Silicon-containing sulfonium salt compound, composition for forming silicon-containing resist underlayer film, and pattern forming method

Abstract

The invention relates to a silicon-containing sulfonium salt compound, a silicon-containing composition for forming a resist underlayer film, and a pattern forming method. Provided are: a composition for forming a silicon-containing resist underlayer film, which is capable of forming a silicon-containing resist underlayer film that has an appropriate etching rate in a multi-layer resist method and is capable of improving LWR and CDU in an ultra-fine pattern; a silicon-containing sulfonium salt compound contained in the composition; and a pattern forming method using the composition. A silicon-containing sulfonium salt compound characterized by being a substance represented by general formula (A-1). [chemical] # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a sulfur-containing salt compound containing silicon, a composition for forming a silicon-containing anti-reflective lower layer film containing the foregoing compound, and a patterning method using the foregoing composition. Background Art

[0002] With the high integration and high speed of large-scale integrated circuits (LSIs), the miniaturization of pattern sizes has advanced rapidly. In lithography technology, with this miniaturization, by shortening the wavelength of the light source and appropriately selecting the corresponding resist composition, the formation of fine patterns has been achieved. The central one is a positive photoresist composition used in a single layer. This single-layer positive photoresist composition has a skeleton in the resist resin that has etching resistance to dry etching using chlorine-based or fluorine-based gas plasmas and a switching mechanism that causes the exposed portion to dissolve. Thereby, the exposed portion is dissolved to form a pattern, and the remaining resist pattern is used as an etching mask to dry-etch the substrate to be processed.

[0003] However, if the film thickness of the directly used photoresist film is miniaturized, that is, if the pattern width is further reduced, the resolution performance of the photoresist film will decrease, and if the photoresist film is to be pattern-developed using a developer, the so-called aspect ratio will become too large, and as a result, there will be a problem of pattern collapse. Therefore, with the miniaturization of patterns, the photoresist film becomes thinner and thinner.

[0004] On the other hand, in the processing of the substrate to be processed, a method of using the formed pattern photoresist film as an etching mask and dry-etching the substrate is usually used. However, in reality, there is no dry-etching method that can achieve complete etching selectivity between the photoresist film and the substrate to be processed. Therefore, in substrate processing, there will be a problem that even the photoresist film is damaged and collapses, and the resist pattern cannot be correctly transferred to the substrate to be processed. With the miniaturization of patterns, higher dry-etching resistance is required for the resist composition. However, on the other hand, in order to improve the resolution, the resin used in the photoresist composition increasingly requires a resin with low light absorption at the exposure wavelength. Therefore, as the exposure light progresses to shorter wavelengths of i-ray, KrF, and ArF, the resin also changes to novolak resin, polyhydroxystyrene, and a resin with an aliphatic polycyclic skeleton. However, in reality, the etching rate under the dry-etching conditions during substrate processing becomes faster, and the latest photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] Therefore, it is necessary to dry-etch the substrate to be processed with a thinner and weaker etching-resistant photoresist film, and ensuring the materials and processes in this processing step has become an urgent matter.

[0006] As one of the methods for solving such problems, there is a multilayer resist method. In this method, a photoresist film (i.e., the upper resist film) is inserted between the upper resist film and the substrate to be processed, and a lower resist film with different etching selectivity is used. After obtaining a pattern on the upper resist film, the pattern of the upper resist film is used as a dry etching mask, and the pattern is transferred to the lower resist film by dry etching. Then, the lower resist film is used as a dry etching mask, and the pattern is transferred to the substrate to be processed by dry etching.

[0007] One of the multilayer resist methods is a three-layer resist method that can be implemented using the general resist compositions used in the single-layer resist method. In this three-layer resist method, for example, an organic film obtained by forming a novolak resin or the like on the substrate to be processed is used as the lower resist film, a silicon-containing resist intermediate film is formed thereon as the resist intermediate film, and a normal organic photoresist film is formed thereon as the upper resist film. When dry etching is performed using a fluorine-based gas plasma, the organic upper resist film can obtain a good etching selectivity ratio with respect to the silicon-containing resist intermediate film. Therefore, the pattern of the upper resist film can be transferred to the silicon-containing resist intermediate film by dry etching using the 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 the substrate or a resist composition that does not have sufficient dry etching resistance for substrate processing is used, if the pattern can be transferred to the silicon-containing resist intermediate film and then the pattern is transferred by dry etching using an oxygen-based or hydrogen-based gas plasma, a pattern of an organic film made of novolak resin or the like with sufficient dry etching resistance for substrate processing can be obtained. After the formation of the organic film pattern, the remaining silicon-containing resist intermediate film is generally removed by dry etching using a fluorine-based gas plasma or wet etching using an etching solution such as an alkali-based or fluorine-based solution to avoid becoming a residue that causes defects. When the etching speed is insufficient, residues from the silicon-containing resist intermediate film will remain and become defects, or a long etching process may be required, which may increase the possibility of problems such as damage to the substrate to be processed. Thus, for correct patterning and smooth removal, the silicon-containing resist intermediate film requires an appropriate etching speed.

[0008] On the other hand, in recent years, due to the emergence of ArF immersion lithography, EUV lithography, etc., finer patterns can be formed. However, along with this, the thinning of the photoresist film will progress further. Such thinning of the photoresist film will cause deterioration of the line width roughness (LWR) and the critical dimension uniformity (CDU) of the hole pattern in ultra-fine patterns. Therefore, the improvement of 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 hardening catalyst has been proposed (Patent Documents 1 and 2). This hardening catalyst has a structure suitable for catalyzing the condensation reaction of silanols and promoting the formation of siloxane bonds that form the main skeleton of the silicon-containing resist intermediate film. Also, it has gradually become clear that the selection of the hardening catalyst has various effects on the properties of the silicon-containing resist intermediate film. For example, acidity / alkalinity, hydrophilicity / hydrophobicity, hardness, film density, etching rate, etc. Such a hardening catalyst has a similar structure to the sensitivity adjuster in the upper resist. Therefore, if it diffuses into the upper resist due to heating or exposure, it will have a significant impact on the pattern formation ability of the photoresist, becoming a problem. In particular, it will affect the performance of LWR and CDU, so it is necessary to develop a hardening catalyst that can suppress diffusion into the upper resist.

[0010] On the other hand, in order to improve LWR and CDU, a photosensitive upper photoresist material containing a compound having a cation and an anion in the molecule has been known (Patent Document 3). However, for today's ultra-fine patterns, higher-precision LWR and CDU are required, and it is also necessary to improve the performance of the silicon-containing resist intermediate film.

[0011] [Prior Art Documents]

[0012] [Patent Documents]

[0013] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-302873

[0014] [Patent Document 2] International Publication No. 2013 / 161372

[0015] [Patent Document 3] Japanese Patent Application Laid-Open No. 2011-016746 Summary of the Invention

[0016] [Problems to be Solved by the Invention]

[0017] An object of the present invention is to provide a composition for forming a silicon-containing resist lower layer film that can form a silicon-containing resist lower layer film having an appropriate etching rate in a multilayer resist method and can improve LWR and CDU in ultra-fine patterns, a silicon-containing sulfonium salt compound contained in the foregoing composition, and a pattern forming method using the foregoing composition.

[0018] [Means for Solving the Problems]

[0019] In order to solve the above problems, the present invention provides a silicon-containing sulfonium salt compound represented by the following general formula (A-1).

[0020] [Chemical Formula 1]

[0021]

[0022] In the formula, Ar 1 , Ar 2 , and Ar 3 are each 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. Further, any two or more selected from Ar 1 , Ar 2 , and Ar 3 may also be bonded to each other and form a ring together with the sulfur atom in the formula. a, b, and c are each independently an integer representing 0 to 3, and 1 ≤ a + b + c ≤ 9. X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, which may be the same or different from each other. A - represents an organic or inorganic anion which is a counter ion forming a sulfonium cation.

[0023] If such a silicon-containing sulfonium salt compound is added to a composition for forming a silicon-containing resist underlayer film, it acts as a hardening catalyst and can promote its thermal hardening. Further, since the silicon-containing sulfonium salt compound of the present invention has a high affinity for a silicon polymer, by adding it to a composition for forming a silicon-containing resist underlayer film, diffusion to the upper resist can be suppressed, and a silicon-containing resist underlayer film having good LWR and CDU characteristics can be formed. Further, due to the effect of the silicon atom, a silicon-containing resist underlayer film having a good etching rate can be formed.

[0024] Further, the present invention provides a composition for forming a silicon-containing resist underlayer film, which contains the above-described silicon-containing sulfonium salt compound and a thermally crosslinkable polysiloxane.

[0025] If such a composition for forming a silicon-containing resist underlayer film is used, a silicon-containing resist underlayer film having an appropriate etching rate in a multilayer resist method and capable of improving LWR and CDU in an ultra-fine pattern can be formed.

[0026] It is preferable that the above-described thermally crosslinkable polysiloxane contains any one or more of a repeating unit represented by the following general formula (Sx-1), a repeating unit represented by the following general formula (Sx-2), and a partial structure represented by the following general formula (Sx-3).

[0027] [Chemical formula 2]

[0028]

[0029] [Chemical formula 3]

[0030]

[0031] [Chemical formula 4]

[0032]

[0033] In the formula, R1 , R 2 , and R 3 are each independently a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different.

[0034] When the above-mentioned thermally crosslinkable polysiloxane contains the above-mentioned specific structure, the effects of the present invention can be more fully exerted.

[0035] Preferably, the composition for forming a silicon-containing underlayer film of a resist further contains an acid generator.

[0036] By adding an acid generator as needed, the pattern shape, exposure sensitivity, etc. can be finely adjusted.

[0037] Preferably, the aforementioned acid generator is a photoacid generator that generates an acid upon the action of high-energy radiation.

[0038] In this case, other performance degradation can be suppressed to a minimum, and at the same time, the pattern shape, exposure sensitivity, etc. of the upper layer resist film can be moderately adjusted. In addition, it is sometimes effective in reducing residues from the upper layer resist film.

[0039] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a workpiece, comprising the following steps:

[0040] forming an organic film on the workpiece using a coating-type organic film material,

[0041] forming a silicon-containing underlayer film of a resist on the aforementioned organic film using the composition for forming a silicon-containing underlayer film of a resist described above,

[0042] forming an upper layer resist film on the aforementioned silicon-containing underlayer film of a resist using a composition for an upper layer resist film composed of a photoresist composition,

[0043] forming a circuit pattern on the aforementioned upper layer resist film,

[0044] using the aforementioned upper layer resist film on which the circuit pattern has been formed as a mask, and transferring the pattern to the aforementioned silicon-containing underlayer film of a resist by etching,

[0045] using the aforementioned silicon-containing underlayer film of a resist on which the pattern has been transferred as a mask, and transferring the pattern to the aforementioned organic film by etching,

[0046] using the aforementioned organic film on which the pattern has been transferred as a mask, and transferring the pattern to the aforementioned workpiece by etching.

[0047] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a workpiece, comprising the following steps:

[0048] forming a hard mask on the workpiece by CVD method,

[0049] On the foregoing hard mask, a silicon-containing lower resist film is formed using the composition for forming a silicon-containing lower resist film described above.

[0050] On the foregoing silicon-containing lower resist film, an upper resist film is formed using the composition for an upper resist film composed of a photoresist composition.

[0051] A circuit pattern is formed on the foregoing upper resist film.

[0052] Using the foregoing upper resist film on which the circuit pattern has been formed as a mask, the pattern is transferred to the foregoing silicon-containing lower resist film by etching.

[0053] Using the foregoing silicon-containing lower resist film on which the pattern has been transferred as a mask, the pattern is transferred to the foregoing hard mask by dry etching.

[0054] Using the foregoing hard mask on which the pattern has been transferred as a mask, the pattern is transferred to the foregoing workpiece by dry etching.

[0055] In the above pattern formation method, collapse of the pattern of the upper resist film is suppressed, and pattern transfer to the silicon-containing lower resist film by dry etching is excellent. Further, removal of the remaining silicon-containing lower resist film after patterning is easy, and defects are not easily generated due to residues. Therefore, it is a pattern formation method particularly useful for forming fine patterns.

[0056] As a method for forming a circuit pattern on the foregoing upper resist film, it is preferable to use optical lithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination thereof.

[0057] When the method for forming a circuit pattern on the above upper resist film is the above specific method, the effects of the present invention can be more fully exhibited.

[0058] As the foregoing workpiece, a semiconductor device substrate, or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed on the semiconductor device substrate can be used.

[0059] When the above specific workpiece is used, the effects of the present invention can be more fully exhibited.

[0060] Further, as the foregoing 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.

[0061] When the metal constituting the above workpiece is the above specific metal, the effects of the present invention can be more fully exhibited.

[0062] [Effects of the Invention]

[0063] As described above, in the case of the sulfur-containing salt compound containing silicon of the present invention, by adding it to a composition for forming a silicon-containing resist underlayer film containing a thermally crosslinkable polysiloxane as a hardening catalyst, not only can a superfine upper resist pattern with good LWR and CDU be formed, but also the dry etching selectivity with respect to the resist upper layer film and an organic film or a hard mask is excellent, and a pattern for a semiconductor device can be formed on a substrate with a good yield. Further, for the formed silicon-containing resist underlayer film, a high etching selectivity can be obtained with respect to an organic material, so the formed upper resist pattern can be sequentially transferred to the silicon-containing resist underlayer film and an organic film or a hard mask by dry etching treatment. Moreover, the formed silicon-containing resist underlayer film has a sufficient etching rate, so it is easy to remove the remaining silicon-containing resist underlayer film after patterning, and it is not easy to generate defects due to residues. Therefore, it is particularly useful for forming a fine pattern. Detailed Description of the Invention

[0064] As described above, there is a demand for developing a composition for forming a silicon-containing resist underlayer film, a sulfur-containing salt compound containing silicon contained in the composition, and a pattern forming method using the composition, which can form a silicon-containing resist underlayer film having an appropriate etching rate in a multilayer resist method and can improve LWR and CDU in a superfine pattern.

[0065] The inventors of the present application diligently studied to achieve the above object, and as a result, found that by incorporating a sulfur-containing salt compound containing silicon having a specific structure into a composition for forming a silicon-containing resist underlayer film, a silicon-containing resist underlayer film having improved LWR and CDU in a superfine pattern in a multilayer resist method and having an etching rate suitable for processing can be obtained, and thus the present invention was completed.

[0066] That is, the present invention is a sulfur-containing salt compound containing silicon represented by the following general formula (A-1).

[0067] [Chemical Formula 5]

[0068]

[0069] In the formula, Ar 1 , Ar 2 , and Ar 3 are each independently an aromatic group having 6 to 20 carbon atoms which may have a substituent, or a heteroaromatic group having 4 to 20 carbon atoms which may have a substituent. Further, selected from Ar 1 , Ar 2 , and Ar 3Two or more of them may also be bonded to each other and form a ring together with the sulfur atom in the formula. a, b, and c are each independently an integer representing 0 to 3, and 1 ≤ a + b + c ≤ 9. X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, which may be the same or different from each other. A - represents an organic or inorganic anion that is the counter ion of the sulfonium cation.

[0070] The present invention will be described in detail below, but the present invention is not limited thereto.

[0071] <Composition for forming a silicon-containing anti-reflective lower layer film>

[0072] The composition for forming a silicon-containing anti-reflective lower layer film of the present invention contains a silicon-containing sulfonium salt compound represented by the following general formula (A-1) and a thermally crosslinkable polysiloxane. In addition to these, optional components may be contained.

[0073] Each component contained in the composition for forming a silicon-containing anti-reflective lower layer film of the present invention will be described in detail below.

[0074] <Silicon-containing sulfonium salt compound>

[0075] 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 hardening catalyst.

[0076] [Chemical formula 6]

[0077]

[0078] In the formula, Ar 1 , Ar 2 , and Ar 3 are each independently an aromatic group having 6 to 20 carbon atoms which may have a substituent, or a heteroaromatic group having 4 to 20 carbon atoms which may have a substituent. Also, two or more of Ar 1 , Ar 2 , and Ar 3 may be bonded to each other and form a ring together with the sulfur atom in the formula. a, b, and c are each independently an integer representing 0 to 3, and 1 ≤ a + b + c ≤ 9. X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, which may be the same or different from each other. A - represents an organic or inorganic anion that is the counter ion of the sulfonium cation.

[0079] The silicon-containing sulfonium salt compound of the present invention, when added to a composition for forming a silicon-containing anti-reflective coating film, can act as a hardening catalyst and promote thermal hardening. During hardening, since the affinity of this compound for the silicon polymer is high, diffusion into the upper-layer resist is suppressed, which helps to improve LWR and CDU. Also, the formed silicon-containing anti-reflective coating film has a moderate composition / structure and is considered to have a sufficient etching rate for processing.

[0080] In the present specification, a film formed below the upper-layer resist film is referred to as a lower-layer film, and includes what is called an anti-reflective coating lower-layer film and a silicon-containing anti-reflective coating intermediate film.

[0081] In the above general formula (A-1), Ar 1 、Ar 2 、and Ar 3 each independently represents 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. Examples of the aromatic group having 6 to 20 carbon atoms include, specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. Examples of the heteroaromatic group having 4 to 20 carbon atoms include, specifically, a furyl group, a thienyl group, a pyrrolyl group, a benzofuryl group, a pyridyl group, an indolyl group, an oxazolyl group, an imidazolyl group, and a benzimidazolyl group. Substituents that may be present include, for example, a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, a heteroaromatic group, an alkoxy group, a hydroxyl group, an ester group, a carbonyl group, an amino group, a halogen group, a thioether group, a carboxyl group, a sulfo group, an acylamino group, an imide group, a cyano group, an aldehyde group, an imino group, a ureido group, a carbamate group, a carbonate group, a nitro group, a sulfonyl group, and a group formed by combining these groups. From the viewpoint of more effectively presenting the effects of the present invention, a phenyl group, a naphthyl group, a furyl group, a thienyl group, a pyrrolyl group, and a pyridyl group are preferable, and a phenyl group and a naphthyl group are more preferable. Also, any two or more of Ar 1 、Ar 2 、and Ar 3 may be bonded to each other to form a ring together with the sulfur atom in the formula, and from the viewpoints of solubility and stability, it is more preferable that no ring is formed.

[0082] In the above general formula (A-1), X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, which may be the same or different from each other. Examples of the monovalent organic group having 1 to 14 carbon atoms include, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, an adamantyl group, an alkenyl group, an oxoalkyl group, an aryl group, an aralkyl group, an aryloxoalkyl group, etc.

[0083] Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group.

[0084] Oxoalkyl groups, such as 2-oxocyclopentyl, 2-oxocyclohexyl, etc., 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, 2-(4-methylcyclohexyl)-2-oxoethyl, etc.

[0085] Aryl groups, such as phenyl, naphthyl, etc., p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, m-tert-butoxyphenyl, etc. alkoxyphenyls, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, etc. alkylphenyls, methylnaphthyl, ethylnaphthyl, etc. alkylnaphthyls, methoxynaphthyl, ethoxynaphthyl, etc. alkoxynaphthyls, dimethylnaphthyl, diethylnaphthyl, etc. dialkylnaphthyls, dimethoxynaphthyl, diethoxynaphthyl, etc. dialkoxynaphthyls, etc.

[0086] Aralkyl groups, such as benzyl, phenylethyl, styryl, etc.

[0087] Aryloxoalkyl groups, such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, 2-(2-naphthyl)-2-oxoethyl, etc. 2-aryl-2-oxoethyls, etc.

[0088] In order to more effectively present the effects of the present invention, methyl, ethyl, and isopropyl are preferred, and methyl and ethyl are more preferred.

[0089] In the above general formula (A-1), A - represents an organic or inorganic anion that is the relative ion of the sulfonium cation. Specifically, for organic anions, for example, formate, acetate, propionate, butyrate, hexanoate, benzoate, tert-butylbenzoate, trichloroacetate, trifluoroacetate, 2-hydroxy-2,2-bis(trifluoromethyl)acetate, trimethylacetate, pentafluoropropionate, methanesulfonate, butanesulfonate, benzenesulfonate, toluenesulfonate, trifluoromethanesulfonate, methyl sulfate, etc. For inorganic anions, specifically, for example, chloride ion, bromide ion, iodide ion, fluoride ion, cyanide ion, nitrate ion, nitrite ion, hydroxide ion, etc. Among the said anions, chloride ion, iodide ion, fluoride ion, nitrate ion, nitrite ion, hydroxide ion are preferred, and chloride ion and nitrate ion are more preferred.

[0090] In the present invention, the silicon-containing sulfonium salt compound represented by the above general formula (A-1) can be used alone or in combination of two or more. The blending amount of the silicon-containing sulfonium salt compound represented by the above general formula (A-1) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, relative to 100 parts by mass of the thermally crosslinkable polysiloxane (Sx) described later.

[0091] The sulfuronium salt compound containing silicon represented by the above general formula (A-1), more specifically, the following compounds can be cited but are not limited thereto. In the following formula, Me represents a methyl group, and the same applies hereinafter.

[0092] [Chemical formula 7]

[0093]

[0094] [Chemical formula 8]

[0095]

[0096] [Chemical formula 9]

[0097]

[0098] [Thermally crosslinkable polysiloxane]

[0099] The composition for forming a silicon-containing anti-reflective lower layer film of the present invention further contains a thermally crosslinkable polysiloxane in addition to one or more of the silicon-containing sulfuronium salt compounds represented by the above general formula (A-1).

[0100] The thermally crosslinkable polysiloxane (Sx) used in the present invention preferably contains any one or more of the repeating units represented by the following general formula (Sx-1), the repeating units represented by the following general formula (Sx-2), and the partial structure represented by the following general formula (Sx-3).

[0101] [Chemical formula 10]

[0102]

[0103] [Chemical formula 11]

[0104]

[0105] [Chemical formula 12]

[0106]

[0107] In the formula, R 1 , R 2 , and R 3 are each independently a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different.

[0108] The above thermally crosslinkable polysiloxane (Sx) can be produced, for example, by hydrolytic condensation of the following hydrolyzable monomers (Sm).

[0109] Hydrolyzable monomers (Sm), specifically, for example, 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, isopropyltripropoxysilane, isopropyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltriisopropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, isobutyltriisopropoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltripropoxysilane, sec-butyltriisopropoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butyltripropoxysilane, tert-butyltriisopropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, allyltriisopropoxysilane, cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane, cyclopropyltripropoxysilane, cyclopropyltriisopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyltripropoxysilane, cyclobutyltriisopropoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltripropoxysilane, cyclopentyltriisopropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, cyclohexyltriisopropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltripropoxysilane, bicycloheptenyltriisopropoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyltripropoxysilane, bicycloheptyltriisopropoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyltripropoxysilane, adamantyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 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, dibutyldiisopropoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldipropoxysilane, di-sec-butyldiisopropoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldipropoxysilane, di-tert-butyldiisopropoxysilane, dicyclopropyldimethoxysilane, dicyclopropyldiethoxysilane, dicyclopropyldipropoxysilane, dicyclopropyldiisopropoxysilane, dicyclobutyldimethoxysilane, dicyclobutyldiethoxysilane, dicyclobutyldipropoxysilane, dicyclobutyldiisopropoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentyldipropoxysilane, dicyclopentyldiisopropoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane, dicyclohexyldiisopropoxysilane, dicyclohexenyldimethoxysilane, dicyclohexenyldiethoxysilane, dicyclohexenyldipropoxysilane, dicyclohexenyldiisopropoxysilane, dicyclohexenylethyldimethoxysilane, dicyclohexenylethyldiethoxysilane, dicyclohexenylethyldipropoxysilane, dicyclohexenylethyldiisopropoxysilane, dicyclooctyldimethoxysilane, dicyclooctyldiethoxysilane, dicyclooctyldipropoxysilane, dicyclooctyldiisopropoxysilane, dicyclopentadienylpropyldimethoxysilane, dicyclopentadienylpropyldiethoxysilane, dicyclopentadienylpropyldipropoxysilane, dicyclopentadienylpropyldiisopropoxysilane, bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis(bicycloheptenyl)dipropoxysilane, bis(bicycloheptenyl)diisopropoxysilane, bis(bicycloheptyl)dimethoxysilane,Bis(bicycloheptyl)diethoxysilane, bis(bicycloheptyl)dipropoxysilane, bis(bicycloheptyl)diisopropoxysilane, diadamantyldimethoxysilane, diadamantyldiethoxysilane, diadamantyldipropoxysilane, diadamantyldiisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethylbenzylmethoxysilane, dimethylbenzylethoxysilane, dimethylphenethylmethoxysilane, dimethylphenethylethoxysilane, etc.

[0110] Preferably, the above compounds are, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane, etc.

[0111] The above R 1 、R 2 、and R 3 Other examples of the organic group represented are, for example, an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, an organic group having one or more groups selected from the group consisting of an ether bond, an ester bond, an alkoxy group, a hydroxyl group, etc. This example is represented by the following general formula (Sm-R), for example.

[0112] (P-Q1-(S1) v1 -Q2-) u -(T) v2-Q3-(S2) v3 -Q4-

[0113] (Sm-R)

[0114] 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 alkylcarbonyloxy group having 2 to 6 carbon atoms, or an alkylcarbonyl group having 2 to 6 carbon atoms, and Q1, Q2, Q3, and Q4 are each independently -C q H (2q-p) P p -(wherein, P is as described above, p is an integer of 0 to 3, q is an integer of 0 to 10 (however, when q = 0, it represents a single bond)), u is an integer of 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 composed of a divalent atom other than carbon, an alicyclic ring, an aromatic ring, or a heterocyclic ring.)

[0115] Examples of the alicyclic ring, aromatic ring, or heterocyclic ring that may contain a heteroatom such as an oxygen atom for T are shown below. The bonding position of Q2 and Q3 in T is not particularly limited, and it can be appropriately selected in consideration of reactivity due to steric factors, availability of commercially available reagents used in the reaction, etc.)

[0116] [Chemical formula 13]

[0117]

[0118] Preferred examples of the organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (Sm-R) are listed below. Also, in the following formulas, (Si) is described to indicate the bonding position to Si.)

[0119] [Chemical formula 14]

[0120]

[0121] [Chemical formula 15]

[0122]

[0123] Also, for R 1 、R 2 、and R 3 Examples of the organic group can also use an organic group containing a silicon-silicon bond. Specifically, they are listed below.)

[0124] [Chemical formula 16]

[0125]

[0126] Also, for R 1 、R 2, and R 3 Examples of the organic group of 3 include organic groups having a protecting group decomposed by an acid. Specifically, examples include the organic groups listed in paragraphs

[0043] to

[0048] of Japanese Patent Application Laid-Open No. 2013-167669 and organic groups obtained from the silicon compounds disclosed in paragraph

[0056] of Japanese Patent Application Laid-Open No. 2013-224279.

[0127] Also, for R 1 , R 2 , and R 3 Examples of the organic group of 3 include organic groups having a fluorine atom. Specifically, examples include organic groups obtained from the silicon compounds disclosed in paragraphs

[0059] to

[0065] of Japanese Patent Application Laid-Open No. 2012-053253.

[0128] In the above hydrolyzable monomer (Sm), one, two, or three chlorine, bromine, iodine, acetoxy, methoxy, ethoxy, propoxy, or butoxy groups, etc., are bonded to the silicon represented by (Si) in the above partial structure as hydrolyzable groups.

[0129] [Synthesis Method of Thermally Crosslinkable Polysiloxane (Sx)]

[0130] (Synthesis Method 1: Acid Catalyst)

[0131] The thermally crosslinkable polysiloxane (Sx) used in the present invention can be produced by subjecting a mixture of one or more hydrolyzable monomers (Sm) to hydrolysis and condensation in the presence of an acid catalyst.

[0132] The acid catalyst used at this time includes, for example, organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid, and inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid. The amount of the catalyst used is preferably 1×10 -6 to 10 moles, more preferably 1×10 -5 to 5 moles, and even more preferably 1×10 -4 to 1 mole, per 1 mole of the monomer.

[0133] When obtaining the thermally crosslinkable polysiloxane (Sx) by hydrolysis and condensation of the monomer, the amount of water added is, for example, 0.01 to 100 moles, more preferably 0.05 to 50 moles, and even more preferably 0.1 to 30 moles, per 1 mole of the hydrolyzable substituent bonded to the monomer. If it is 100 moles or less, the apparatus used for the reaction is reduced, which is economical. If it is 0.01 mole or more, the reaction proceeds sufficiently.

[0134] Operation method, for example: monomers can be added to the catalyst aqueous solution to initiate the hydrolysis and condensation reaction. At this time, an organic solvent can be added to the catalyst aqueous solution, or the monomers can be diluted with an organic solvent, or both can be carried out. The reaction temperature can be set, for example, at 0 to 100 °C, preferably 5 to 80 °C. A method of maintaining the temperature at 5 to 80 °C during the monomer addition and then aging it at 20 to 80 °C is preferred.

[0135] The organic solvent that can be added to the catalyst aqueous solution or used to dilute the monomers is preferably methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, ethylene glycol, propylene glycol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl pentanone, butylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monoterbutyl ether acetate, γ-butyrolactone, and mixtures thereof, etc.

[0136] Among the above solvents, water-soluble solvents are more desirable. For example: alcohols such as methanol, ethanol, 1-propanol, 2-propanol, etc., polyols such as ethylene glycol, propylene glycol, polyol condensate derivatives such as butylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butylene glycol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, acetone, acetonitrile, tetrahydrofuran, etc. Among them, solvents with a boiling point of 100 °C or lower are particularly desirable.

[0137] Furthermore, the amount of the organic solvent used can be set, for example, at 0 to 1,000 ml, particularly preferably 0 to 500 ml, relative to 1 mole of the monomers. If the amount of the organic solvent used is small, the reaction vessel can be reduced, which is economical.

[0138] After that, 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 the basic substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used as the catalyst. As long as this basic substance is alkaline in water, it can be any substance.

[0139] Then, it is preferable to remove by-products such as alcohols generated in the hydrolysis condensation reaction from the reaction mixture by reduced pressure or the like. At this time, the temperature at which the reaction mixture is heated depends on the types of the added organic solvent and the alcohols generated by the reaction, preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. Also, the degree of reduced pressure at this time varies depending on the types of the organic solvent and alcohols to be removed, the exhaust device, the condensation device, and the heating temperature, preferably below atmospheric pressure, more preferably below an absolute pressure of 80 kPa, and even more preferably below an absolute pressure of 50 kPa. The amount of alcohol removed at this time is difficult to accurately determine, but it is desirable to remove more than about 80% by mass of the generated alcohols and the like.

[0140] Then, the acid catalyst used in the hydrolysis condensation can also be removed from the reaction mixture. The method for removing the acid catalyst is to mix water with the thermally crosslinkable polysiloxane solution and extract the thermally crosslinkable polysiloxane solution with an organic solvent. The organic solvent used at this time is preferably one that can dissolve the thermally crosslinkable polysiloxane and will form 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, methyl amyl ketone, butylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butylene glycol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monoterbutyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof, etc.

[0141] Alternatively, a mixture of a water-soluble organic solvent and a water-insoluble organic solvent can also be used. For example: methanol-ethyl acetate mixture, ethanol-ethyl acetate mixture, 1-propanol-ethyl acetate mixture, 2-propanol-ethyl acetate mixture, ethylene glycol monomethyl ether acetate-ethyl acetate mixture, propylene glycol monomethyl ether acetate-ethyl acetate mixture, ethylene glycol monomethyl ether-ethyl acetate mixture, ethylene glycol monoethyl ether acetate-ethyl acetate mixture, propylene glycol monoethyl ether acetate-ethyl acetate mixture, ethylene glycol monoethyl ether-ethyl acetate mixture, ethylene glycol monopropyl ether acetate-ethyl acetate mixture, propylene glycol monopropyl ether acetate-ethyl acetate mixture, ethylene glycol monopropyl ether-ethyl acetate mixture, methanol-methyl isobutyl ketone mixture, ethanol-methyl isobutyl ketone mixture, 1-propanol-methyl isobutyl ketone mixture, 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-cyclopentyl methyl ether mixture, ethanol-cyclopentyl methyl ether mixture, 1-propanol-cyclopentyl methyl ether mixture, 2-propanol-cyclopentyl methyl ether mixture, propylene glycol monomethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monomethyl ether-cyclopentyl methyl ether mixture, propylene glycol monoethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monoethyl ether-cyclopentyl methyl ether mixture, propylene glycol monopropyl ether-cyclopentyl methyl ether mixture, ethylene glycol monopropyl ether-cyclopentyl methyl ether mixture, 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, propylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, ethylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, propylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, ethylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, propylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, ethylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, etc. are preferred, but the combinations are not limited to these combinations.

[0142] Alternatively, the mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent can be appropriately selected. For 100 parts by mass of the water-insoluble organic solvent, for example, the water-soluble organic solvent can be set to 0.1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, and more preferably 2 to 100 parts by mass.

[0143] Then, it can also be washed with neutral water. This water is usually deionized water or ultrapure water. The amount of this water is preferably 0.01 - 100 L, more preferably 0.05 - 50 L, and even more preferably 0.1 - 5 L relative to 1 L of the thermally crosslinkable polysiloxane solution. For this washing method, the two can be placed in the same container, stirred and mixed, and then left to stand to separate the water layer. The number of washing times can be 1 or more, but since washing 10 or more times does not necessarily achieve the corresponding washing effect, it is preferably about 1 - 5 times.

[0144] Other methods for removing the acid catalyst include, for example, using an ion exchange resin, or neutralizing with an epoxide such as ethylene oxide or propylene oxide and then removing it. These methods can be appropriately selected according to the acid catalyst used in the reaction.

[0145] By means of the water washing operation at this time, a part of the thermally crosslinkable polysiloxane will escape into the water layer, and sometimes an effect substantially equivalent to the fractionation operation can be obtained. Therefore, the number of water washing times and the amount of washing water can be appropriately selected according to the catalyst removal effect and the fractionation effect.

[0146] In either case of the thermally crosslinkable polysiloxane solution with the acid catalyst remaining or the thermally crosslinkable polysiloxane solution with the acid catalyst removed, by adding the final solvent and performing solvent exchange under reduced pressure, the desired thermally crosslinkable polysiloxane solution can be obtained. At this time, the temperature of the solvent exchange depends on the types of the reaction solvent and extraction solvent to be removed, and is preferably 0 - 100 °C, more preferably 10 - 90 °C, and even more preferably 15 - 80 °C. Also, the degree of reduced pressure at this time varies depending on the type of the extraction solvent to be removed, the exhaust device, the condensation device, and the heating temperature, and is preferably below atmospheric pressure, more preferably 80 kPa or below in terms of absolute pressure, and even more preferably 50 kPa or below in terms of absolute pressure.

[0147] At this time, the thermally crosslinkable polysiloxane may become unstable when the solvent is changed. This occurs depending on the compatibility between the final solvent and the thermally crosslinkable polysiloxane. To prevent this, a monohydric or polyhydric alcohol having a cyclic ether as a substituent described in paragraphs (0181) - (0182) of Japanese Patent Laid-Open No. 2009-126940 can also be added as a stabilizer. The addition amount is 0 - 25 parts by mass, preferably 0 - 15 parts by mass, more preferably 0 - 5 parts by mass, relative to 100 parts by mass of the thermally crosslinkable polysiloxane in the solution before solvent exchange, but when added, it is preferably 0.5 parts by mass or more. If necessary, a monohydric or polyhydric alcohol having a cyclic ether as a substituent can also be added to the solution before solvent exchange and then the solvent exchange operation can be carried out.

[0148] The thermally crosslinkable polysiloxane should be prepared in a solution state with an appropriate concentration in advance. The concentration at this time should be 0.1 to 20% by mass. At such a concentration, the condensation reaction will not proceed further, so it will not become a state where it is no longer soluble in organic solvents. Also, since the amount of the solvent is small, it is economically ideal.

[0149] The final solvent added to the thermally crosslinkable polysiloxane solution should be an alcohol-based solvent, and particularly preferably monoalkyl ether derivatives such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and butylene glycol. Specifically, butylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butylene glycol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol, etc. are preferred.

[0150] If these solvents are the main components, a non-alcohol-based solvent can also be added as an auxiliary solvent. Examples of the auxiliary solvent include acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monoter-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0151] Also, for another reaction operation using an acid catalyst, water or a water-containing organic solvent can be added to the monomer or the organic solution of the monomer to start the hydrolysis reaction. At this time, the catalyst can be added to the monomer or the organic solution of the monomer, or can be added to the water or the water-containing organic solvent. The reaction temperature is, for example, 0 to 100 °C, preferably 10 to 80 °C. A method of heating to 10 to 50 °C when dropping water and then raising the temperature to 20 to 80 °C for aging is preferred.

[0152] When using an organic solvent, it should be water-soluble, and examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butylene glycol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, etc., polyol condensate derivatives and their mixtures.

[0153] The amount of the organic solvent used is 0 to 1,000 ml, particularly preferably 0 to 500 ml, relative to 1 mole of the monomer. When the amount of the organic solvent used is small, the reaction vessel is smaller and more economical. The post-treatment of the obtained reaction mixture can be carried out in the same manner as the above method to obtain the thermally crosslinkable polysiloxane.

[0154] (Synthesis Method 2: Base Catalyst)

[0155] Furthermore, the thermally crosslinkable polysiloxane (Sx) can be produced by hydrolytic condensation of one or more hydrolyzable monomers (Sm) in the presence of a base catalyst... The base catalysts used at this time are methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, methylpyridine, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. The amount of the catalyst used is preferably 1×10 -6 moles to 10 moles, more preferably 1×10 -5 moles to 5 moles, and even more preferably 1×10 -4 moles to 1 mole, per 1 mole of the monomer.

[0156] When obtaining the thermally crosslinkable polysiloxane by hydrolytic condensation from the above monomers, the amount of water per 1 mole of the hydrolyzable substituent bonded to the monomer is preferably 0.1 to 50 moles. If it is 50 moles or less, the reaction apparatus used is smaller and more economical. If it is 0.1 mole or more, the reaction can proceed sufficiently.

[0157] The operation method is to add the monomer to the catalyst aqueous solution to start the hydrolytic condensation reaction. At this time, an organic solvent can also be added to the catalyst aqueous solution, the monomer can also be diluted with an organic solvent, or both can be implemented. The reaction temperature can be set, for example, at 0 to 100 °C, preferably 5 to 80 °C. A method of maintaining the temperature at 5 to 80 °C during the monomer dropping and then aging it at 20 to 80 °C is preferred.

[0158] The organic solvent that can be added to the base catalyst aqueous solution or the organic solvent that can dilute the monomer is preferably the same as those exemplified as the organic solvents that can be added to the acid catalyst aqueous solution. In addition, in order to carry out the reaction economically, the amount of the organic solvent used is preferably 0 to 1,000 ml per 1 mole of the monomer.

[0159] Thereafter, 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 the acidic substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the basic substance used as the catalyst. If the acidic substance is acidic in water, it can be any substance.

[0160] Then, it is advisable to remove by-products such as alcohols generated by the hydrolysis condensation reaction from the reaction mixture by means of decompression removal or the like. At this time, the temperature for heating the reaction mixture depends on the types of the organic solvent added and the alcohol generated by the reaction, but it is preferably 0 to 100°C, more preferably 10 to 90°C, and still more preferably 15 to 80°C. Also, the degree of decompression at this time varies depending on the types of the organic solvent and alcohol to be removed, the exhaust device, the condensation device, and the heating temperature, and it is preferably below atmospheric pressure, more preferably 80 kPa or less in terms of absolute pressure, and still more preferably 50 kPa or less in terms of absolute pressure. Although it is not easy to accurately know the amount of alcohol removed at this time, it is desirable to remove about 80% by mass or more of the generated alcohol.

[0161] Then, in order to remove the catalyst used for 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. Examples of the organic solvent include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monoterbutyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0162] A mixture of a water-soluble organic solvent and a water-insoluble organic solvent may also be used.

[0163] Specific examples of the organic solvent used for removing the base catalyst can be the above-mentioned organic solvents specifically exemplified as those used for removing the acid catalyst, or those similar to the mixture of the water-soluble organic solvent and the water-insoluble organic solvent.

[0164] In addition, the mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent can be appropriately selected. With respect to 100 parts by mass of the water-insoluble organic solvent, the water-soluble organic solvent can be 0.1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, and more preferably 2 to 100 parts by mass.

[0165] Then, it is washed with neutral water. It is sufficient to use water generally known as deionized water or ultrapure water. The amount of the water is, for example, 0.01 to 100 L, preferably 0.05 to 50 L, and more preferably 0.1 to 5 L with respect to 1 L of the thermally crosslinkable polysiloxane solution. The washing method may be to put the two into the same container, stir, and then leave it to stand to separate the water layer. The number of washing times may be 1 or more. Even if it is washed more than 10 times, no corresponding washing effect can be obtained. Therefore, it is preferably about 1 to 5 times.

[0166] A final solvent is added to the washed thermally crosslinkable polysiloxane solution, and solvent exchange is carried out under reduced pressure to obtain a desired thermally crosslinkable polysiloxane solution. At this time, the temperature of the solvent exchange depends on the type of extraction solvent to be removed, and is preferably 0 to 100 °C, more preferably 10 to 90 °C, and even more preferably 15 to 80 °C. Also, 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, and is preferably below atmospheric pressure, more preferably 80 kPa or less in terms of absolute pressure, and even more preferably 50 kPa or less in terms of absolute pressure.

[0167] The final solvent added to the thermally crosslinkable polysiloxane solution is preferably an alcohol-based solvent, and particularly preferably monoalkyl ethers such as ethylene glycol, diethylene glycol, and triethylene glycol, and monoalkyl ether derivatives such as propylene glycol and dipropylene glycol. Specifically, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol, etc. are preferred.

[0168] Another reaction operation using an alkali catalyst is to add water or a water-containing organic solvent to a monomer or an organic solution of the monomer to start the hydrolysis reaction. At this time, the catalyst can be added to the monomer or the organic solution of the monomer, or can be added to the water or the water-containing organic solvent. The reaction temperature is, for example, preferably 0 to 100 °C, and preferably 10 to 80 °C. A method of heating to 10 to 50 °C when dropping water and then raising the temperature to 20 to 80 °C for aging is preferred.

[0169] The organic solvent that can be used as the organic solution or the water-containing organic solvent of the monomer is preferably water-soluble, and examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, and other polyol condensate derivatives, and mixtures thereof.

[0170] The molecular weight of the thermally crosslinkable polysiloxane obtained by using 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. When using those with a weight-average molecular weight of 100,000 or less, there will be no generation of foreign substances and no coating unevenness, so it is preferably 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. In addition, the data related to the above weight-average molecular weight is represented by converting to polystyrene using gel permeation chromatography (GPC) with RI as the detector and tetrahydrofuran as the elution solvent, and using polystyrene as the standard substance.

[0171] The physical properties of the thermally crosslinkable polysiloxane used in the present invention vary depending on the type of acid or base catalyst used during hydrolysis and condensation and the reaction conditions. Therefore, it can be appropriately selected according to the performance of the resist underlayer film as the purpose.

[0172] Furthermore, 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 the composition for forming a resist underlayer film, which is prepared under the conditions of using the aforementioned acid or base catalyst.

[0173] [Chemical formula 17]

[0174] U(OR 7 ) m7 (OR 8 ) m8 (Mm)

[0175] In the general formula (Mm), R 7 , and R 8 are each independently an organic group having 1 to 30 carbon atoms, m7 + m8 and the valence determined by the type of U are the same number, m7 and m8 are integers of 0 or more, and U is an element of Group III, Group IV, or Group V of the periodic table and excludes carbon and silicon.

[0176] The hydrolyzable metal compounds represented by the above general formula (Mm) used at this time can be exemplified as follows. When U is boron, the hydrolyzable metal compounds represented by the general formula (Mm) can include boron methoxide, boron ethoxide, boron propoxide, boron butoxide, boron pentoxide, boron hexoxide, cyclopentyl boron oxide, cyclohexyl boron oxide, allyl boron oxide, phenyl boron oxide, methoxyethyl boron oxide, boric acid, boron oxide, etc.

[0177] In the case where U is aluminum, the hydrolyzable metal compounds represented by the general formula (Mm) include methylaluminum oxide, ethylaluminum oxide, propylaluminum oxide, butylaluminum oxide, pentylaluminum oxide, hexylaluminum oxide, cyclopentylaluminum oxide, cyclohexylaluminum oxide, allylaluminum oxide, phenylaluminum oxide, methoxyethylaluminum oxide, ethoxyethylaluminum oxide, dipropoxyethyl acetoacetate aluminum, dibutoxyethyl acetoacetate aluminum, propoxybisethyl acetoacetate aluminum, butoxybisethyl acetoacetate aluminum, aluminum 2,4-pentanedionate, aluminum 2,2,6,6-tetramethyl-3,5-heptanedionate, etc.

[0178] In the case where U is gallium, the hydrolyzable metal compounds represented by the general formula (Mm) include methylgallium oxide, ethylgallium oxide, propylgallium oxide, butylgallium oxide, pentylgallium oxide, hexylgallium oxide, cyclopentylgallium oxide, cyclohexylgallium oxide, allylgallium oxide, phenylgallium oxide, methoxyethylgallium oxide, ethoxyethylgallium oxide, dipropoxyethyl acetoacetate gallium, dibutoxyethyl acetoacetate gallium, propoxybisethyl acetoacetate gallium, butoxybisethyl acetoacetate gallium, gallium 2,4-pentanedionate, gallium 2,2,6,6-tetramethyl-3,5-heptanedionate, etc.

[0179] In the case where U is yttrium, the hydrolyzable metal compounds represented by the general formula (Mm) include methylyttrium oxide, ethylyttrium oxide, propylyttrium oxide, butylyttrium oxide, pentylyttrium oxide, hexylyttrium oxide, cyclopentylyttrium oxide, cyclohexylyttrium oxide, allylyttrium oxide, phenylyttrium oxide, methoxyethylyttrium oxide, ethoxyethylyttrium oxide, dipropoxyethyl acetoacetate yttrium, dibutoxyethyl acetoacetate yttrium, propoxybisethyl acetoacetate yttrium, butoxybisethyl acetoacetate yttrium, yttrium 2,4-pentanedionate, yttrium 2,2,6,6-tetramethyl-3,5-heptanedionate, etc.

[0180] In the case where U is germanium, the hydrolyzable metal compounds represented by the general formula (Mm) include methylgermanium oxide, ethylgermanium oxide, propylgermanium oxide, butylgermanium oxide, pentylgermanium oxide, hexylgermanium oxide, cyclopentylgermanium oxide, cyclohexylgermanium oxide, allylgermanium oxide, phenylgermanium oxide, methoxyethylgermanium oxide, ethoxyethylgermanium oxide, etc.

[0181] In the case where U is titanium, the hydrolyzable metal compounds represented by the general formula (Mm) include methyltitanium oxide, ethyltitanium oxide, propyltitanium oxide, butyltitanium oxide, pentyltitanium oxide, hexyltitanium oxide, cyclopentyltitanium oxide, cyclohexyltitanium oxide, allyltitanium oxide, phenyltitanium oxide, methoxyethyltitanium oxide, ethoxyethyltitanium oxide, dipropoxybisethyl acetoacetate titanium, dibutoxybisethyl acetoacetate titanium, dipropoxybis(2,4-pentanedionate) titanium, dibutoxybis(2,4-pentanedionate) titanium, etc.

[0182] In the case where U is hafnium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include hafnium methoxide, hafnium ethoxide, hafnium propoxide, hafnium butoxide, hafnium pentoxide, hafnium hexoxide, hafnium cyclopentoxide, hafnium cyclohexoxide, hafnium allyloxide, hafnium phenoxide, hafnium methoxyethoxide, hafnium ethoxyethoxide, hafnium dipropoxybis(ethylacetoacetate), hafnium dibutoxybis(ethylacetoacetate), hafnium dipropoxybis(2,4-pentanedionate), hafnium dibutoxybis(2,4-pentanedionate), etc.

[0183] In the case where U is tin, examples of the hydrolyzable metal compound represented by the general formula (Mm) include tin methoxide, tin ethoxide, tin propoxide, tin butoxide, tin phenoxide, tin methoxyethoxide, tin ethoxyethoxide, tin 2,4-pentanedionate, tin 2,2,6,6-tetramethyl-3,5-heptanedionate, etc.

[0184] In the case where U is arsenic, examples of the hydrolyzable metal compound represented by the general formula (Mm) include arsenic methoxide, arsenic ethoxide, arsenic propoxide, arsenic butoxide, arsenic phenoxide, etc.

[0185] In the case where U is antimony, examples of the hydrolyzable metal compound represented by the general formula (Mm) include antimony methoxide, antimony ethoxide, antimony propoxide, antimony butoxide, antimony phenoxide, antimony acetate, antimony propionate, etc.

[0186] In the case where U is niobium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include niobium methoxide, niobium ethoxide, niobium propoxide, niobium butoxide, niobium phenoxide, etc.

[0187] In the case where U is tantalum, examples of the hydrolyzable metal compound represented by the general formula (Mm) include tantalum methoxide, tantalum ethoxide, tantalum propoxide, tantalum butoxide, tantalum phenoxide, etc.

[0188] In the case where U is bismuth, examples of the hydrolyzable metal compound represented by the general formula (Mm) include bismuth methoxide, bismuth ethoxide, bismuth propoxide, bismuth butoxide, bismuth phenoxide, etc.

[0189] In the case where U is phosphorus, examples of the hydrolyzable metal compound represented by the general formula (Mm) include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, phosphorus pentoxide, etc.

[0190] In the case where U is vanadium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include vanadium bis(2,4-pentanedionate) oxide, vanadium 2,4-pentanedionate, vanadium tributoxide oxide, vanadium tripropoxide oxide, etc.

[0191] In the case where U is zirconium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include zirconium methoxide, zirconium ethoxide, zirconium propoxide, zirconium butoxide, zirconium phenoxide, bis(2,4-pentanedionato)zirconium dibutoxide, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)zirconium dipropoxide, and the like.

[0192] In the composition for forming a silicon-containing anti-reflective lower layer film of the present invention, the blending amount of the thermally crosslinkable polysiloxane (Sx) is preferably, for example, 0.1 to 10% by mass relative to the solvent.

[0193] [Acid generator]

[0194] The composition for forming a silicon-containing anti-reflective lower layer film of the present invention preferably further contains an acid generator. One or more acid generators can be blended. Any substance that acts as an acid precursor such as a thermal acid generator, a photoacid generator, or an acid proliferator can be used as the acid generator. However, in the present invention, the aforementioned acid generator is preferably a photoacid generator that generates an acid by the action of high-energy rays, and a photoacid generator that is a sulfonium salt and generates an acid by the action of high-energy rays is more preferable. More specifically, materials described in paragraphs

[0160] to

[0179] of Japanese Patent Application Laid-Open No. 2009-126940 can be cited, but are not limited thereto. The blending amount of the acid generator is preferably 0 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the thermally crosslinkable polysiloxane (Sx).

[0195] [Other components]

[0196] (Crosslinking catalyst)

[0197] In the composition for forming a silicon-containing anti-reflective lower layer film of the present invention, in addition to the silicon-containing sulfonium salt compound represented by the general formula (A-1), other crosslinking catalysts (Xc) can also be blended. Examples of the crosslinking catalyst (Xc) that can be blended include compounds represented by the following general formula (Xc0).

[0198] L a H b A(Xc0)

[0199] In the general formula (Xc0), L is lithium, sodium, potassium, rubidium, cesium, sulfonium, iodonium, phosphonium, or ammonium, A is a non-nucleophilic counter ion, a is an integer of 1 or more, b is 0 or an integer of 1 or more, and a + b is the valence of the non-nucleophilic counter ion.

[0200] Specific compounds represented by the general formula (Xc0) include, as the crosslinking catalyst (Xc) used in the present invention, sulfonium salts of the following general formula (Xc-1), iodonium salts of (Xc-2), phosphonium salts of (Xc-3), ammonium salts of (Xc-4), alkali metal salts, and the like.

[0201] Examples of sulfonium salts (Xc-1), oxosulfonium salts (Xc-2), phosphonium salts (Xc-3), and ammonium salts (Xc-4) are as follows.

[0202] [Chemical formula 18]

[0203]

[0204] [Chemical formula 19]

[0205]

[0206] In the formula, R 204 , R 205 , R 206 , and R 207 each represent a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms. Some or all of the hydrogen atoms of these groups may also be substituted with alkoxy groups or the like. Further, R 205 and R 206 may also form a ring. When forming a ring, R 205 , R 206 each represent an alkylene group having 1 to 6 carbon atoms. A - represents a non-nucleophilic counter ion. R 208 , R 209 , R 210 , and R 211 and R 204 , R 205 , R 206 , and R 207 are the same, but may also be hydrogen atoms. R 208 and R 209 , or R 208 and R 209 and R 210 may also form a ring. When forming a ring, R 208 and R 209 , and R 208 and R 209 and R 210 represent an alkylene group having 3 to 10 carbon atoms.

[0207] The above R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , and R 211They may be the same as or different from each other. Specifically, examples of the alkyl group 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 the alkenyl group include vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl, etc. Examples of the oxoalkyl group include 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, 2-(4-methylcyclohexyl)-2-oxoethyl, etc. Examples of the oxoalkenyl group include 2-oxopropenyl, 2-oxobutenyl, 2-oxohexenyl, 2-oxocyclopentenyl, 2-oxocyclohexenyl, etc. Examples of the aryl group include phenyl, naphthyl, etc., p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, m-tert-butoxyphenyl, etc. alkoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, etc. alkylphenyl, methylnaphthyl, ethylnaphthyl, etc. alkylnaphthyl, methoxynaphthyl, ethoxynaphthyl, etc. alkoxynaphthyl, dimethylnaphthyl, diethylnaphthyl, etc. dialkylnaphthyl, dimethoxynaphthyl, diethoxynaphthyl, etc. dialkoxynaphthyl, etc. Examples of the aralkyl group include benzyl, phenylethyl, phenyl ethyl, etc. Examples of the aryloxoalkyl group include 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, 2-(2-naphthyl)-2-oxoethyl, etc. 2-aryl-2-oxoethyl, etc.

[0208] A - non-nucleophilic relative ions, such as hydroxide ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion, caproate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleate ion, linolenate ion, benzoate ion, phthalate ion, isophthalate ion, terephthalate ion, salicylate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, trichloroacetate ion, fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion, nitrite ion, chlorate ion, bromate ion, methanesulfonate ion, p-toluenesulfonate ion, monomethyl sulfate ion, etc. monovalent ions, monovalent or divalent oxalate ion, malonate ion, methylmalonate ion, ethylmalonate ion, propylmalonate ion, butylmalonate ion, dimethylmalonate ion, diethylmalonate ion, succinate ion, methylsuccinate ion, glutarate ion, adipate ion, itaconate ion, maleate ion, fumarate ion, citraconate ion, citrate ion, carbonate ion, sulfate ion, etc.

[0209] Alkali metal salts, such as hydroxides, formates, acetates, propionates, butyrates, valerates, hexanoates, heptanoates, octanoates, nonanoates, decanoates, oleates, stearates, linoleates, linolenates, benzoates, phthalates, isophthalates, terephthalates, salicylates, trifluoroacetates, monochloroacetates, dichloroacetates, trichloroacetates, etc. of lithium, sodium, potassium, cesium, magnesium, calcium, as well as monovalent salts, monovalent or divalent oxalates, malonates, methylmalonates, ethylmalonates, propylmalonates, butylmalonates, dimethylmalonates, diethylmalonates, succinates, methylsuccinates, glutarates, adipates, itaconates, maleates, fumarates, citraconates, citrates, carbonates, etc.

[0210] Specifically, examples of sulfonium salts (Xc-1) include triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionate, triphenylsulfonium butyrate, triphenylsulfonium benzoate, triphenylsulfonium phthalate, triphenylsulfonium isophthalate, triphenylsulfonium terephthalate, triphenylsulfonium salicylate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium monochloroacetate, triphenylsulfonium dichloroacetate, triphenylsulfonium trichloroacetate, triphenylsulfonium hydroxide, triphenylsulfonium nitrate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium oxalate, triphenylsulfonium malonate, triphenylsulfonium methylmalonate, triphenylsulfonium ethylmalonate, triphenylsulfonium propylmalonate, triphenylsulfonium butylmalonate, triphenylsulfonium dimethylmalonate, triphenylsulfonium diethylmalonate, triphenylsulfonium succinate, triphenylsulfonium methylsuccinate, triphenylsulfonium glutarate, triphenylsulfonium adipate, triphenylsulfonium itaconate, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylsulfonium citraconate, triphenylsulfonium citrate, triphenylsulfonium carbonate, bis(triphenylsulfonium) oxalate, bis(triphenylsulfonium) maleate, bis(triphenylsulfonium) fumarate, bis(triphenylsulfonium) citraconate, bis(triphenylsulfonium) citrate, bis(triphenylsulfonium) carbonate, etc.

[0211] Furthermore, examples of iodonium salts (Xc-2) include diphenyliodonium formate, diphenyliodonium acetate, diphenyliodonium propionate, diphenyliodonium butyrate, diphenyliodonium benzoate, diphenyliodonium phthalate, diphenyliodonium isophthalate, diphenyliodonium terephthalate, diphenyliodonium salicylate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium monochloroacetate, diphenyliodonium dichloroacetate, diphenyliodonium trichloroacetate, diphenyliodonium hydroxide, diphenyliodonium nitrate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide, diphenyliodonium oxalate, diphenyliodonium maleate, diphenyliodonium fumarate, diphenyliodonium citraconate, diphenyliodonium citrate, diphenyliodonium carbonate, bis(diphenyliodonium) oxalate, bis(diphenyliodonium) maleate, bis(diphenyliodonium) fumarate, bis(diphenyliodonium) citraconate, bis(diphenyliodonium) citrate, bis(diphenyliodonium) carbonate, etc.

[0212] Furthermore, phosphonium salts (Xc-3), specifically, examples thereof include tetraethylphosphonium formate, tetraethylphosphonium acetate, tetraethylphosphonium propionate, tetraethylphosphonium butyrate, tetraethylphosphonium benzoate, tetraethylphosphonium phthalate, tetraethylphosphonium isophthalate, tetraethylphosphonium terephthalate, tetraethylphosphonium salicylate, tetraethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoroacetate, tetraethylphosphonium chloroacetate, 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, bis(tetraethylphosphonium) oxalate, bis(tetraethylphosphonium) maleate, bis(tetraethylphosphonium) fumarate, bis(tetraethylphosphonium) citraconate, bis(tetraethylphosphonium) citrate, bis(tetraethylphosphonium) carbonate, tetraphenylphosphonium formate, tetraphenylphosphonium acetate, tetraphenylphosphonium propionate, tetraphenylphosphonium butyrate, tetraphenylphosphonium benzoate, tetraphenylphosphonium phthalate, tetraphenylphosphonium isophthalate, tetraphenylphosphonium terephthalate, tetraphenylphosphonium salicylate, tetraphenylphosphonium trifluoromethanesulfonate, tetraphenylphosphonium trifluoroacetate, tetraphenylphosphonium chloroacetate, 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, bis(tetraphenylphosphonium) oxalate, bis(tetraphenylphosphonium) maleate, bis(tetraphenylphosphonium) fumarate, bis(tetraphenylphosphonium) citraconate, bis(tetraphenylphosphonium) citrate, bis(tetraphenylphosphonium) carbonate, etc.

[0213] On the other hand, ammonium salts (Xc-4), specifically, for example, tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetramethylammonium phthalate, tetramethylammonium isophthalate, tetramethylammonium terephthalate, tetramethylammonium salicylate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium chloroacetate, tetramethylammonium dichloroacetate, tetramethylammonium trichloroacetate, tetramethylammonium hydroxide, tetramethylammonium nitrate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium monomethyl sulfate, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium maleate, tetramethylammonium fumarate, tetramethylammonium citraconate, tetramethylammonium citrate, tetramethylammonium carbonate, bis(tetramethylammonium) oxalate, bis(tetramethylammonium) malonate, bis(tetramethylammonium) maleate, bis(tetramethylammonium) fumarate, bis(tetramethylammonium) citraconate, bis(tetramethylammonium) citrate, bis(tetramethylammonium) carbonate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetraethylammonium phthalate, tetraethylammonium isophthalate, tetraethylammonium terephthalate, tetraethylammonium salicylate, tetraethylammonium trifluoromethanesulfonate, tetraethylammonium trifluoroacetate, tetraethylammonium chloroacetate, tetraethylammonium dichloroacetate, tetraethylammonium trichloroacetate, tetraethylammonium hydroxide, tetraethylammonium nitrate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium monomethyl sulfate, tetraethylammonium oxalate, tetraethylammonium malonate, tetraethylammonium maleate, tetraethylammonium fumarate, tetraethylammonium citraconate, tetraethylammonium citrate, tetraethylammonium carbonate, bis(tetraethylammonium) oxalate, bis(tetraethylammonium) malonate, bis(tetraethylammonium) maleate, bis(tetraethylammonium) fumarate, bis(tetraethylammonium) citraconate, bis(tetraethylammonium) citrate, bis(tetraethylammonium) carbonate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium chloroacetate, tetrapropylammonium dichloroacetate, tetrapropylammonium trichloroacetate, tetrapropylammonium hydroxide, tetrapropylammonium nitrate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrapropylammonium monomethyl sulfate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium maleate, tetrapropylammonium fumarate, tetrapropylammonium citraconate, tetrapropylammonium citrate, tetrapropylammonium carbonate, bis(tetrapropylammonium) oxalate, bis(tetrapropylammonium) malonate, bis(tetrapropylammonium) maleate, bis(tetrapropylammonium) fumarate, bis(tetrapropylammonium) citraconate, bis(tetrapropylammonium) citrate, bis(tetrapropylammonium) carbonate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, tetrabutylammonium benzoate, tetrabutylammonium phthalate, tetrabutylammonium isophthalate, tetrabutylammonium terephthalate, tetrabutylammonium salicylate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluoroacetate, tetrabutylammonium chloroacetate, tetrabutylammonium dichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, tetrabutylammonium nitrate,Tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium methanesulfonate, tetrabutylammonium monomethyl sulfate, tetrabutylammonium oxalate, tetrabutylammonium malonate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citraconate, tetrabutylammonium citrate, tetrabutylammonium carbonate, bis(tetrabutylammonium) oxalate, bis(tetrabutylammonium) malonate, bis(tetrabutylammonium) maleate, bis(tetrabutylammonium) fumarate, bis(tetrabutylammonium) citraconate, bis(tetrabutylammonium) citrate, bis(tetrabutylammonium) carbonate, etc.

[0214] Alkali metal salts, such as lithium formate, lithium acetate, lithium propionate, lithium butyrate, lithium benzoate, lithium phthalate, lithium isophthalate, lithium terephthalate, lithium salicylate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium monochloroacetate, lithium dichloroacetate, lithium trichloroacetate, lithium hydroxide, lithium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium methanesulfonate, lithium hydrogen oxalate, lithium hydrogen malonate, lithium hydrogen maleate, lithium hydrogen fumarate, lithium hydrogen citraconate, lithium hydrogen citrate, lithium hydrogen carbonate, lithium oxalate, lithium malonate, lithium maleate, lithium fumarate, lithium citraconate, lithium citrate, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butyrate, sodium benzoate, sodium phthalate, sodium isophthalate, sodium terephthalate, sodium salicylate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, sodium dichloroacetate, sodium trichloroacetate, sodium hydroxide, sodium nitrate, sodium chloride, sodium bromide, sodium iodide, sodium methanesulfonate, sodium hydrogen oxalate, sodium hydrogen malonate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium hydrogen citraconate, sodium hydrogen citrate, sodium hydrogen carbonate, sodium oxalate, sodium malonate, sodium maleate, sodium fumarate, sodium citraconate, sodium citrate, sodium carbonate, potassium formate, potassium acetate, potassium propionate, potassium butyrate, potassium benzoate, potassium phthalate, potassium isophthalate, potassium terephthalate, potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, potassium trichloroacetate, potassium hydroxide, potassium nitrate, potassium chloride, potassium bromide, potassium iodide, potassium methanesulfonate, potassium hydrogen oxalate, potassium hydrogen malonate, potassium hydrogen maleate, potassium hydrogen fumarate, potassium hydrogen citraconate, potassium hydrogen citrate, potassium hydrogen carbonate, potassium oxalate, potassium malonate, potassium maleate, potassium fumarate, potassium citraconate, potassium citrate, potassium carbonate, etc.

[0215] In the present invention, a polysiloxane (Xc-10) having a part of the structure as an ammonium salt, sulfonium salt, phosphonium salt, or iodonium salt can also be incorporated as a crosslinking catalyst (Xc) into the composition for forming an underlayer film of a resist.

[0216] Again, as a raw material for (Xc-10) used for manufacturing, a compound represented by the following general formula (Xm) can be used.

[0217] R 1A A1 R 2A A2 R 3A A3 Si(OR0A ) (4-A1-A2-A3)

[0218] (Xm)

[0219] In the general formula (Xm), R 0A is a hydrocarbon group having 1 to 6 carbon atoms, and R 1A , R 2A , and R 3A Among them, at least one is an organic group having an ammonium salt, a sulfonium salt, a phosphonium salt, or an iodonium salt, and the rest are hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms. A1, A2, and A3 are 0 or 1, and 1 ≤ A1 + A2 + A3 ≤ 3.

[0220] Here, R 0A may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl.

[0221] Xm, for example: a hydrolyzable silicon compound in which a part of the structure has a sulfonium salt, a compound represented by the following general formula (Xm-1).

[0222] [Chemical formula 20]

[0223]

[0224] In the general formula (Xm-1), R SA1 , and R SA2 each represent a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 20 carbon atoms. Part or all of the hydrogen atoms of these groups may also be substituted with alkoxy groups, amino groups, alkylamino groups, halogen atoms, etc. Also, R SA1 and R SA2 may also form a ring together with the sulfur atom to which they are bonded. When forming a ring, R SA1 , and R SA2 each represent an alkylene group having 1 to 6 carbon atoms. R SA3 represents a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Part or all of the hydrogen atoms of these groups may also be substituted with alkoxy groups, amino groups, alkylamino groups, etc.

[0225] Also, in the above general formula (Xm-1), (Si) is described to indicate the bonding site to Si.

[0226] X -For example, hydroxide ion, fluoride ion, chloride ion, bromide ion, iodide ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion, caproate ion, enanthate ion, caprylate ion, pelargonate ion, caprate ion, oleate ion, stearate ion, linoleate ion, linolenate ion, benzoate ion, p-toluate ion, p-tert-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, monomethyl sulfate ion, hydrogen sulfate ion, oxalate ion, malonate ion, methylmalonate ion, ethylmalonate ion, propylmalonate ion, butylmalonate ion, dimethylmalonate ion, diethylmalonate ion, succinate ion, methylsuccinate ion, glutarate ion, adipate ion, itaconate ion, maleate ion, fumarate ion, citraconate ion, citrate ion, carbonate ion, etc.

[0227] The cationic part of the compound represented by the above general formula (Xm-1) can specifically include the following ions.

[0228] [Chemical formula 21]

[0229]

[0230] Xm, for example: a hydrolyzable silicon compound having a part of the structure with an onium salt, can include the compounds represented by the following general formula (Xm-2).

[0231] [Chemical formula 22]

[0232]

[0233] In the general formula (Xm-2), R IA1 represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 20 carbon atoms, and a part or all of the hydrogen atoms of these groups can also be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, etc. R IA2 represents a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and a part or all of the hydrogen atoms of these groups can also be substituted with an alkoxy group, an amino group, an alkylamino group, etc.

[0234] Also, in the above general formula (Xm-2), (Si) is described to indicate the bonding site with Si. X - As described above.

[0235] The cationic moiety of the compound represented by the above general formula (Xm-2) can specifically include the following ions.

[0236] [Chemical formula 23]

[0237]

[0238] Xm. For example, for a hydrolyzable silicon compound having a phosphonium salt in a part of its structure, compounds represented by the following general formula (Xm-3) can be cited.

[0239] [Chemical formula 24]

[0240]

[0241] In the general formula (Xm-3), R PA1 , R PA2 , and R PA each represent a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 20 carbon atoms. Part or all of the hydrogen atoms of these groups may also be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, etc. Also, R PA1 and R PA2 may also form a ring together with the phosphorus atom to which they are bonded. When forming a ring, R PA1 , and R PA2 each represent an alkylene group having 1 to 6 carbon atoms. R PA4 is a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Part or all of the hydrogen atoms of these groups may also be substituted with an alkoxy group, an amino group, an alkylamino group, etc.

[0242] Also, in the above general formula (Xm-3), (Si) is described to indicate the bonding site to Si. X - is the same as described above.

[0243] The cationic moiety of the compound represented by the above general formula (Xm-3) can specifically include the following ions.

[0244] [Chemical formula 25]

[0245]

[0246] [Chemical formula 26]

[0247]

[0248] Xm. For example, for a hydrolyzable silicon compound having an ammonium salt in a part of its structure, compounds represented by the following general formula (Xm-4) can be cited.

[0249] [Chemical formula 27]

[0250]

[0251] In the general formula (Xm-4), R NA1 , R NA2 , and R NA3 each represent a hydrogen atom, a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 20 carbon atoms. Some or all of the hydrogen atoms in these groups may also be substituted with alkoxy groups, amino groups, alkylamino groups, etc. Also, R NA1 and R NA2 may also form a ring together with the nitrogen atom to which they are bonded. When forming a ring, R NA1 , and R NA2 each represent an alkylene group having 1 to 6 carbon atoms, a nitrogen-containing cyclic heterocycle, or a heteroaromatic ring. R NA4 represents a linear, branched, or cyclic alkylene or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Some or all of the hydrogen atoms in these groups may also be substituted with alkoxy groups, amino groups, alkylamino groups, etc. When R NA1 and R NA2 , or R NA1 and R NA4 form a cyclic structure and further contain unsaturated nitrogen, n N3 = 0, and the rest is n N3 = 1.

[0252] Also, in the above general formula (Xm-4), (Si) is described to indicate the bonding site to Si. X - is the same as described above.

[0253] The cationic part of the compound represented by the above general formula (Xm-4) can specifically include the following ions.

[0254] [Chemical formula 28]

[0255]

[0256] [Chemical formula 29]

[0257]

[0258] [Chemical formula 30]

[0259]

[0260] [Chemical formula 31]

[0261]

[0262] [Chemical formula 32]

[0263]

[0264] [Chemical formula 33]

[0265]

[0266] [Chemical formula 34]

[0267]

[0268] [Chemical formula 35]

[0269]

[0270] [Chemical formula 36]

[0271]

[0272] [Chemical formula 37]

[0273]

[0274] [Chemical formula 38]

[0275]

[0276] [Chemical formula 39]

[0277]

[0278] [Chemical formula 40]

[0279]

[0280] The hydrolyzable silicon compound used in combination with the above (Xm-1), (Xm-2), (Xm-3), and (Xm-4) for manufacturing (Xc-10) may include the above hydrolyzable monomer (Sm). The hydrolyzable metal compound (Mm) represented by the above general formula (Mm) may also be further added.

[0281] One or more of the monomers (Xm-1), (Xm-2), (Xm-3), and (Xm-4) as shown above, one or more of (Sm), and if necessary, one or more selected from (Mm) may be mixed before or during the reaction as the reaction raw materials for forming (Xc-10). The reaction conditions may be the same as those for the synthesis method of the thermally crosslinkable polysiloxane (Sx).

[0282] The molecular weight of the obtained crosslinking catalyst (Xc-10) can be adjusted not only by the choice of monomers but also by controlling the reaction conditions during polymerization. If the weight-average molecular weight is 100,000 or less, there will be no occurrence of foreign substances or coating unevenness. Therefore, those with a weight-average molecular weight of 100,000 or less are used, more preferably 200 to 50,000, and even more preferably 300 to 30,000. Also, regarding the data of the above weight-average molecular weight, it is expressed in terms of polystyrene conversion using gel permeation chromatography (GPC) with RI as the detector and tetrahydrofuran as the elution solvent, and polystyrene as the standard substance.

[0283] Also, the above crosslinking catalysts (Xc-1), (Xc-2), (Xc-3), (Xc-4), and (Xc-10) can be used alone or in combination of two or more. The addition amount of the crosslinking catalyst is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, relative to 100 parts by mass of the base polymer (the thermally crosslinkable polysiloxane (Sx) obtained by the above method).

[0284] (organic acid)

[0285] In order to improve the stability of the composition for forming a silicon-containing anti-reflective lower layer film of the present invention, it is preferable to add a monobasic or dibasic or higher organic acid having 1 to 30 carbon atoms. The acids added at this time are, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric 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 preferable. Also, in order to maintain stability, two or more acids can be mixed and used. The addition amount of the organic acid 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, relative to 100 parts by mass of silicon contained in the composition for forming a silicon-containing anti-reflective lower layer film of the present invention.

[0286] Alternatively, the above organic acid can be incorporated so that the pH of the composition for forming a silicon-containing anti-reflective lower layer film of the present invention is preferably 0 ≤ pH ≤ 7, more preferably 0.3 ≤ pH ≤ 6.5, and even more preferably 0.5 ≤ pH ≤ 6.

[0287] (water)

[0288] In the present invention, water can also be added to the composition for forming a silicon-containing underlayer film of a resist. When water is added, the polysiloxane compound in the composition for forming a silicon-containing underlayer film of a resist of the present invention will be hydrated, so that the lithography performance is improved. In the solvent component of the composition for forming a silicon-containing underlayer film of a resist of the present invention, the water content rate is preferably more than 0% by mass and less than 50% by mass, more preferably 0.3 to 30% by mass, and still more preferably 0.5 to 20% by mass. If the added amount of water is less than 50% by mass, the uniformity of the silicon-containing underlayer film of a resist is good, and eye holes will not occur. On the other hand, if the added amount of water exceeds 0% by mass, the lithography performance will be good.

[0289] The usage amount of all solvents containing water is preferably 100 to 100,000 parts by mass, more preferably 200 to 50,000 parts by mass, relative to 100 parts by mass of the base polymer thermally crosslinkable polysiloxane.

[0290] (Stabilizer)

[0291] Furthermore, in the present invention, a stabilizer can be added to the composition for forming a silicon-containing underlayer film of a resist. Regarding the stabilizer, a monohydric or polyhydric alcohol having a cyclic ether as a substituent can be added. In particular, if the stabilizer described in paragraphs

[0181] to

[0182] of Japanese Patent Laid-Open No. 2009-126940 is added, the stability of the composition for forming a silicon-containing underlayer film of a resist can be improved. The blending amount of the stabilizer is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, relative to 100 parts by mass of the base polymer thermally crosslinkable polysiloxane (Sx).

[0292] (Surfactant)

[0293] Furthermore, in the present invention, a surfactant can be blended in the composition for forming a silicon-containing underlayer film of a resist as needed. Such a surfactant can specifically be a material described in paragraph

[0185] of Japanese Patent Laid-Open No. 2009-126940. The blending amount of the surfactant is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, relative to 100 parts by mass of the base polymer thermally crosslinkable polysiloxane (Sx).

[0294] (High-boiling solvent)

[0295] Further, in the present invention, a high-boiling solvent having a boiling point of 180 °C or higher may be added to the composition as needed. Examples of such high-boiling solvents include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, γ-butyrolactone, tripropylene glycol monomethyl ether, diacetone alcohol, n-nonyl acetate, ethylene glycol monoethyl ether acetate, 1,2-diacetoxyethane, 1-acetoxy-2-methoxyethane, 1,2-diacetoxypropane, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, etc. The blending amount of the high-boiling solvent in the solvent component is preferably 0 to 20% by mass, more preferably 0 to 10% by mass.

[0296] [Pattern formation method]

[0297] One of the pattern formation methods of the present invention is a pattern formation method (so-called "multi-layer resist method"), which is a method of forming a pattern on a workpiece, and includes the following steps:

[0298] Forming an organic film on the workpiece using a coating-type organic film material,

[0299] Forming a silicon-containing resist underlayer film on the aforementioned organic film using the composition for forming a silicon-containing resist underlayer film described above,

[0300] Forming a resist upper layer film on the aforementioned silicon-containing resist underlayer film using a composition for a resist upper layer film composed of a photoresist composition,

[0301] Forming a circuit pattern on the aforementioned resist upper layer film,

[0302] Using the aforementioned resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the aforementioned silicon-containing resist underlayer film by etching,

[0303] Using the aforementioned silicon-containing resist underlayer film on which the pattern has been transferred as a mask, transferring the pattern to the aforementioned organic film by etching,

[0304] Using the aforementioned organic film on which the pattern has been transferred as a mask, transferring the pattern to the aforementioned workpiece by etching.

[0305] One of the pattern formation methods of the present invention is a pattern formation method (so-called "multi-layer resist method"), which is a method of forming a pattern on a workpiece, and includes the following steps:

[0306] A hard mask is formed on the workpiece by CVD method.

[0307] A silicon-containing lower resist film is formed on the above-mentioned hard mask using the composition for forming a silicon-containing lower resist film described above.

[0308] A resist upper film is formed on the above-mentioned silicon-containing lower resist film using the composition for resist upper film composed of a photoresist composition.

[0309] A circuit pattern is formed on the above-mentioned resist upper film.

[0310] Using the above-mentioned resist upper film on which the circuit pattern has been formed as a mask, the pattern is transferred to the above-mentioned silicon-containing lower resist film by etching.

[0311] Using the above-mentioned silicon-containing lower resist film on which the pattern has been transferred as a mask, the pattern is transferred to the above-mentioned hard mask by dry etching.

[0312] Using the above-mentioned hard mask on which the pattern has been transferred as a mask, the pattern is transferred to the above-mentioned workpiece by dry etching.

[0313] One of the pattern formation methods of the present invention is a pattern formation method (so-called "multi-layer resist method"), which is a method of forming a pattern on a workpiece, and includes the following steps:

[0314] A silicon-containing lower resist film is formed on the workpiece using the composition for forming a silicon-containing lower resist film described above.

[0315] A resist upper film is formed on the above-mentioned silicon-containing lower resist film using the composition for resist upper film composed of a photoresist composition.

[0316] A circuit pattern is formed on the above-mentioned resist upper film.

[0317] Using the above-mentioned resist upper film on which the circuit pattern has been formed as a mask, the pattern is transferred to the above-mentioned silicon-containing lower resist film by etching.

[0318] Using the above-mentioned silicon-containing lower resist film on which the pattern has been transferred as a mask, the pattern is transferred to the above-mentioned workpiece by dry etching.

[0319] The pattern obtained by incorporating the sulfurium salt compound containing silicon of the present invention into the composition for forming a silicon-containing lower resist film can, as described above, optimize the combination of the hard mask and the organic film, and can form a fine pattern with excellent LWR and CDU on the substrate. In addition, the remaining silicon-containing lower resist film after pattern formation can be easily removed by etching or the like, so that residues that cause defects can be suppressed, and damage to the substrate due to excessive etching conditions can also be prevented.

[0320] In the method for forming a positive pattern, a photoresist film (upper resist film) is formed, exposed after heat treatment, and alkali-developed using an alkali developer solution, usually, to obtain a positive resist pattern. Further, it is preferable to perform post-exposure baking (PEB) after exposure.

[0321] As the above alkali developer solution, an aqueous solution of tetramethylammonium hydroxide (TMAH) or the like can be used.

[0322] In the method for forming a circuit pattern on the above upper resist film, a pattern formation method using optical lithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination thereof is preferably used.

[0323] As the above object to be processed, a semiconductor device substrate, or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed on the semiconductor device substrate is preferably used.

[0324] As the above 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 is preferably used.

[0325] [Examples]

[0326] The following presents synthesis examples, comparative synthesis examples, examples, and comparative examples for specific description of the present invention, but the present invention is not limited to the described records. Further, in the following examples, % represents mass %, and the molecular weight Mw represents the weight-average molecular weight in terms of polystyrene measured by GPC.

[0327] [Synthesis Example 1-1]

[0328] To a mixture of 120 g of methanol, 0.1 g of 10% nitric acid, and 60 g of deionized water, a mixture of 30.6 g of compound (101), 38.1 g of compound (102), and 5.9 g of compound (110) (molar ratio: 40 / 50 / 10) was added, and the mixture was maintained at 40 °C for 12 hours to cause hydrolysis and condensation. After completion of the reaction, 600 g of propylene glycol monoethyl ether (PGEE) was added, and the water for hydrolysis and condensation and the by-produced alcohol were distilled off 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 to be Mw = 2,900.

[0329] Under the same conditions as in [Synthesis Example 1-1], [Synthesis Example 1-2] to [Synthesis Example 1-18] were carried out using the monomers shown in Table 1 to obtain the respective target products as polysiloxane compounds 2 to 18.

[0330] [Table 1]

[0331]

[0332] PhSi(OCH3)3 ··· Compound (100) CH3Si(OCH3)3 ··· Compound (101) Si(OCH3)4 ··· Compound (102)

[0333] [Chemical formula 41]

[0334]

[0335] [Synthesis Example of Crosslinking Catalyst]

[0336] [Synthesis Example 2 - 1] Synthesis of Compound A (Intermediate 1)

[0337] [Chemical formula 42]

[0338]

[0339] Dissolve 55 g of trimethylsilylmagnesium bromide in 190 g of tetrahydrofuran. In this solution, dissolve 14 g of thionyl chloride in 35 g of tetrahydrofuran and add dropwise at 0 °C. After aging at room temperature for 6 hours, add 10% hydrochloric acid to quench, then dilute the reaction solution with dichloromethane and wash with water. After that, add water to the organic layer and perform liquid separation 3 times. Then concentrate the obtained organic layer under reduced pressure, decant the obtained oil with hexane and filter, and then dry the obtained solid under reduced pressure to obtain 52 g of white crystals of Compound A as the target product (yield 69%).

[0340] [Synthesis Example 2 - 2] Synthesis of Compound B

[0341] [Chemical formula 43]

[0342]

[0343] Dissolve 10 g of Compound A prepared in Synthesis Example 2 - 1 in 50 g of dichloromethane, and add 9 g of chlorotrimethylsilane dropwise thereto under ice cooling. Then add dropwise the separately prepared Grignard reagent under ice cooling. After aging at room temperature for 1.5 hours, add an aqueous ammonium chloride solution under ice cooling, then add dichloromethane, separate the organic layer, and add water to the organic layer 5 times and perform liquid separation. Then concentrate the obtained organic layer under reduced pressure, decant the obtained oil with diisopropyl ether, filter, and dry the obtained solid under reduced pressure to obtain 12 g of white crystals of Compound B as the target product (yield 92%).

[0344] [Synthesis Example 2 - 3] Synthesis of Compound B'

[0345] [Chemical formula 44]

[0346]

[0347] Dissolve 7 g of Compound B7g prepared in Synthesis Example 2-2 in 100 g of dichloromethane. Add 25 g of a 7% aqueous nitric acid solution thereto, and separate the organic layer. Repeat the same operation twice. Then add water to the organic layer and separate the layers four times. Thereafter, concentrate the obtained organic layer under reduced pressure. Decant the obtained oily substance with diisopropyl ether, filter, and dry the obtained solid under reduced pressure to obtain 7 g of white crystals of Compound B' as the target product (yield: 94%).

[0348] Under the same conditions as in Synthesis Examples 2-2 and 2-3, using the raw materials and acids shown in Table 2, carry out [Synthesis Example 2-4] to [Synthesis Example 2-13] to obtain the respective target products.

[0349] [Table 2]

[0350] Synthesis Example Reaction Raw Materials Target Product (Yield) 2-4 <![CDATA[Diphenyl sulfide, CH3SiPhMgBr]]> Compound (C): (88%) 2-5 <![CDATA[Compound (A), CH3SiPhMgBr, nitric acid]]> Compound (D): (96%) 2-6 Compound (A), FPhMgBr, p-Toluenesulfonic Acid Compound (E): (90%) 2-7 <![CDATA[Compound (A), CF3PhMgBr, trifluoroacetic acid]]> Compound (F): (92%) 2-8 <![CDATA[Compound (A), CH3OPhMgBr, trifluoromethanesulfonic acid]]> Compound (G): (89%) 2-9 Compound (A), Compound (H) Compound (I): (85%) 2-10 Compound (A), Compound (J) Compound (K): (87%) 2-11 <![CDATA[Compound (L), CH3SiPhMgBr, nitric acid]]> Compound (M): (89%) 2-12 Compound (A), Compound (N), Nitric Acid Compound (O): (85%) 2-13 Compound (A), Compound (P), Nitric Acid Compound (Q): (81%)

[0351] [Reaction raw materials]

[0352] [Chemical formula 45]

[0353]

[0354] [Target product]

[0355] [Chemical formula 46]

[0356]

[0357] [Comparative Synthesis Example 1-1] Synthesis of Sulfonium Salt-Containing Polysiloxane Compound R

[0358] Add a mixture of 61.3 g of Compound (101) and 24.4 g of Compound (120) to a mixture of 120 g of methanol, 0.1 g of 10% nitric acid, and 60 g of deionized water, and keep it at 40 °C for 12 hours to carry out hydrolysis and condensation. After the reaction is completed, add 300 g of propylene glycol monoethyl ether (PGEE), and distill off the water for hydrolysis and condensation and the by-produced alcohol under reduced pressure to obtain 250 g of a PGEE solution of sulfonium salt-containing polysiloxane compound R (compound concentration: 20%). Measure the polystyrene-equivalent molecular weight of polysiloxane compound R, and it is Mw = 2,000.

[0359] [Examples 1-1 to 1-55, and Comparative Examples 1-1 to 1-4]

[0360] The polysiloxane compounds 1 to 18 obtained in the above synthesis examples, the silicon-containing sulfonium salt compound represented by the above general formula (A-1) as a crosslinking catalyst, or a crosslinking catalyst for comparison, an acid, a photoacid generator (PAG-1 to 7 described in Table 6), a solvent, and water were mixed in the proportions shown in Tables 3 to 5, filtered through a 0.1-μm fluororesin filter, and a composition solution for forming a silicon-containing lower layer film was prepared, and named Sol.1 to 59, respectively.

[0361] [Table 3]

[0362]

[0363] [Table 4]

[0364]

[0365] [Table 5]

[0366]

[0367] The crosslinking catalysts used are as follows.

[0368] XL-1... Compound (B)

[0369] XL-2... Compound (B’)

[0370] XL-3... Compound (C)

[0371] XL-4... Compound (D)

[0372] XL-5... Compound (E)

[0373] XL-6... Compound (F)

[0374] XL-7... Compound (G)

[0375] XL-8... Compound (I)

[0376] XL-9... Compound (K)

[0377] XL-10... Compound (M)

[0378] XL-11... Compound (O)

[0379] XL-12... Compound (Q)

[0380] XL-13... Triphenylsulfonium nitrate

[0381] XL-14... Tetramethylammonium nitrate

[0382] XL-15... Tetraoctylammonium nitrate

[0383] XL-16···Polysiloxane compound (R) containing sulfonium salt

[0384] The solvents used are as follows.

[0385] PGEE···Propylene glycol monoethyl ether

[0386] PGME···Propylene glycol monomethyl ether

[0387] GBL···γ-Butyrolactone

[0388] DAA···Diacetone alcohol

[0389] [Table 6]

[0390]

[0391] (EUV patterning test)

[0392] On a silicon wafer, the compositions Sol.1 to 59 for forming a silicon-containing underlayer film of a resist were spin-coated on a Si substrate and heated at 220 °C for 60 seconds to form silicon-containing underlayer films Film1 to 59 with a film thickness of 25 nm.

[0393] Then, a photoresist material obtained by dissolving the following components in the proportions shown in Table 7 was spin-coated on Film1 to 59, prebaked on a hot plate at 105 °C for 60 seconds to form a resist upper layer film with a film thickness of 60 nm. It was exposed using an EUV scanning exposure machine NXE3300 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, mask with a hole pattern having a pitch of 46 nm and a +20% deviation in size on the wafer) manufactured by ASML, PEB was performed on a hot plate at 100 °C for 60 seconds, and developed with a 2.38 mass% aqueous TMAH solution for 30 seconds to obtain a hole pattern with a size of 23 nm.

[0394] Using a length-measuring SEM (CG5000) manufactured by Hitachi High-Technologies Corporation, the exposure dose when the hole size was formed to 23 nm was measured and defined as the sensitivity. Also, the sizes of 50 holes at this time were measured to obtain the size variation (CDU, 3σ). The results are shown in Tables 8 and 9.

[0395] The polymers, quenchers, sensitizers, surfactants, and organic solvents used as the photoresist materials are as follows.

[0396] [Chemical formula 47]

[0397]

[0398] [Chemical formula 48]

[0399]

[0400] [Chemical 49]

[0401]

[0402] Surfactant: FC-4430 made by 3M Company PGMEA: Propylene glycol monomethyl ether acetate CyHO: Cyclohexanone

[0403] PGME: Propylene glycol monomethyl ether

[0404] [Table 7]

[0405]

[0406] (Etching test of the silicon-containing resist underlayer film)

[0407] On a silicon wafer, the compositions Sol.1 to 59 for forming a silicon-containing resist underlayer film were spin-coated on a Si substrate and heated at 220°C for 60 seconds to fabricate silicon-containing resist underlayer films Film1 to 59 with a film thickness of 25 nm.

[0408] The following etching conditions were used to conduct an etching test on the silicon-containing resist underlayer film.

[0409] Etching test with CHF3 / CF4-based gas

[0410] Equipment: Dry etching equipment Telius SP made by Tokyo Electron Limited

[0411] Etching test:

[0412]

[0413] [Table 8]

[0414]

[0415] [Table 9]

[0416]

[0417] As shown in Comparative Examples 1-1 to 1-4 of Tables 8 and 9, for Films 56 to 59 that did not use the silicon-containing sulfonium salt compound represented by the above general formula (A-1) of the present invention as a crosslinking catalyst, CDU deterioration or insufficient etching rate was confirmed. On the other hand, as shown in Examples 1-1 to 1-55, for Films 1 to 55 that used the silicon-containing sulfonium salt compound represented by the above general formula (A-1) of the present invention as a crosslinking catalyst, the affinity with the silicon polymer was high, so the diffusion to the upper-layer resist was suppressed, and it had a CDU improvement effect and a sufficient etching rate.

[0418] [Examples 2-1 to 2-14, and Comparative Examples 2-1 to 2-4]

[0419] (ArF Patterning Test)

[0420] A spin-on carbon film ODL-102 (carbon content 89% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was formed on a silicon wafer with a film thickness of 200 nm. On top of it, the compositions Sol.1-4, 10-12, 26-29, 50-52, 56-59 for forming a silicon-containing underlayer resist film were coated on the spin-on carbon film, and heated at 220 °C for 60 seconds to fabricate silicon-containing underlayer resist films Film1-4, 10-12, 26-29, 50-52, 56-59 with a film thickness of 20 nm.

[0421] Then, the positive-developing ArF resist solution (PR-1) described in Table 10 was coated on the above silicon-containing underlayer resist film, baked at 110 °C for 60 seconds to form a photoresist film with a film thickness of 100 nm. Then, the wetting protective film material (TC-1) described in Table 11 was coated on the photoresist film, baked at 90 °C for 60 seconds to form a protective film with a film thickness of 50 nm.

[0422] Next, they were exposed using an ArF immersion exposure apparatus (manufactured by ASML; XT-1900i, NA 1.35, σ 0.97 / 0.77, 35-degree dipole polarization illumination), baked at 100 °C for 60 seconds (PEB), and developed for 30 seconds with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) to obtain a 40 nm 1:1 positive line-and-space pattern. For its dimensions, the LWR was observed using an electron microscope (CG5000) manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 12.

[0423] [Table 10]

[0424]

[0425] ArF Resist Polymer 1 [Molecular Weight (Mw) = 7,800, Dispersion Degree (Mw / Mn) = 1.78]:

[0426] [Chemical Formula 50]

[0427]

[0428] Acid Generator: PAG-A

[0429] [Chemical Formula 51]

[0430]

[0431] Base: Quencher

[0432] [Chemical Formula 52]

[0433]

[0434] Surfactant: FC-4430 manufactured by 3M Company

[0435] [Table 11]

[0436]

[0437] Protective film polymer [Molecular weight (Mw) = 8,800, Dispersity (Mw / Mn) = 1.69] [Chemical formula 53]

[0438]

[0439] [Table 12]

[0440] Silicon-Containing Antireflective Underlayer Film LWR Example 2-1 Film1 2.1 Example 2-2 Film2 2.0 Example 2-3 Film3 2.0 Example 2-4 Film4 2.0 Example 2-5 Film10 2.1 Example 2-6 Film11 2.1 Example 2-7 Film12 2.2 Example 2-8 Film26 2.1 Example 2-9 Film27 2.0 Example 2-10 Film28 2.1 Example 2-11 Film29 2.1 Example 2-12 Film50 2.2 Example 2-13 Film51 2.2 Example 2-14 Film52 2.1 Comparative Example 2-1 Film56 3.5 Comparative Example 2-2 Film57 3.6 Comparative Example 2-3 Film58 3.2 Comparative Example 2-4 Film59 3.4

[0441] As shown in Examples 2-1 to 2-14 of Table 12, Films 1 to 4, 10 to 12, 26 to 29, and 50 to 52 using the silicon-containing sulfonium salt compound represented by the above general formula (A-1) of the present invention as a crosslinking catalyst have high affinity with the silicon polymer, so the diffusion into the upper-layer resist is suppressed, and an LWR improvement effect can be seen.

[0442] On the other hand, as shown in Comparative Examples 2-1 to 2-4, Films 56 to 59 that do not use the silicon-containing sulfonium salt compound represented by the above general formula (A-1) of the present invention as a crosslinking catalyst show deterioration in LWR.

[0443] This specification includes the following aspects.

[0444] [1]: A silicon-containing sulfonium salt compound, characterized by being represented by the following general formula (A-1).

[0445] [Chemical formula 54]

[0446]

[0447] In the formula, Ar 1 、Ar 2 、and Ar 3 are each 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. Also, any two or more selected from Ar 1 、Ar 2 、and Ar 3 may be bonded to each other and form a ring together with the sulfur atom in the formula. a, b, and c are each independently an integer representing 0 to 3, and 1 ≤ a + b + c ≤ 9. X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, which may be the same or different from each other. A -An organic or inorganic anion that represents a relative ion that becomes a sulfonium cation.

[0448] [2]: A composition for forming a silicon-containing underlayer film for a resist, characterized by containing a silicon-containing sulfonium salt compound as in [1] and a thermally crosslinkable polysiloxane.

[0449] [3]: The composition for forming a silicon-containing underlayer film for a resist as in [2], wherein the thermally crosslinkable polysiloxane contains any one or more of a repeating unit represented by the following general formula (Sx-1), a repeating unit represented by the following general formula (Sx-2), and a partial structure represented by the following general formula (Sx-3).

[0450] [Chemical formula 55]

[0451]

[0452] [Chemical formula 56]

[0453]

[0454] [Chemical formula 57]

[0455]

[0456] In the formula, R 1 , R 2 , and R 3 are each independently a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different.

[0457] [4]: The composition for forming a silicon-containing underlayer film for a resist as in [2] or [3], further containing an acid generator.

[0458] [5]: The composition for forming a silicon-containing underlayer film for a resist as in [4], wherein the acid generator is a photoacid generator that generates an acid upon exposure to high-energy radiation.

[0459] [6]: A method of forming a pattern, which is a method of forming a pattern on a workpiece, characterized by including the following steps:

[0460] Forming an organic film on the workpiece using a coating-type organic film material.

[0461] Forming a silicon-containing underlayer film for a resist on the organic film using the composition for forming a silicon-containing underlayer film for a resist according to any one of [2] to [5].

[0462] Forming a resist upper layer film on the silicon-containing underlayer film for a resist using a composition for a resist upper layer film composed of a photoresist composition.

[0463] Forming a circuit pattern on the resist upper layer film.

[0464] Using the upper resist film having the circuit pattern formed thereon as a mask, transfer the pattern to the lower silicon-containing resist film by etching.

[0465] Using the lower silicon-containing resist film having the pattern transferred thereon as a mask, transfer the pattern to the organic film by etching.

[0466] Using the organic film having the pattern transferred thereon as a mask, transfer the pattern to the workpiece to be processed by etching.

[0467] [7]: A pattern forming method, which is a method for forming a pattern on a workpiece to be processed, characterized by including the following steps:

[0468] Form a hard mask on the workpiece to be processed by CVD method.

[0469] Form a lower silicon-containing resist film on the hard mask using the composition for forming a lower silicon-containing resist film according to any one of [2] to [5].

[0470] Form an upper resist film on the lower silicon-containing resist film using the composition for forming an upper resist film composed of a photoresist composition.

[0471] Form a circuit pattern on the upper resist film.

[0472] Using the upper resist film having the circuit pattern formed thereon as a mask, transfer the pattern to the lower silicon-containing resist film by etching.

[0473] Using the lower silicon-containing resist film having the pattern transferred thereon as a mask, transfer the pattern to the hard mask by dry etching.

[0474] Using the hard mask having the pattern transferred thereon as a mask, transfer the pattern to the workpiece to be processed by dry etching.

[0475] [8]: The pattern forming method according to [6] or [7], using optical lithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination thereof as the method for forming a circuit pattern on the upper resist film.

[0476] [9]: The pattern forming method according to any one of [6] to [8], using a semiconductor device substrate, or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed as the workpiece to be processed.

[0477]

[10] : The pattern forming method as in [9], 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 aforementioned metal.

[0478] Furthermore, the present invention is not limited to the above embodiments. The above embodiments are illustrative, and those having substantially the same configuration and exhibiting the same effects as the technical idea described in the claims of the present invention are all included within the technical scope of the present invention.

Claims

1. A sulfur-containing salt compound containing silicon, characterized by the following represented by the general formula (A-1); In the formula, Ar 1 , Ar 2 , and Ar 3 are each independently an aromatic group having 6 to 20 carbon atoms which may have a substituent, or a heteroaromatic group having 4 to 20 carbon atoms which may have a substituent; further, two or more selected from Ar 1 , Ar 2 , and Ar 3 may be bonded to each other and together with the sulfur atom in the formula form a ring; a, b, and c each independently represent an integer of 0 to 3, and 1 ≤ a + b + c ≤ 9; X, Y, and Z are monovalent organic groups having 1 to 14 carbon atoms, which may be the same or different from each other; A - represents an organic or inorganic anion which is a counter ion forming a sulfonium cation.

2. A composition for forming a silicon-containing resist underlayer film, characterized in that: containing the sulfurium salt compound containing silicon according to claim 1 and a thermally crosslinkable polysiloxane.

3. The composition for forming a silicon-containing anti-reflective lower layer film according to claim 2, wherein, The thermally crosslinkable polysiloxane contains any one or more of the repeating units represented by the following general formula (Sx-1), the repeating units represented by the following general formula (Sx-2), and the partial structure represented by the following general formula (Sx-3). In the formula, R 1 , R 2 , and R 3 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different from each other.

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

5. The composition for forming a silicon-containing resist underlayer film according to claim 4, wherein, The acid generator is a photoacid generator that generates an acid by the action of high-energy rays.

6. A pattern forming method, which is a method for forming a pattern on a workpiece, characterized by comprising the following steps: forming an organic film on the workpiece using a coating-type organic film material; forming a silicon-containing resist underlayer film on the organic film using the composition for forming a silicon-containing resist underlayer film according to any one of claims 2 to 5; forming a resist upper layer film on the silicon-containing resist underlayer film using a resist upper layer film composition composed of a photoresist composition; forming a circuit pattern on the resist upper layer film; using the resist upper layer film on which the circuit pattern has been formed as a mask, and transferring the pattern to the silicon-containing resist underlayer film by etching; using the silicon-containing resist underlayer film on which the pattern has been transferred as a mask, and transferring the pattern to the organic film by etching; using the organic film on which the pattern has been transferred as a mask, and transferring the pattern to the workpiece by etching.

7. A pattern forming method, which is a method for forming a pattern on a workpiece, characterized by comprising the following steps: forming a hard mask on the workpiece by CVD method; forming a silicon-containing resist underlayer film on the hard mask using the composition for forming a silicon-containing resist underlayer film according to any one of claims 2 to 5; forming a resist upper layer film on the silicon-containing resist underlayer film using a resist upper layer film composition composed of a photoresist composition; forming a circuit pattern on the resist upper layer film; using the resist upper layer film on which the circuit pattern has been formed as a mask, and transferring the pattern to the silicon-containing resist underlayer film by etching; using the silicon-containing resist underlayer film on which the pattern has been transferred as a mask, and transferring the pattern to the hard mask by dry etching; using the hard mask on which the pattern has been transferred as a mask, and transferring the pattern to the workpiece by dry etching.

8. The pattern forming method according to claim 6, using optical lithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination thereof as the method for forming a circuit pattern on the resist upper layer film.

9. The pattern forming method according to claim 7, using optical lithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination thereof as the method for forming a circuit pattern on the resist upper layer film.

10. The pattern forming method according to claim 6, wherein a semiconductor device substrate, or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed on the semiconductor device substrate is used as the object to be processed.

11. The pattern forming method according to claim 7, wherein a semiconductor device substrate, or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed on the semiconductor device substrate is used as the object to be processed.

12. The pattern forming method according to claim 10, wherein silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof is used as the metal.

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

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