 1 , R 2 , and R 3 Each is a monovalent organic group having 1 to 30 carbon atoms, which may be identical or different. Claim 4 A composition for forming a silicon-containing resist underlayer, characterized by further containing an acid-generating agent in paragraph 2. Claim 5 A composition for forming a silicon-containing resist underlayer, characterized in that, in claim 4, the acid generator is a photo-generating agent that generates acid by the action of high-energy rays. Claim 6 A method for forming a pattern on a workpiece, comprising: a process of forming an organic film on a workpiece using a coating-type organic film material; a process of forming a silicon-containing resist lower film on the organic film using a composition for forming a silicon-containing resist lower film as described in any one of claims 2 to 5; a process of forming a resist upper film on the silicon-containing resist lower film using a composition for forming a resist upper film including a photoresist composition; a process of forming a circuit pattern on the resist upper film; a process of transferring the pattern by etching to the silicon-containing resist lower film using the resist upper film having the circuit pattern formed thereon as a mask; a process of transferring the pattern by etching to the organic film using the silicon-containing resist lower film having the transferred pattern as a mask; and a process of transferring the pattern by etching to the workpiece using the organic film having the transferred pattern as a mask. Claim 7 A method for forming a pattern on a workpiece, comprising: a process of forming a hard mask on a workpiece by a CVD method; a process of forming a silicon-containing resist lower layer on the hard mask using a composition for forming a silicon-containing resist lower layer described in any one of claims 2 to 5; a process of forming a resist upper layer on the silicon-containing resist lower layer using a composition for forming a resist upper layer including a photoresist composition; a process of forming a circuit pattern on the resist upper layer; a process of transferring the pattern to the silicon-containing resist lower layer by etching using the resist upper layer on which the circuit pattern is formed as a mask; a process of transferring the pattern to the hard mask by dry etching using the silicon-containing resist lower layer on which the pattern is transferred as a mask; and a process of transferring the pattern to the workpiece by dry etching using the hard mask on which the pattern is transferred as a mask. Claim 8 A pattern formation method according to claim 6, characterized by using photolithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof as a method for forming a circuit pattern on the upper layer of the resist. Claim 9 A pattern formation method according to claim 7, wherein the method for forming a circuit pattern on the upper layer of the resist is characterized by using photolithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof. Claim 10 A pattern forming method according to claim 6, characterized in that, as the workpiece, a semiconductor device substrate, or any one of 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 is formed on the semiconductor device substrate. Claim 11 A pattern forming method according to claim 7, characterized in that, as the workpiece, a semiconductor device substrate, or any one of 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 is formed on the semiconductor device substrate. Claim 12 A pattern forming method according to claim 10, characterized in that, as the metal, silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof. Claim 13 A pattern forming method according to claim 11, characterized in that, as the metal, silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

Images