Silicon-containing resist underlayer film-forming composition and pattern forming method

Abstract

The present invention relates to a silicon-containing resist underlayer film forming composition and a pattern forming method. The subject of the present invention is to provide a silicon-containing resist underlayer film that has a high effect of suppressing the collapse of ultrafine patterns in a multilayer resist method and has an appropriate etching rate. The solution to this problem is a silicon-containing resist underlayer film forming composition, which contains at least one or more quaternary ammonium salts represented by the following general formula (A-1) and a thermally crosslinkable polysiloxane (Sx). [Chemical 1] In the formula, Ar 1 R represents an aromatic group having 6 to 20 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms. 11 Z represents an alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted. ‑ It represents an organic or inorganic anion that serves as a counter ion to a quaternary ammonium cation.

Description

Technical Field

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

[0002] With the high integration and high speed of large-scale integrated circuits (LSI), the miniaturization of pattern size is progressing rapidly. With this miniaturization, photolithography technology has achieved the formation of fine patterns by using the shorter wavelength of the light source and the appropriate selection of the corresponding resist composition. The center is the positive photoresist composition used in a single layer. The single-layer positive photoresist composition is formed by making the resist resin have a skeleton with etching resistance to dry etching using chlorine or fluorine gas plasma, and having a switching mechanism such as the exposure part will dissolve, so that the exposure part dissolves to form a pattern, and the remaining resist pattern is used as an etching mask to perform dry etching on the processed substrate.

[0003] However, when miniaturization is performed while maintaining the film thickness of the photoresist film used, that is, when the pattern width is reduced, the resolution performance of the photoresist film is reduced. In addition, when the photoresist film is used for pattern development with a developer, the so-called aspect ratio becomes too large, resulting in pattern collapse. Therefore, as the pattern is miniaturized, the photoresist film is gradually thinned.

[0004] On the other hand, the processing of the processed substrate usually uses the following method: using a photoresist film with a pattern as an etching mask and using dry etching to process the substrate; but in reality, there is no dry etching method that can obtain complete etching selectivity between the photoresist film and the processed substrate. Therefore, there will be problems such as the resist film being damaged and collapsed during the processing of the substrate, and the resist pattern cannot be correctly transferred to the processed substrate. Therefore, with the miniaturization of the pattern, the photoresist composition is gradually seeking higher dry etching resistance. However, on the other hand, in order to improve the resolution, the resin used in the photoresist composition has gradually sought a resin with low light absorption at the exposure wavelength. Therefore, as the exposure light becomes shorter in wavelength and becomes i-ray, KrF, and ArF, the resin used in the photoresist composition has gradually changed to a novolac resin, a resin with a polyhydroxystyrene, and an aliphatic polycyclic skeleton, but in reality, the etching speed under dry etching conditions during substrate processing gradually becomes faster, and the recent photoresist composition with high resolution tends to weaken the etching resistance.

[0005] In view of this situation, it has become necessary to perform dry etching processing on the substrate to be processed using a photoresist film that is thin and has weak etching resistance, and securing materials and processes in this processing step has become increasingly urgent.

[0006] The multilayer resist method is one of the methods for solving such problems. This method is to insert a lower film having a different etching selectivity from the photoresist film (i.e., the upper resist film) between the upper resist film and the substrate to be processed, and after the upper resist film has a pattern, the upper resist film pattern is used as a dry etching mask to transfer the pattern to the lower film by dry etching, and then the lower film is used as a dry etching mask to transfer the pattern 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 a general resist composition used in a single-layer resist method. The three-layer resist method, for example, is as follows: an organic film derived from a novolac resin or the like is formed on a substrate to be processed, a silicon-containing resist lower film is formed thereon, and a normal organic photoresist film is formed thereon as a resist upper film. When dry etching using fluorine-based gas plasma is performed, the organic resist upper film can obtain a good etching selectivity compared to the silicon-containing resist lower film, so the resist upper film pattern can be transferred to the silicon-containing resist lower film by dry etching using fluorine-based gas plasma. According to this method, even if a resist composition that is difficult to form a pattern with sufficient film thickness for directly processing the substrate to be processed is used, or a resist composition that does not have sufficient dry etching resistance for the processing of the substrate, the pattern can still be transferred to a silicon-containing film (resist lower film), and then a pattern transfer using dry etching by oxygen or hydrogen gas plasma is implemented, so that an organic film pattern derived from a novolac resin or the like with sufficient dry etching resistance for the processing of the substrate can be obtained. The silicon-containing film remaining after the organic film pattern is formed is usually removed in a manner that does not become a residue causing a defect by dry etching by fluorine gas plasma or wet etching by etching solutions such as alkali and fluorine. When the etching rate is insufficient, the possibility of problems such as residues remaining from the silicon-containing film remaining and becoming defects or requiring a long etching process to damage the substrate to be processed increases. In this way, for correct patterning and smooth removal, the silicon-containing resist lower film requires an appropriate etching rate.

[0008] On the one hand, ArF immersion lithography and EUV lithography have been developed in recent years, which will gradually make it possible to form finer patterns. On the other hand, ultra-fine patterns are very easy to collapse due to their small ground area, and suppressing pattern collapse is a very big issue. Therefore, the development of a silicon-containing resist underlayer film that has a high effect of suppressing pattern collapse has become a top priority.

[0009] Here, someone proposes a composition for forming a silicon-containing resist lower film for ArF or EUV lithography containing a curing catalyst (patent documentation 1, 2). The curing catalyst catalyzes the condensation reaction of silanols and has a structure suitable for promoting the formation of a siloxane-bonded main skeleton of the silicon-containing resist lower film. In addition, it is now gradually understood that the selection of a curing catalyst can have various effects on the properties of the resist lower film. For example, acid-alkalinity degree, hydrophilic-hydrophobicity, hardness, film density, etching rate, etc. can be cited. Through them, and then also the interaction with the upper resist is affected, and the pattern collapse or the shape of the resist tailing caused by the deterioration of adhesion is caused, and the last substrate processing is poor and can become a serious problem.

[0010] In addition, a silicon-containing resist underlayer film-forming composition containing a silane compound having a group acting as a curing catalyst has been proposed as a silicon-containing resist underlayer film-forming composition containing a curing catalyst (Patent Document 3). However, in the most advanced applications where miniaturization is further advanced using EUV lithography, pattern collapse may sometimes become a problem, and improvement is needed.

[0011] Prior art documents

[0012] Patent Literature

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

[0014] [Patent Document 2] WO2013 / 161372

[0015] [Patent Document 3] WO2010 / 021290 Summary of the invention

[0016] Problem that the invention aims to solve

[0017] An object of the present invention is to provide a resist underlayer film containing silicon which has a high effect of suppressing collapse of ultrafine patterns in a multilayer resist method, can form a good resist pattern, and has an appropriate etching rate.

[0018] Solutions for solving problems

[0019] The present invention is made to solve the above-mentioned problems and provides a silicon-containing resist underlayer film-forming composition characterized by containing at least one or two or more quaternary ammonium salts represented by the following general formula (A-1) and a thermally crosslinkable polysiloxane (Sx).

[0020] [Chemistry 1]

[0021]

[0022] In the formula, Ar1 represents an aromatic group having 6 to 20 carbon atoms, or a heteroaromatic group having 4 to 20 carbon atoms, which may have a substituent. 11 R each independently represents a linear, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl or aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted. 11 Two of them may also be bonded to each other to form a ring. - It represents an organic or inorganic anion that serves as a counter ion to a quaternary ammonium cation.

[0023] The quaternary ammonium salt represented by the general formula (A-1) contained in the silicon-containing resist underlayer film-forming composition of the present invention functions as a crosslinking catalyst to promote the thermal curing of the silicon-containing resist underlayer film. The thermally cured underlayer film has a sufficient etching rate, an effect of preventing the pattern collapse of the upper resist, and an effect of forming a good resist pattern.

[0024] In the present invention, the quaternary ammonium salt represented by the above general formula (A-1) is preferably represented by the following general formula (A-2).

[0025] [Chemistry 2]

[0026]

[0027] In the formula, R 11 As above. Z1 - represents an organic or inorganic anion that is a counter ion to the quaternary ammonium cation, and Z1 - The boiling point of the conjugate acid Z1-H is below 200°C.

[0028] When the quaternary ammonium salt represented by the above general formula (A-1) is represented by the above general formula (A-2), the effects of the present invention are more fully exhibited.

[0029] The heat-crosslinkable polysiloxane (Sx) preferably contains at least one 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).

[0030] [Chemistry 3]

[0031]

[0032] [Chemistry 4]

[0033]

[0034] [Chemistry 5]

[0035]

[0036] In the formula, R 1 , R 2 , R 3 They are respectively monovalent organic groups having 1 to 30 carbon atoms and may be the same or different.

[0037] When the thermally crosslinkable polysiloxane (Sx) contains the specific structure, the effects of the present invention are more fully exhibited.

[0038] The silicon-containing resist underlayer film-forming composition of the present invention may further contain an acid generator.

[0039] By adding an acid generator as needed, the pattern shape, exposure sensitivity, etc. can be fine-tuned.

[0040] When the silicon-containing resist underlayer film-forming composition of the present invention contains an acid generator, the acid generator is preferably a sulfonium salt, and is preferably a photoacid generator that generates an acid by the action of high-energy rays.

[0041] In this case, the degradation of other properties can be minimized, and the pattern shape, exposure sensitivity, etc. of the resist upper layer film can be appropriately adjusted. In addition, it may be effective in reducing residues from the resist upper layer film.

[0042] The present invention provides a pattern forming method, which is characterized by comprising the following steps: forming an organic film on a workpiece using a coating type organic film material, forming a silicon-containing resist underlayer film on the organic film using the above-described silicon-containing resist underlayer film forming composition, forming a resist upper layer film using a resist upper layer film composition composed of a photoresist composition on the silicon-containing resist underlayer film, forming a circuit pattern on the resist upper layer film, using the resist upper layer film on which the circuit pattern is formed as a mask and transferring the pattern to the silicon-containing resist underlayer film by etching, using the silicon-containing resist underlayer film to which the pattern is transferred as a mask and transferring the pattern to the organic film by etching, and using the organic film to which the pattern is transferred as a mask and transferring the pattern to the workpiece by etching.

[0043] In addition, the present invention provides a pattern forming method, which is characterized by comprising the following steps: forming a hard mask with carbon as a main component on a workpiece by a CVD method, forming a silicon-containing resist underlayer film on the aforementioned hard mask using the silicon-containing resist underlayer film forming composition described above, forming a resist upper layer film using a resist upper layer film composition composed of a photoresist composition on the aforementioned silicon-containing resist underlayer film, forming a circuit pattern on the aforementioned resist upper layer film, using the aforementioned resist upper layer film with the circuit pattern formed as a mask and transferring the pattern to the aforementioned silicon-containing resist underlayer film by etching, using the aforementioned silicon-containing resist underlayer film with the pattern transferred as a mask and transferring the pattern to the aforementioned hard mask by dry etching, and using the aforementioned hard mask with the pattern transferred as a mask and transferring the pattern to the aforementioned workpiece by dry etching.

[0044] The above pattern forming method can suppress the pattern collapse of the resist upper film and provide a good resist pattern. In addition, the pattern transfer to the silicon-containing resist lower film by dry etching is excellent. In addition, the silicon-containing resist lower film remaining after patterning is easy to remove and is not prone to defects caused by residues. Therefore, it is a practical pattern forming method especially when forming a fine pattern.

[0045] The patterning in the step of forming a circuit pattern on the resist upper film is preferably performed by optical lithography with a wavelength of 10 nm to 300 nm, direct writing using an electron beam, nanoimprinting, or a combination thereof.

[0046] When the resist upper layer film pattern forming method is the above-mentioned specific pattern forming method, the effect of the present invention is more fully exerted.

[0047] The object to be processed may be a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film or a metal oxide nitride film.

[0048] When the above-mentioned object to be processed is the above-mentioned specific object, the effect of the present invention is more fully exerted.

[0049] In addition, the metal constituting the above-mentioned processed body is preferably silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt or an alloy thereof.

[0050] When the metal constituting the above-mentioned object to be processed is the above-mentioned specific metal, the effect of the present invention is more fully exerted.

[0051] Effects of the Invention

[0052] The silicon-containing resist lower film forming composition of the present invention containing a quaternary ammonium salt of a specific structure can not only form an ultra-fine upper resist pattern without collapse, but also form a good pattern shape. In addition, since the dry etching selectivity of the resist upper film and the organic film or hard mask is excellent, the pattern of the semiconductor device can be formed on the substrate with a good yield. In addition, the silicon-containing resist lower film forming composition of the present invention can obtain high etching selectivity between the organic material, so the formed photoresist pattern can be transferred to the silicon-containing resist lower film, the organic film or the hard mask in sequence using dry etching. In addition, in the present invention, since the silicon-containing resist lower film formed has a sufficient etching speed, the silicon-containing resist lower film remaining after the patterning is completed can be easily removed, and it is not easy to produce defects caused by residues, so it is particularly effective in the formation of fine patterns. DETAILED DESCRIPTION

[0053] The present invention relates to a composition for forming a coating type silicon-containing film used for photolithography in a manufacturing step of a semiconductor element or the like, and a pattern forming method using the composition.

[0054] As described above, a composition for forming a silicon-containing resist underlayer film is sought that can provide a silicon-containing resist underlayer film that has a high effect of suppressing ultrafine pattern collapse in a multilayer resist method, can form a good resist pattern, and has an appropriate etching rate, and a method for forming an ultrafine pattern using the composition is sought.

[0055] The present inventors have conducted in-depth studies to achieve the above-mentioned purpose and have found that by formulating a quaternary ammonium salt of a specific structure into a composition for forming a silicon-containing resist underlayer film, a silicon-containing resist underlayer film can be provided that can suppress the collapse of ultrafine patterns in a multilayer resist method, form a good resist pattern, and have an appropriate etching rate during processing, thereby completing the present invention.

[0056] That is, the present invention is a silicon-containing resist underlayer film-forming composition comprising at least one or two or more quaternary ammonium salts represented by the general formula (A-1) described below and a thermally crosslinkable polysiloxane (Sx).

[0057] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0058] <Resist Underlayer Film-Forming Composition>

[0059] The silicon-containing resist underlayer film-forming composition of the present invention is a silicon-containing resist underlayer film-forming composition containing at least one or two or more quaternary ammonium salts represented by the following general formula (A-1) and a thermally crosslinkable polysiloxane (Sx).

[0060] [Chemistry 6]

[0061]

[0062] In the formula, Ar 1 represents an aromatic group having 6 to 20 carbon atoms, or a heteroaromatic group having 4 to 20 carbon atoms, which may have a substituent. 11 R each independently represents a linear, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl or aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted. 11 Two of them may also be bonded to each other to form a ring. - It represents an organic or inorganic anion that serves as a counter ion to a quaternary ammonium cation.

[0063] [Quaternary ammonium salt represented by general formula (A-1) or (A-2)]

[0064] The silicon-containing resist underlayer film-forming composition of the present invention contains at least one or more quaternary ammonium salts represented by the above-mentioned general formula (A-1). The quaternary ammonium salt functions as a crosslinking catalyst, thereby promoting thermal curing, and the formed silicon-containing resist underlayer film is composed of an appropriate composition and structure, and has an etching rate sufficient for processing. In addition, it is generally believed that in the quaternary ammonium salt, the unshared electron pairs possessed by the nitrogen atoms are not concentrated in the directly bonded aromatic rings, so the basicity can be maintained at a moderate level, suppressing the tailing shape of the upper resist while becoming an appropriate surface state, thereby suppressing the pattern collapse of the upper resist.

[0065] In the above general formula, Ar 1 It represents an aromatic group having 6 to 20 carbon atoms, or a heteroaromatic group having 4 to 20 carbon atoms, which may also have a substituent. Specific examples of the aromatic group having 6 to 20 carbon atoms include phenyl, naphthyl, anthracenyl, phenanthrenyl, and pyrenyl. Specific examples of the heteroaromatic group having 4 to 20 carbon atoms include furanyl, thiophenyl, pyrrolyl, benzofuranyl, pyridyl, indolyl, oxazolyl, imidazolyl, and benzimidazolyl. Substituents that may also be present include linear, branched, or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups, heteroaromatic groups, alkoxy groups, hydroxyl groups, ester groups, carbonyl groups, amino groups, halogen groups, thioether groups, carboxyl groups, sulfonyl groups, amide groups, imide groups, cyano groups, aldehyde groups, imino groups, urea groups, carbamate groups, carbonate groups, nitro groups, sulfonyl groups, and groups formed by combining these groups.

[0066] In the above general formula, R 11Each independently represents a linear, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl or aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted by an alkoxy group or the like. 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, and adamantyl. Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Examples of the oxoalkyl group include 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxopropyl, 2-oxoethyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl. Examples of the oxoalkenyl group include 3-oxopropenyl. Examples of the aryl group include phenyl, naphthyl, thienyl, etc., or alkoxyphenyl groups such as 4-hydroxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4-tert-butoxyphenyl, 3-tert-butoxyphenyl; alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-n-butylphenyl, 2,4-dimethylphenyl; alkylnaphthyl groups such as methylnaphthyl and ethylnaphthyl; alkoxynaphthyl groups such as methoxynaphthyl, ethoxynaphthyl, n-propoxynaphthyl, n-butoxynaphthyl; dialkylnaphthyl groups such as dimethylnaphthyl and diethylnaphthyl; dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl. Examples of the aralkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, etc. Examples of the aryloxyalkyl group include 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, 2-(2-naphthyl)-2-oxoethyl and other 2-aryl-2-oxoethyl groups. Examples of the alkoxy group include methoxy, ethoxy and tert-butoxy. 11 In this case, two R 11 The divalent group formed can be specifically exemplified by trimethylene, tetramethylene, pentamethylene, 3-oxopentamethylene, and 3-oxopentamethylene.

[0067] In the above general formula, Z -It represents an organic or inorganic anion that becomes a counter ion of a quaternary ammonium cation. Specific examples of organic anions include formate, acetate, propionate, butyrate, hexanoate, benzoate, tert-butylbenzoate, trichloroacetate, trifluoroacetate, 2-hydroxy-2,2-bis(trifluoromethyl)acetate, trimethylacetate, pentafluoropropionate, methanesulfonate, butanesulfonate, benzenesulfonate, toluenesulfonate, trifluoromethanesulfonate, and methylsulfate ions. Specific examples of inorganic anions include chloride ions, bromide ions, iodide ions, fluoride ions, cyanide ions, nitrate ions, nitrite ions, and hydroxide ions.

[0068] In the present invention, the quaternary ammonium salt represented by the general formula (A-1) may be used alone or in combination of two or more. The amount of the quaternary ammonium salt represented by the general formula (A-1) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, relative to 100 parts by mass of the base polymer (Sx) described later.

[0069] Furthermore, the quaternary ammonium salt represented by the above general formula (A-1) is preferably represented by the following general formula (A-2).

[0070] [Chemistry 7]

[0071]

[0072] In the formula, R 11 As above. Z1 - represents an organic or inorganic anion that is a counter ion to the quaternary ammonium cation, and Z1 - The boiling point of the conjugate acid Z1-H is below 200°C.

[0073] The counter ion Z1 of the quaternary ammonium salt represented by the above general formula (A-2) - The conjugate acid Z1-H is selected so that the boiling point is 200° C. or less. If the boiling point of the conjugate acid is 200° C. or less, there is no concern that it will have a negative effect on resist pattern collapse. The lower limit of the boiling point of the conjugate acid is not particularly limited, but is preferably -90° C. or more.

[0074] In the above general formula (A-2), R 11 Same as above. The characteristic is Z1 - represents an organic or inorganic anion that is a counter ion to the quaternary ammonium cation, and Z1 - The boiling point of the conjugate acid Z1-H is below 200°C. -Specific examples include: formate, acetate, propionate, butyrate, isobutyrate, trichloroacetate, trifluoroacetate, monochlorodifluoroacetate, 2-hydroxy-2,2-bis(trifluoromethyl)acetate, trimethylacetate, pentafluoropropionate, perfluorobutyrate, methanesulfonate, trifluoromethanesulfonate, chloride ion, bromide ion, iodide ion, fluoride ion, cyanide ion, nitrate ion, nitrite ion, and hydroxide ion. In terms of improving the effect of the present invention, trifluoroacetate, 2-hydroxy-2,2-bis(trifluoromethyl)acetate, pentafluoropropionate, chloride ion, bromide ion, iodide ion, and nitrate ion are more preferred.

[0075] The quaternary ammonium salt represented by the general formula (A-1) or (A-2) may be exemplified by the following compounds, but is not limited thereto. In the following formula, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group, and the same applies to the following.

[0076] [Chemistry 8]

[0077]

[0078] [Chemistry 9]

[0079]

[0080] [Chemistry 10]

[0081]

[0082] [Thermal crosslinking polysiloxane (Sx)]

[0083] The silicon-containing resist underlayer film-forming composition of the present invention contains a heat-crosslinkable polysiloxane (Sx) in addition to one or two or more quaternary ammonium salts represented by the above general formula (A-1) or (A-2).

[0084] The heat-crosslinkable polysiloxane (Sx) used in the present invention preferably contains at least one 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).

[0085] [Chemistry 11]

[0086]

[0087] [Chemistry 12]

[0088]

[0089] [Chemistry 13]

[0090]

[0091] In the formula, R 1 , R 2 , R 3 They are respectively monovalent organic groups having 1 to 30 carbon atoms and may be the same or different.

[0092] The thermally crosslinkable polysiloxane (Sx) can be produced by hydrolyzing and condensing the following hydrolyzable monomer (Sm).

[0093] Specific examples of the hydrolyzable monomer (Sm) include 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, and isopropyl tripropoxysilane, isopropyl triisopropoxysilane, butyl trimethoxysilane, butyl triethoxysilane, butyl tripropoxysilane, butyl triisopropoxysilane, sec-butyl trimethoxysilane, sec-butyl triethoxysilane, sec-butyl tripropoxysilane, sec-butyl triisopropoxysilane, tert-butyl trimethoxysilane, tert-butyl triethoxysilane, tert-butyl tripropoxysilane, tert-butyl triisopropoxysilane, cyclopropyl trimethoxysilane, cyclopropyl triethoxysilane, cyclopropyl tripropoxysilane, cyclopropyl triisopropoxysilane, cyclobutyl trimethoxysilane, cyclobutyl triethoxysilane, cyclobutyl tripropoxysilane, cyclobutyl triisopropoxysilane, cyclopentyl trimethoxysilane, cyclopentyl triethoxysilane, cyclopentyl tripropoxysilane 、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, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltripropoxysilane,Methoxybenzyltriisopropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltripropoxysilane, tolyltriisopropoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltripropoxysilane, phenethyltriisopropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltripropoxysilane, naphthyltriisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, dipropyldimethoxysilane, di Propyldiethoxysilane, dipropyldipropoxysilane, dipropyldiisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxysilane, dibutyldiisopropoxysilane, di(sec-butyl)dimethoxysilane, di(sec-butyl)diethoxysilane, di(sec-butyl)dipropoxysilane, di(sec-butyl)diisopropoxysilane, di(tert-butyl)dimethoxysilane, di(tert-butyl)diethoxysilane, di(tert-butyl)dipropoxysilane, di(tert-butyl)diisopropoxysilane, dicyclopropyldimethoxysilane, dicyclopropyldiethoxysilane, dicyclopropyl Dipropoxysilane, dicyclopropyl diisopropoxysilane, dicyclobutyl dimethoxysilane, dicyclobutyl diethoxysilane, dicyclobutyl dipropoxysilane, dicyclobutyl diisopropoxysilane, dicyclopentyl dimethoxysilane, dicyclopentyl diethoxysilane, dicyclopentyl dipropoxysilane, dicyclopentyl diisopropoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, dicyclohexyl dipropoxysilane, dicyclohexyl diisopropoxysilane, dicyclohexenyl dimethoxysilane, dicyclohexenyl diethoxysilane, dicyclohexenyl dipropoxysilane, dicyclohexenyl diisopropoxysilane, dicyclohexenyl ethyl dimethoxysilane, dicyclohexenyl ethyl diethoxysilane, dicyclohexenyl ethyl dipropoxysilane, dicyclohexenyl Alkenylethyldiisopropoxysilane, 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.

[0094] Preferred examples of the above compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, and cyclohexenyltrimethoxysilane. , cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane, etc.

[0095] The above R corresponding to the compound exemplified as the hydrolyzable monomer (Sm) 1 , R 2 , R 3 Another example of the organic group represented by can be an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, it is an organic group having one or more groups selected from the group consisting of ether bonds, ester bonds, alkoxy groups, hydroxyl groups, etc. This example can be an organic group represented by the following general formula (Sm-R).

[0096] (P-Q1-(S1) v1 -Q2-) u -(T) v2 -Q3-(S2) v3-Q4-(Sm-R)

[0097] 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 1 to 6 carbon atoms, or an alkylcarbonyl group having 1 to 6 carbon atoms, and Q1, Q2, Q3, and Q4 are each independently -C q H (2q-p) P p -, wherein P is the same as above, p is an integer of 0 to 3, q ​​is an integer of 0 to 10, but q=0 represents a single bond, u is an integer of 0 to 3, 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 consisting of a divalent atom other than carbon, an alicyclic ring, an aromatic ring or a heterocyclic ring. Examples of T being an alicyclic ring, an aromatic ring or a heterocyclic ring which may also contain a heteroatom such as an oxygen atom are shown below. The positions at which T and Q2 are bonded to Q3 are not particularly limited and can be appropriately selected in consideration of the reactivity due to stereogenic factors, the availability of commercially available reagents used in the reaction, etc.

[0098] [Chemistry 14]

[0099]

[0100] 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 as follows: In the following formula, (Si) is described to indicate the bonding position to Si.

[0101] [Chemistry 15]

[0102]

[0103] [Chemistry 16]

[0104]

[0105] In addition, R 1 , R 2 , R 3 As examples of the organic group, an organic group containing a silicon-silicon bond can also be used. Specifically, the following organic groups can be mentioned.

[0106] [Chemistry 17]

[0107]

[0108] In addition, R 1 , R 2 , R 3Examples of the organic group may include organic groups having a protective group that decomposes due to acid. Specifically, organic groups listed in paragraphs (0043) to (0048) of Japanese Patent Application Laid-Open No. 2013-167669 and organic groups derived from silicon compounds exemplified in paragraph (0056) of Japanese Patent Application Laid-Open No. 2013-224279 may be mentioned.

[0109] In addition, R 1 , R 2 , R 3 Examples of the organic group include organic groups having a fluorine atom, and specifically, organic groups derived from silicon compounds exemplified in paragraphs (0059) to (0065) of JP-A-2012-53253.

[0110] The hydrolyzable monomer (Sm) is a monomer having one, two or three chlorine, bromine, iodine, acetoxy, methoxy, ethoxy, propoxy or butoxy groups bonded to silicon represented by (Si) in the partial structure as hydrolyzable groups.

[0111] [Method for synthesizing heat-crosslinkable polysiloxane (Sx)]

[0112] (Synthesis method 1: acid catalyst)

[0113] The heat-crosslinkable polysiloxane (Sx) of the present invention can be produced by subjecting one hydrolyzable monomer (Sm) or a mixture of two or more thereof to hydrolysis and condensation in the presence of an acid catalyst.

[0114] The acid catalyst used at this time includes organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, methanesulfonic acid, benzenesulfonic acid, 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 1×10 -6 ~10 mol, preferably 1×10 -5 ~5 mol, more preferably 1×10 -4 ~1 mol.

[0115] When obtaining the heat-crosslinkable polysiloxane (Sx) from these monomers by hydrolysis condensation, the amount of water added is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, and even more preferably 0.1 to 30 mol per 1 mol of the hydrolyzable substituent bonded to the monomer. If it is 100 mol or less, the equipment used for the reaction is small and economical.

[0116] The operation method is to add monomers to the catalyst aqueous solution and start the hydrolysis condensation reaction. At this time, an organic solvent may be added to the catalyst aqueous solution, the monomers may be diluted with an organic solvent, or both may be performed. The reaction temperature is 0 to 100°C, preferably 5 to 80°C. It is preferably a method in which the temperature is maintained at 5 to 80°C during the dropwise addition of the monomers and then matured at 20 to 80°C.

[0117] The organic solvent that can be added to the aqueous catalyst solution or the organic solvent that can dilute the monomer is preferably methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, 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 mono-tert-butyl ether acetate, γ-butyrolactone and a mixture thereof.

[0118] Among these solvents, water-soluble solvents are preferred. Examples include: alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; polyols such as ethylene glycol and propylene glycol; polyol condensation product derivatives such as butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, and ethylene glycol monopropyl ether; acetone, acetonitrile, tetrahydrofuran, etc. Among them, solvents having a boiling point of 100°C or less are particularly preferred.

[0119] The amount of the organic solvent used is 0 to 1,000 ml, particularly preferably 0 to 500 ml, based on 1 mol of the monomer. When the amount of the organic solvent used is small, the reaction vessel can be smaller, which is more economical.

[0120] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture. At this time, the amount of the alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used for the catalyst. The alkaline substance may be any substance as long as it exhibits alkalinity in water.

[0121] Then, it is preferred to remove byproducts such as alcohol generated by the hydrolysis condensation reaction from the reaction mixture by reduced pressure removal. The temperature of the heating reaction mixture at this time depends on the type of alcohol etc. produced by the added organic solvent and the reaction, preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and further preferably 15 to 80 ° C. In addition, the degree of reduced pressure at this time depends on the type of organic solvent and alcohol etc. to be removed, the exhaust device, the condensation concentration device and the heating temperature, preferably below atmospheric pressure, more preferably below 80 kPa by absolute pressure, and further preferably below 50 kPa by absolute pressure. It is not easy to correctly know the amount of alcohol removed at this time, but it is ideal to remove the alcohol generated by about 80% by mass or more.

[0122] Then, the acid catalyst used for the hydrolysis condensation can 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 with an organic solvent. The organic solvent used at this time is preferably an organic solvent that can dissolve the thermally crosslinkable polysiloxane and separate into two layers when mixed with water. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0123] Furthermore, a mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent may also be used. For example, preferred are methanol-ethyl acetate mixtures, ethanol-ethyl acetate mixtures, 1-propanol-ethyl acetate mixtures, 2-propanol-ethyl acetate mixtures, butanediol monomethyl ether-ethyl acetate mixtures, propylene glycol monomethyl ether-ethyl acetate mixtures, ethylene glycol monomethyl ether-ethyl acetate mixtures, butanediol monoethyl ether-ethyl acetate mixtures, propylene glycol monoethyl ether-ethyl acetate mixtures, ethylene glycol monoethyl ether-ethyl acetate mixtures, butanediol monopropyl ether-ethyl acetate mixtures, propylene glycol monopropyl ether-ethyl acetate mixtures, ethylene glycol monopropyl ether-ethyl acetate mixtures, methanol-methyl isobutyl ketone mixtures, ethanol-methyl isobutyl ketone mixtures, 1-propanol-methyl isobutyl ketone mixtures, 2-propanol-methyl isobutyl ketone mixtures, propylene glycol monomethyl ether-methyl isobutyl ketone mixtures, ethylene glycol monomethyl ether-methyl isobutyl ketone mixtures, propylene glycol monoethyl ether-methyl isobutyl ketone mixtures, ethylene glycol monoethyl ether-methyl isobutyl ketone mixtures, propylene glycol monopropyl ether-methyl isobutyl ketone mixtures, ethylene glycol monopropyl ether-methyl isobutyl ketone mixtures, Butyl 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, ethyl The combinations include, but are not limited to, a propylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, a 1-propanol-propylene glycol methyl ether acetate mixture, a 2-propanol-propylene glycol methyl ether acetate mixture, a propylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, a propylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, a ethylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, a propylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, and a ethylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture.

[0124] The mixing ratio of the water-soluble organic solvent and the poorly water-soluble organic solvent can be appropriately selected, and the water-soluble organic solvent is 0.1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, and more preferably 2 to 100 parts by mass based on 100 parts by mass of the poorly water-soluble organic solvent.

[0125] Then, it can also be washed with neutral water. The water can be what is generally called deionized water or ultrapure water. The amount of water is 0.01 to 100 L, preferably 0.05 to 50 L, and more preferably 0.1 to 5 L relative to 1 L of the thermally crosslinkable polysiloxane solution. The washing method can be to put the two into the same container, stir them, and then stand to separate the water layer. The number of washings can be more than 1 time. Even if washing more than 10 times, the corresponding washing effect cannot be obtained, so it is preferably about 1 to 5 times.

[0126] Other methods for removing the acid catalyst include a method using an ion exchange resin and a method of removing the acid catalyst after neutralization with an epoxy compound such as ethylene oxide or propylene oxide. These methods can be appropriately selected according to the acid catalyst used in the reaction.

[0127] The water washing operation at this time may cause part of the thermally crosslinkable polysiloxane to escape into the water layer, and may provide substantially the same effect as the classification operation. Therefore, the number of water washings and the amount of washing water may be appropriately selected depending on the catalyst removal effect and the classification effect.

[0128] Regardless of whether the final solvent is added to any one of the heat-crosslinkable polysiloxane solution with residual acid catalyst and the heat-crosslinkable polysiloxane solution with the acid catalyst removed, and the solvent exchange is performed under reduced pressure, the desired heat-crosslinkable polysiloxane solution will be obtained. The temperature of the solvent exchange at this time depends on the type of reaction solvent and extraction solvent to be removed, preferably 0 to 100°C, more preferably 10 to 90°C, and more preferably 15 to 80°C. In addition, the degree of decompression at this time depends on the type of extraction solvent to be removed, the exhaust device, the condensation concentration device and the heating temperature, and is preferably below atmospheric pressure, more preferably below 80kPa by absolute pressure, and more preferably below 50kPa by absolute pressure.

[0129] At this time, the thermally crosslinkable polysiloxane may become unstable due to the change of solvent. This depends on the compatibility of the final solvent and the thermally crosslinkable polysiloxane. In order to prevent this, a monovalent or divalent alcohol having a cyclic ether as a substituent as described in paragraphs (0181) to (0182) of Japanese Patent Publication No. 2009-126940 may be added as a stabilizer. The amount added is 0 to 25 parts by mass, preferably 0 to 15 parts by mass, more preferably 0 to 5 parts by mass, relative to 100 parts by mass of the thermally crosslinkable polysiloxane in the solution before the solvent exchange, but preferably 0.5 parts by mass or more when added. If necessary, a monovalent or divalent alcohol having a cyclic ether as a substituent may be added to the solution before the solvent exchange and then the solvent exchange operation may be performed.

[0130] If the heat-crosslinkable polysiloxane is concentrated to a certain concentration or more, the condensation reaction may proceed further and the polysiloxane may become insoluble in an organic solvent, so it is preferably prepared in advance in a solution state of appropriate concentration. In addition, if the concentration is too thin, the amount of solvent becomes too much, so it is economical and ideal to prepare in advance in a solution state of appropriate concentration. The concentration at this time is preferably 0.1 to 20% by mass.

[0131] The final solvent added to the thermally crosslinkable polysiloxane solution is preferably an alcohol solvent, and particularly preferably a monoalkyl ether derivative of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, etc. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol, etc. are preferred.

[0132] If these solvents are the main components, non-alcoholic solvents may be added as auxiliary solvents. Examples of the auxiliary solvents 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 monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, and cyclopentyl methyl ether.

[0133] In addition, another reaction operation using an acid catalyst is to add water or a water-containing organic solvent to the monomer or the organic solution of the monomer and start the hydrolysis reaction. In this case, the catalyst can be added to the monomer or the organic solution of the monomer, or to water or a water-containing organic solvent. The reaction temperature is 0 to 100°C, preferably 10 to 80°C. It is preferably a method of heating to 10 to 50°C when water is added dropwise, and then raising the temperature to 20 to 80°C to mature it.

[0134] When an organic solvent is used, a water-soluble organic solvent is preferred, and examples thereof include polyol condensate derivatives such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, and mixtures thereof.

[0135] The amount of the organic solvent used is 0 to 1,000 ml, particularly preferably 0 to 500 ml, relative to 1 mol of the monomer. The smaller the amount of the organic solvent used, the smaller the reaction vessel, which is more economical. The post-treatment of the obtained reaction mixture can be performed in the same manner as the above method to obtain a thermally crosslinkable polysiloxane.

[0136] (Synthesis method 2: base catalyst)

[0137] In addition, the heat-crosslinkable polysiloxane (Sx) can be produced by subjecting one hydrolyzable monomer (Sm) or a mixture of two or more thereof to hydrolysis and condensation in the presence of a base catalyst. Examples of the base catalyst used in this case include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclocyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like. The amount of catalyst used is 1×10 -6 mol~10 mol, preferably 1×10 -5 mol to 5 mol, more preferably 1×10 -4 Mole~1 mole.

[0138] When obtaining the heat-crosslinkable polysiloxane from the above monomers by hydrolysis condensation, the amount of water added is preferably 0.1 to 50 mol per 1 mol of the hydrolyzable substituent bonded to the monomer. If it is 50 mol or less, the equipment used for the reaction is small and economical.

[0139] The operation method is to add monomers to the catalyst aqueous solution and start the hydrolysis condensation reaction. At this time, an organic solvent may be added to the catalyst aqueous solution, the monomers may be diluted with an organic solvent, or both may be performed. The reaction temperature is 0 to 100°C, preferably 5 to 80°C. It is preferably a method in which the temperature is maintained at 5 to 80°C during the dropwise addition of the monomers and then matured at 20 to 80°C.

[0140] The organic solvent that can be added to the aqueous base catalyst solution or the organic solvent that can dilute the monomer is preferably the same as the organic solvent exemplified as the organic solvent that can be added to the aqueous acid catalyst solution. In order to carry out the reaction economically, the amount of the organic solvent used is preferably 0 to 1,000 ml per 1 mol of the monomer.

[0141] 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 alkaline substance used for the catalyst. The acidic substance may be any substance as long as it is acidic in water.

[0142] Then, it is preferred to remove byproducts such as alcohol generated by the hydrolysis condensation reaction from the reaction mixture by reduced pressure removal. The temperature of the heating reaction mixture at this time depends on the type of alcohol produced by the added organic solvent and the reaction, but is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and further preferably 15 to 80 ° C. In addition, the degree of reduced pressure at this time depends on the type of organic solvent and alcohol to be removed, the exhaust device, the condensation concentration device and the heating temperature, preferably below atmospheric pressure, more preferably below 80 kPa by absolute pressure, and further preferably below 50 kPa by absolute pressure. It is not easy to correctly know the amount of alcohol removed at this time, but it is ideal to remove more than about 80% by mass of the generated alcohol.

[0143] Then, in order to remove the alkali catalyst used for the hydrolysis condensation, the heat-crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used at this time is preferably an organic solvent that can dissolve the heat-crosslinkable polysiloxane and separate into two layers when mixed with water. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0144] Furthermore, a mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent may also be used.

[0145] Specific examples of the organic solvent used in removing the base catalyst include the organic solvents specifically exemplified above as those used in removing the acid catalyst, or mixtures of the water-soluble organic solvent and the water-resistant organic solvent.

[0146] The mixing ratio of the water-soluble organic solvent to the poorly water-soluble organic solvent can be appropriately selected, and the water-soluble organic solvent is 0.1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, and more preferably 2 to 100 parts by mass based on 100 parts by mass of the poorly water-soluble organic solvent.

[0147] Then, wash with neutral water. The water may be deionized water or ultrapure water. The amount of water is 0.01 to 100 L, preferably 0.05 to 50 L, and more preferably 0.1 to 5 L relative to 1 L of the thermally crosslinkable polysiloxane solution. The washing method is to put the two into the same container, stir them, and then stand to separate the water layer. The number of washing times may be more than 1 time. Even if washing more than 10 times, the corresponding washing effect cannot be obtained, so it is preferably about 1 to 5 times.

[0148] The final solvent is added to the washed heat-crosslinkable polysiloxane solution, and solvent exchange is performed under reduced pressure to obtain the desired heat-crosslinkable polysiloxane solution. The temperature of the solvent exchange at this time depends on the type of extraction solvent to be removed, preferably 0 to 100°C, more preferably 10 to 90°C, and further preferably 15 to 80°C. In addition, the degree of decompression at this time varies depending on the type of extraction solvent to be removed, the exhaust device, the condensation concentration device, and the heating temperature, and is preferably below atmospheric pressure, more preferably below 80 kPa in absolute pressure, and further preferably below 50 kPa in absolute pressure.

[0149] The final solvent added to the thermally crosslinkable polysiloxane solution is preferably an alcohol solvent, and particularly preferably a monoalkyl ether of ethylene glycol, diethylene glycol, triethylene glycol, or the like, or a monoalkyl ether of propylene glycol, dipropylene glycol, or the like. 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, or the like are preferred.

[0150] In addition, another reaction operation using a base catalyst is to add water or a water-containing organic solvent to the monomer or the organic solution of the monomer and start the hydrolysis reaction. In this case, the catalyst can be added to the monomer or the organic solution of the monomer, or to water or a water-containing organic solvent. The reaction temperature is 0 to 100°C, preferably 10 to 80°C. It is preferably a method of heating to 10 to 50°C when water is added dropwise, and then heating to 20 to 80°C to mature it.

[0151] The organic solvent that can be used as an organic solution or an aqueous organic solvent for the monomer is preferably a water-soluble one, and examples thereof include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, 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 condensation product derivatives and mixtures thereof.

[0152] The molecular weight of the heat-crosslinkable polysiloxane obtained by the above-mentioned synthesis method 1 or 2 can be adjusted not only by the selection of monomers, but also by controlling the reaction conditions during polymerization. It is preferred to use a weight average molecular weight of 100,000 or less, more preferably 200 to 50,000, and further preferably 300 to 30,000. If the weight average molecular weight is 100,000 or less, there will be no foreign matter or uneven coating. In addition, the data related to the above weight average molecular weight is obtained by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an elution solvent, and polystyrene is used as a standard substance to express the molecular weight in terms of polystyrene.

[0153] The physical properties of the heat-crosslinkable polysiloxane used in the present invention vary depending on the type of acid or base catalyst used in the hydrolysis condensation and the reaction conditions, and therefore can be appropriately selected in accordance with the desired properties of the resist underlayer film.

[0154] Furthermore, a polysiloxane derivative produced by mixing one or more hydrolyzable monomers (Sm) with a hydrolyzable metal compound represented by the following general formula (Mm) using the above-mentioned acid or base catalyst can also be used as a component of the resist underlayer film forming composition.

[0155] [Chemistry 18]

[0156] U(OR 7 ) m7 (OR 8 ) m8 (Mm)

[0157] In the formula, R 7 , R 8 It is an organic group having 1 to 30 carbon atoms, m7+m8 is a number determined according to the type of U and having the same valence number, m7 and m8 are integers greater than 0, and U is an element of Group III, Group IV, or Group V of the periodic table, excluding carbon and silicon.

[0158] Examples of the hydrolyzable metal compound represented by the general formula (Mm) used in this case include the following.

[0159] When U is boron, examples of the compound represented by the general formula (Mm) include methoxyboron, ethoxyboron, propoxyboron, butoxyboron, pentylboron, hexylboron, cyclopentylboron, cyclohexylboron, allylboron, phenoxyboron, methoxyethoxyboron, boric acid, boron oxide, and the like as monomers.

[0160] When U is aluminum, examples of the compound represented by the general formula (Mm) include methoxyaluminum, ethoxyaluminum, propoxyaluminum, butoxyaluminum, pentoxyaluminum, hexoxyaluminum, cyclopentoxyaluminum, cyclohexyloxyaluminum, allyloxyaluminum, phenoxyaluminum, methoxyethoxyaluminum, ethoxyethoxyaluminum, dipropoxyethylacetoacetic aluminum, dibutoxyethylacetoacetic aluminum, propoxybisethylacetoacetic aluminum, butoxybisethylacetoacetic aluminum, 2,4-pentanedionate aluminum, 2,2,6,6-tetramethyl-3,5-heptanedione aluminum, and the like as monomers.

[0161] When U is gallium, the compound represented by the general formula (Mm) can be exemplified by methoxygallium, ethoxygallium, propoxygallium, butoxygallium, pentyloxygallium, hexyloxygallium, cyclopentyloxygallium, cyclohexyloxygallium, allyloxygallium, phenoxygallium, methoxyethoxygallium, ethoxyethoxygallium, dipropoxyethylacetoacetategallium, dibutoxyethylacetoacetategallium, propoxybisethylacetoacetategallium, butoxybisethylacetoacetategallium, 2,4-pentanedionegallium, 2,2,6,6-tetramethyl-3,5-heptanedionategallium, etc. as a monomer.

[0162] When U is yttrium, the compound represented by the general formula (Mm) can be exemplified by methoxy yttrium, ethoxy yttrium, propoxy yttrium, butoxy yttrium, pentyloxy yttrium, hexyloxy yttrium, cyclopentyloxy yttrium, cyclohexyloxy yttrium, allyloxy yttrium, phenoxy yttrium, methoxyethoxy yttrium, ethoxyethoxy yttrium, dipropoxyethyl acetoacetate yttrium, dibutoxyethyl acetoacetate yttrium, propoxybisethyl acetoacetate yttrium, butoxybisethyl acetoacetate yttrium, 2,4-pentanedione yttrium, 2,2,6,6-tetramethyl-3,5-heptanedione yttrium, etc. as a monomer.

[0163] When U is germanium, the compound represented by the general formula (Mm) can be exemplified by methoxygermanium, ethoxygermanium, propoxygermanium, butoxygermanium, pentyloxygermanium, hexyloxygermanium, cyclopentyloxygermanium, cyclohexyloxygermanium, allyloxygermanium, phenoxygermanium, methoxyethoxygermanium, ethoxyethoxygermanium, etc. as a monomer.

[0164] When U is titanium, the compound represented by the general formula (Mm) can be exemplified by methoxytitanium, ethoxytitanium, propoxytitanium, butoxytitanium, pentoxytitanium, hexoxytitanium, cyclopentyloxytitanium, cyclohexyloxytitanium, allyloxytitanium, phenoxytitanium, methoxyethoxytitanium, ethoxyethoxytitanium, dipropoxybisethylacetoacetate titanium, dibutoxybisethylacetoacetate titanium, dipropoxybis-2,4-pentanedionate titanium, dibutoxybis-2,4-pentanedionate titanium, etc. as a monomer.

[0165] When U is hafnium, the compound represented by the general formula (Mm) can be exemplified by methoxy hafnium, ethoxy hafnium, propoxy hafnium, butoxy hafnium, pentyloxy hafnium, hexyloxy hafnium, cyclopentyloxy hafnium, cyclohexyloxy hafnium, allyloxy hafnium, phenoxy hafnium, methoxyethoxy hafnium, ethoxyethoxy hafnium, dipropoxybisethylacetoacetate hafnium, dibutoxybisethylacetoacetate hafnium, dipropoxybis-2,4-pentanedione hafnium, dibutoxybis-2,4-pentanedione hafnium, and the like as a monomer.

[0166] When U is tin, examples of the compound represented by the general formula (Mm) include methoxytin, ethoxytin, propoxytin, butoxytin, phenoxytin, methoxyethoxytin, ethoxyethoxytin, 2,4-pentanedione tin, 2,2,6,6-tetramethyl-3,5-heptanedionate tin, and the like as monomers.

[0167] When U is arsenic, examples of the compound represented by the general formula (Mm) include methoxyarsenic, ethoxyarsenic, propoxyarsenic, butoxyarsenic, phenoxyarsenic and the like as a monomer.

[0168] When U is antimony, examples of the compound represented by the general formula (Mm) include methoxyantimony, ethoxyantimony, propoxyantimony, butoxyantimony, phenoxyantimony, antimony acetate, antimony propionate, and the like as a monomer.

[0169] When U is niobium, examples of the compound represented by the general formula (Mm) include niobium methoxide, niobium ethoxide, niobium propoxide, niobium butoxide, niobium phenoxide and the like as a monomer.

[0170] When U is tantalum, examples of the compound represented by the general formula (Mm) include tantalum methoxide, tantalum ethoxide, tantalum propoxide, tantalum butoxide, tantalum phenoxide, and the like as a monomer.

[0171] When U is bismuth, examples of the compound represented by the general formula (Mm) include bismuth methoxide, bismuth ethoxide, bismuth propoxide, bismuth butoxide, bismuth phenoxide, and the like as a monomer.

[0172] When U is phosphorus, examples of the compound represented by the general formula (Mm) include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, phosphorus pentoxide and the like as a monomer.

[0173] When U is vanadium, examples of the compound represented by the general formula (Mm) include bis(2,4-pentanedionato)vanadium oxide, 2,4-pentanedionatovanadium, tributoxyvanadium oxide, tripropoxyvanadium oxide, and the like as a monomer.

[0174] When U is zirconium, examples of the compound represented by the general formula (Mm) include methoxyzirconium, ethoxyzirconium, propoxyzirconium, butoxyzirconium, phenoxyzirconium, dibutoxyzirconium bis(2,4-pentanedione) and dipropoxyzirconium bis(2,2,6,6-tetramethyl-3,5-heptanedione).

[0175] (Acid Generator)

[0176] The silicon-containing resist underlayer film-forming composition of the present invention may further contain one or more acid generators. Any acid generator may be used as long as it is a substance that acts in the form of an acid precursor such as a thermal acid generator, a photoacid generator, or an acid proliferator. The acid generator contained in the present invention is more preferably a photoacid generator that generates acid as a sulfonium salt by the action of high-energy rays. More specifically, the materials described in paragraphs (0160) to (0179) of Japanese Patent Application Laid-Open No. 2009-126940 may be exemplified, but are not limited thereto.

[0177] [Other ingredients]

[0178] (Cross-linking catalyst (Xc))

[0179] The silicon-containing resist underlayer film-forming composition of the present invention may contain other crosslinking catalysts (Xc) in addition to the quaternary ammonium salt represented by the general formula (A-1). Examples of the crosslinking catalyst (Xc) that may be contained include compounds represented by the following general formula (Xc0).

[0180] L a H b A (Xc0)

[0181] In the formula, L is lithium, sodium, potassium, rubidium, cesium, sulfonium, iodonium, phosphonium or ammonium, A is a non-nucleophilic counter ion, a is an integer greater than 1, b is an integer greater than 0 or 1, and a+b is the valence of the non-nucleophilic counter ion.

[0182] As for specific (Xc0), the crosslinking catalyst (Xc) used in the present invention can be listed as the sulfonium salt of the following general formula (Xc-1), the iodonium salt of (Xc-2), the phosphonium salt of (Xc-3), the ammonium salt of (Xc-4), the alkali metal salt, etc.

[0183] Examples of the sulfonium salt (Xc-1), iodonium salt (Xc-2), and phosphonium salt (Xc-3) include the following.

[0184] [Chemistry 19]

[0185]

[0186] In addition, the ammonium salt (Xc-4) can be exemplified as follows.

[0187] [Chemistry 20]

[0188]

[0189] In the formula, R 204 , R 205 , R 206 , R 207They represent a linear, branched or cyclic alkyl, alkenyl, oxyalkyl or oxyalkenyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl or aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with alkoxy groups. 205 and R 206 It can also form a ring. When it forms a ring, R 205 , R 206 Each of them represents an alkylene group having 1 to 6 carbon atoms. - Represents a non-nucleophilic counterion. 208 , R 209 , R 210 , R 211 Yes and R 204 , R 205 , R 206 , R 207 Likewise, it can also be a hydrogen atom. 208 and R 209 , R 208 and R 209 and R 210 It can also form a ring. When it forms a ring, R 208 and R 209 and R 208 and R 209 and R 210 It represents an alkylene group having 3 to 10 carbon atoms.

[0190] The above R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211They may be the same or different from each other, and specifically include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl; cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl. Alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Oxoalkyl groups include 2-oxocyclopentyl and 2-oxocyclohexyl, and 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl. Examples of the aryl group include phenyl, naphthyl, or alkoxyphenyl such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butyloxyphenyl, and m-tert-butyloxyphenyl; alkylphenyl such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl; alkylnaphthyl such as methylnaphthyl and ethylnaphthyl; alkoxynaphthyl such as methoxynaphthyl and ethoxynaphthyl; dialkylnaphthyl such as dimethylnaphthyl and diethylnaphthyl; dialkoxynaphthyl such as dimethoxynaphthyl and diethoxynaphthyl. Examples of the aralkyl group include benzyl, phenylethyl, and phenethyl. Examples of the aryloxyalkyl group include 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, and 2-(2-naphthyl)-2-oxoethyl 2-aryl-2-oxoethyl.

[0191] A - Examples of the non-nucleophilic counter ions include hydroxide ions, formate ions, acetate ions, propionate ions, butyrate ions, valerate ions, hexanoate ions, heptanoate ions, octanoate ions, nonanoate ions, decanoate ions, oleate ions, stearate ions, linoleate ions, linolenate ions, benzoate ions, phthalate ions, isophthalate ions, terephthalate ions, salicylate ions, trifluoroacetate ions, monochloroacetate ions, dichloroacetate ions, trichloroacetate ions, fluoride ions, chloride ions, bromide ions, iodide ions, and nitrate ions. , nitrite ion, chlorate ion, bromate ion, methanesulfonate ion, p-toluenesulfonate ion, monomethyl sulfate ion and other 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, citrate ion, citrate ion, carbonate ion, sulfate ion and the like.

[0192] Examples of the alkali metal salt include lithium, sodium, potassium, cesium, magnesium, and calcium hydroxides, formates, acetates, propionates, butyrates, valerates, caproates, heptanoates, octanoates, nonanoates, decanoates, oleates, stearates, linolenates, linolenates, benzoates, phthalates, isophthalates, terephthalates, salicylates, trifluoroacetates, monochloroacetates, dichloroacetates, and trichloroacetates; and monovalent or divalent oxalates, malonates, methylmalonates, ethylmalonates, propylmalonates, butylmalonates, dimethylmalonates, diethylmalonates, succinates, methylsuccinates, glutarates, adipates, itaconates, maleates, fumarates, citrates, citrates, and carbonates.

[0193] Specific examples of the sulfonium salt (Xc-1) include triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionate, triphenylsulfonium butyrate, triphenylsulfonium benzoate, triphenylsulfonium phthalate, triphenylsulfonium isophthalate, triphenylsulfonium terephthalate, triphenylsulfonium salicylate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfon trifluoroacetate, triphenylsulfonium monochloroacetate, triphenylsulfonium dichloroacetate, triphenylsulfonium trichloroacetate, triphenylsulfonium hydroxide, triphenylsulfonium nitrate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium oxalate, triphenylsulfonium malonate, and triphenylsulfonium methylmalonate. triphenylsulfonium oxalate, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylsulfonium citrate, triphenylsulfonium citrate, triphenylsulfonium carbonate, bistriphenylsulfonium oxalate, bistriphenylsulfonium maleate, bistriphenylsulfonium fumarate, bistriphenylsulfonium citrate, bistriphenylsulfonium carbonate, and the like.

[0194] In addition, the iodonium salt (Xc-2) specifically includes 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, hydrogen diphenyliodonium oxide, diphenyliodonium nitrate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide, diphenyliodonium oxalate, diphenyliodonium maleate, diphenyliodonium fumarate, diphenyliodonium citrate, diphenyliodonium citrate, diphenyliodonium carbonate, bisdiphenyliodonium oxalate, bisdiphenyliodonium maleate, bisdiphenyliodonium fumarate, bisdiphenyliodonium citrate, bisdiphenyliodonium citrate, bisdiphenyliodonium carbonate, and the like.

[0195] In addition, the phosphonium salt (Xc-3) specifically includes tetraethylphosphonium formate, tetraethylphosphonium acetate, tetraethylphosphonium propionate, tetraethylphosphonium butyrate, tetraethylphosphonium benzoate, tetraethylphosphonium phthalate, tetraethylphosphonium isophthalate, tetraethylphosphonium terephthalate, tetraethylphosphonium salicylate, tetraethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoroacetate, tetraethylphosphonium monochloroacetate, tetraethylphosphonium dichloroacetate, tetraethylphosphonium tri ...fluoromethanesulfonate, tetraethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium tri Tetraethylphosphonium acetate, tetraethylphosphonium hydroxide, tetraethylphosphonium nitrate, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetraethylphosphonium oxalate, tetraethylphosphonium maleate, tetraethylphosphonium fumarate, tetraethylphosphonium citrate, tetraethylphosphonium citrate, tetraethylphosphonium carbonate, bis-tetraethylphosphonium oxalate, bis-tetraethylphosphonium maleate, bis-tetraethylphosphonium fumarate, bis-tetraethylphosphonium citrate, bis-tetraethylphosphonium citrate , 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 monochloroacetate, tetraphenylphosphonium dichloroacetate, tetraphenylphosphonium trichloroacetate, tetraphenylphosphonium hydroxide Tetraphenylphosphonium, tetraphenylphosphonium nitrate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium oxalate, tetraphenylphosphonium maleate, tetraphenylphosphonium fumarate, tetraphenylphosphonium citrate, tetraphenylphosphonium citrate, tetraphenylphosphonium carbonate, bis(tetraphenylphosphonium oxalate), bis(tetraphenylphosphonium maleate), bis(tetraphenylphosphonium fumarate), bis(tetraphenylphosphonium citrate), bis(tetraphenylphosphonium carbonate), and the like.

[0196] On the other hand, the ammonium salt (Xc-4) specifically includes tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetramethylammonium phthalate, tetramethylammonium isophthalate, tetramethylammonium terephthalate, tetramethylammonium salicylate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium monochloroacetate, tetramethylammonium dichloroacetate, tetramethylammonium trichloroacetate, tetramethylammonium hydroxide, tetramethylammonium nitrate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium monomethylsulfate, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium maleate, tetramethylammonium fumarate, tetramethylammonium citrate, tetramethylammonium carbonate, tetramethylammonium bis(tetramethylammonium oxalate), tetramethylammonium propionate, tetramethylammonium oxalate, tetramethylammonium bis(tetramethylammonium oxalate), ... Ditetramethylammonium diacid, ditetramethylammonium maleate, ditetramethylammonium fumarate, ditetramethylammonium citrate, ditetramethylammonium carbonate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetraethylammonium phthalate, tetraethylammonium isophthalate, tetraethylammonium terephthalate, tetraethylammonium salicylate, tetraethylammonium trifluoromethanesulfonate, tetraethylammonium trifluoroacetate, tetraethylammonium monochloroacetate, tetraethylammonium dichloroacetate, tetraethylammonium trichloroacetate, tetraethylammonium hydroxide, tetraethylammonium nitrate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium monomethyl sulfate, tetraethylammonium oxalate, tetraethylammonium malonate, tetraethylammonium maleate, tetraethylammonium fumarate, citrate Tetraethylammonium conate, tetraethylammonium citrate, tetraethylammonium carbonate, ditetraethylammonium oxalate, ditetraethylammonium malonate, ditetraethylammonium maleate, ditetraethylammonium fumarate, ditetraethylammonium citrate, ditetraethylammonium citrate, ditetraethylammonium carbonate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, tetrapropylammonium dichloroacetate, tetrapropylammonium trichloroacetate, tetrapropylammonium hydroxide, tetrapropylammonium nitrate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrapropylammonium monomethyl sulfate, Tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium maleate, tetrapropylammonium fumarate, tetrapropylammonium citrate, tetrapropylammonium citrate, tetrapropylammonium carbonate, ditetrapropylammonium oxalate, ditetrapropylammonium malonate, ditetrapropylammonium maleate, ditetrapropylammonium fumarate, ditetrapropylammonium citrate, ditetrapropylammonium citrate, ditetrapropylammonium carbonate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, tetrabutylammonium benzoate, tetrabutylammonium phthalate, tetrabutylammonium isophthalate, tetrabutylammonium terephthalate, tetrabutylammonium salicylate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluoroacetate, tetrabutylammonium monochloroacetate, tetrabutylammonium dichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, tetrabutylammonium nitrate,Tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium methanesulfonate, tetrabutylammonium monomethyl sulfate, tetrabutylammonium oxalate, tetrabutylammonium malonate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citrate, tetrabutylammonium citrate, tetrabutylammonium carbonate, ditetrabutylammonium oxalate, ditetrabutylammonium malonate, ditetrabutylammonium maleate, ditetrabutylammonium fumarate, ditetrabutylammonium citrate, ditetrabutylammonium citrate, ditetrabutylammonium carbonate, etc.

[0197] Examples of the alkali metal salt include lithium formate, lithium acetate, lithium propionate, lithium butyrate, lithium benzoate, lithium phthalate, lithium isophthalate, lithium terephthalate, lithium salicylate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium monochloroacetate, lithium dichloroacetate, lithium trichloroacetate, lithium hydroxide, lithium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium methanesulfonate, lithium hydrogen oxalate, lithium hydrogen malonate, lithium hydrogen maleate, lithium hydrogen fumarate, Lithium hydrogen citrate, lithium hydrogen citrate, lithium bicarbonate, lithium oxalate, lithium malonate, lithium maleate, lithium fumarate, lithium citrate, lithium citrate, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butyrate, sodium benzoate, sodium phthalate, sodium isophthalate, sodium terephthalate, sodium salicylate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, sodium dichloroacetate, sodium trichloroacetate, sodium hydroxide, nitric acid Sodium, Sodium Chloride, Sodium Bromide, Sodium Iodide, Sodium Methanesulfonate, Sodium Oxalate, Sodium Malonate, Sodium Maleate, Sodium Fumarate, Sodium Citrate, Sodium Citrate, Sodium Bicarbonate, Sodium Oxalate, Sodium Malonate, Sodium Maleate, Sodium Fumarate, Sodium Citrate, Sodium Citrate, Sodium Carbonate, Potassium Formate, Potassium Acetate, Potassium Propionate, Potassium Butyrate, Potassium Benzoate, Potassium Phthalate, Potassium Isophthalate, Potassium Terephthalate, Water Potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, potassium trichloroacetate, potassium hydroxide, potassium nitrate, potassium chloride, potassium bromide, potassium iodide, potassium methanesulfonate, potassium hydrogen oxalate, potassium hydrogen malonate, potassium hydrogen maleate, potassium hydrogen fumarate, potassium hydrogen citrate, potassium hydrogen citrate, potassium bicarbonate, potassium oxalate, potassium malonate, potassium maleate, potassium fumarate, potassium citrate, potassium citrate, potassium carbonate, etc.

[0198] In the present invention, a polysiloxane (Xc-10) containing an ammonium salt, a sulfonium salt, a phosphonium salt or an iodonium salt as a part of the structure may be formulated in the resist underlayer film-forming composition as the crosslinking catalyst (Xc).

[0199] As the raw material for producing (Xc-10) used here, a compound represented by the following general formula (Xm) can be used.

[0200] R 1A A1 R 2A A2 R 3A A3 Si(OR0A ) (4-A1-A2-A3) (Xm)

[0201] In the formula, R 0A is a hydrocarbon group having 1 to 6 carbon atoms, R 1A , R 2A , 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 others are hydrogen atoms or monovalent organic groups having a carbon number of 1 to 30. A1, A2, and A3 are 0 or 1, and 1≤A1+A2+A3≤3.

[0202] Here, R 0A Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl and phenyl.

[0203] Xm can be exemplified by a compound represented by the following general formula (Xm-1), which is a hydrolyzable silicon compound having a sulfonium salt as a part of the structure.

[0204] [Chemistry 21]

[0205]

[0206] In the formula, R SA1 , R SA2 Each of them represents a linear, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl or aryloxyalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with a monovalent organic group such as an alkoxy group, an amino group, an alkylamino group, a halogen atom, etc. SA1 and R SA2 They can also form a ring with the sulfur atom to which they are bonded. When forming a ring, R SA1 , R SA2 Each of R represents an alkylene group having 1 to 6 carbon atoms. SA3 It is a linear, branched or cyclic alkylene group or alkenylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group or aralkylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with a divalent organic group such as an alkoxy group, an amino group or an alkylamino group. SA1 ~R SA3 It may have an oxygen atom or a nitrogen atom in the middle of the chain or ring.

[0207] In the above general formula (Xm-1), (Si) is described to indicate the bonding position with Si.

[0208] X -Examples thereof include hydroxide ions, fluoride ions, chloride ions, bromide ions, iodide ions, formate ions, acetate ions, propionate ions, butyrate ions, valerate ions, caproate ions, heptanoate ions, octanoate ions, nonanoate ions, decanoate ions, oleate ions, stearate ions, linoleate ions, linolenate ions, benzoate ions, p-toluate ions, p-tert-butylbenzoate ions, phthalate ions, isophthalate ions, terephthalate ions, salicylate ions, trifluoroacetate ions, monochloroacetate ions, dichloroacetate ions, trichloroacetate ions, 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, citrate ion, citrate ion, carbonate ion, etc.

[0209] Specific examples of the cation part of the compound represented by the general formula (Xm-1) include the following ions.

[0210] [Chemistry 22]

[0211]

[0212] For example, the hydrolyzable silicon compound having an iodonium salt as a part of the structure can be exemplified by the following general formula (Xm-2).

[0213] [Chemistry 23]

[0214]

[0215] In the formula, R IA1 It represents a linear, branched or cyclic alkyl, alkenyl, oxyalkyl or oxyalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an aralkyl or aryloxyalkyl group having 7 to 20 carbon atoms, and a part or all of the hydrogen atoms in these groups may be substituted with a monovalent organic group such as an alkoxy group, an amino group, an alkylamino group, a halogen atom, etc. IA2 It is a linear, branched or cyclic alkylene group or alkenylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group or aralkylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with a divalent organic group such as an alkoxy group, an amino group or an alkylamino group. IA1 , R IA2 It may have an oxygen atom or a nitrogen atom in the middle of the chain or ring.

[0216] In the above general formula (Xm-2), (Si) is described to indicate the bonding position with Si. - Same as above.

[0217] Specific examples of the cation part of the compound represented by the general formula (Xm-2) include the following ions.

[0218] [Chemistry 24]

[0219]

[0220] For example, the hydrolyzable silicon compound having a phosphonium salt as a part of the structure can be exemplified by the following general formula (Xm-3).

[0221] [Chemistry 25]

[0222]

[0223] In the formula, R PA1 , R PA2 , R PA3 They represent a linear, branched or cyclic alkyl, alkenyl, oxyalkyl or oxyalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an aralkyl or aryloxyalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, etc. In addition, R PA1 and R PA2 They can also form a ring with the phosphorus atom to which they are bonded. When a ring is formed, R PA1 , R PA2 Each of R represents an alkylene group having 1 to 6 carbon atoms. PA4 It is a linear, branched or cyclic alkylene group, alkenylene group, substituted or unsubstituted arylene group or aralkylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with alkoxy, amino, alkylamino, etc. PA1 ~R PA4 It may have an oxygen atom or a nitrogen atom in the middle of the chain or ring.

[0224] In the above general formula (Xm-3), (Si) is described to indicate the bonding position with Si. - Same as above.

[0225] Specific examples of the cation part of the compound represented by the general formula (Xm-3) include the following ions.

[0226] [Chemistry 26]

[0227]

[0228] [Chemistry 27]

[0229]

[0230] For example, the hydrolyzable silicon compound having an ammonium salt as a part of the structure can be exemplified by the following general formula (Xm-4).

[0231] [Chemistry 28]

[0232]

[0233] In the formula, R NA1 , R NA2 , R NA3 Each of them represents hydrogen, a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an aralkyl group or an aryloxyalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with a monovalent organic group such as an alkoxy group, an amino group, or an alkylamino group. In addition, R NA1 and R NA2 They can also form a ring with the nitrogen atom to which they are bonded. When forming a ring, R NA1 , R NA2 R represents an alkylene group having 1 to 6 carbon atoms or a nitrogen-containing cyclic heterocyclic ring or heteroaromatic ring. NA4 is a linear, branched or cyclic alkylene group, alkenylene group, substituted or unsubstituted arylene group or aralkylene group having 6 to 29 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with a divalent organic group such as an alkoxy group, an amino group, or an alkylamino group, R NA1 and R NA2 , R NA1 and R NA4 When a ring structure is formed and contains unsaturated nitrogen NA3 =0, except that n NA3 =1. NA4 It may have an oxygen atom or a nitrogen atom in the middle of the chain or ring.

[0234] In the above general formula (Xm-4), (Si) is described to indicate the bonding position with Si. - Same as above.

[0235] Specific examples of the cation part of the compound represented by the general formula (Xm-4) include the following ions.

[0236] [Chemistry 29]

[0237]

[0238] [Chemistry 30]

[0239]

[0240] [Chemistry 31]

[0241]

[0242] [Chemistry 32]

[0243]

[0244] [Chemistry 33]

[0245]

[0246] [Chemistry 34]

[0247]

[0248] [Chemistry 35]

[0249]

[0250] [Chemistry 36]

[0251]

[0252] [Chemistry 37]

[0253]

[0254] [Chemistry 38]

[0255]

[0256] [Chemistry 39]

[0257]

[0258] [Chemistry 40]

[0259]

[0260] [Chemistry 41]

[0261]

[0262] The hydrolyzable silicon compound used together with the above-mentioned (Xm-1), (Xm-2), (Xm-3) and (Xm-4) for producing (Xc-10) can be exemplified by the above-mentioned hydrolyzable monomer (Sm). A hydrolyzable metal compound (Mm) represented by the above-mentioned general formula (Mm) can also be added.

[0263] Thus, one or more of the monomers (Xm-1), (Xm-2), (Xm-3), and (Xm-4) exemplified and one or more of (Sm), and if necessary, one or more of (Mm), can be selected and mixed before or during the reaction to prepare the reaction raw materials for forming (Xc-10). The reaction conditions can be the same as the method for synthesizing the thermally crosslinkable polysiloxane (Sx).

[0264] The molecular weight of the obtained silicon-containing compound (Xc-10) can be adjusted not only by the selection of monomers, but also by controlling the reaction conditions during polymerization. It is preferred to use a weight average molecular weight of 100,000 or less, more preferably 200 to 50,000, and further preferably 300 to 30,000. If the weight average molecular weight is 100,000 or less, there will be no foreign matter or uneven coating. In addition, the data related to the above weight average molecular weight are obtained by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an elution solvent, and polystyrene is used as a standard substance to express the molecular weight in terms of polystyrene.

[0265] In addition, the above-mentioned crosslinking catalysts (Xc-1), (Xc-2), (Xc-3), (Xc-4), and (Xc-10) can be used alone or in combination of two or more. The amount of the crosslinking catalyst added is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, expressed as the total amount of the crosslinking catalyst and the quaternary ammonium salt represented by the general formula (A-1), relative to 100 parts by mass of the base polymer (the silicon-containing compound (Sx) obtained by the above method).

[0266] (Organic Acid)

[0267] In order to improve the stability of the silicon-containing resist underlayer film-forming composition of the present invention, it is preferable to add a monovalent or divalent organic acid having a carbon number of 1 to 30. Examples of the acid to be added include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, oleic acid, stearic acid, linolenic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and citric acid. Oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, and citric acid are particularly preferred. Furthermore, in order to maintain stability, two or more acids may be used in combination.

[0268] The amount of the organic acid added is 0.001 to 25 parts by mass, preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of silicon contained in the silicon-containing resist underlayer film-forming composition of the present invention.

[0269] Alternatively, the organic acid may be formulated so that the pH of the silicon-containing resist underlayer film-forming composition of the present invention becomes 0≤pH≤7, more preferably 0.3≤pH≤6.5, and even more preferably 0.5≤pH≤6.

[0270] (water)

[0271] In the present invention, water may also be added to the composition. If water is added, the polysiloxane compound in the silicon-containing resist underlayer film-forming composition of the present invention will be hydrated, so the photolithography performance will be improved. The content of water in the solvent component of the silicon-containing resist underlayer film-forming composition of the present invention exceeds 0% by mass and is less than 50% by mass, and is particularly preferably 0.3 to 30% by mass, and more preferably 0.5 to 20% by mass. If the amount of water added is within the above range, the uniformity of the silicon-containing resist underlayer film is good, there is no concern about the generation of shrinkage cavities, and there is no concern about the reduction of photolithography performance.

[0272] The total amount of the solvent including water used is 100 to 100,000 parts by mass, particularly preferably 200 to 50,000 parts by mass, based on 100 parts by mass of the polysiloxane compound (Sx) which is the base polymer.

[0273] (Stabilizer)

[0274] In addition, the present invention may add a stabilizer to the composition. The stabilizer may be a monovalent or divalent alcohol having a cyclic ether as a substituent. In particular, if a stabilizer described in paragraphs (0181) to (0182) of Japanese Patent Application Publication No. 2009-126940 is added, the stability of the silicon-containing resist underlayer film forming composition can be improved.

[0275] (Surfactant)

[0276] In addition, the present invention may contain a surfactant in the composition as needed. Specifically, such a surfactant may be a material described in paragraph (0185) of JP-A-2009-126940.

[0277] (High boiling point solvent)

[0278] In addition, the present invention can also add a high boiling point solvent with a boiling point of 180 degrees or more to the composition as needed. Examples of the high boiling point solvent include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, γ-butyrolactone ... Glycol monomethyl ether, diacetone alcohol, n-nonyl acetate, ethylene glycol monoethyl acetate, 1,2-diacetoxyethane, 1-acetoxy-2-methoxyethane, 1,2-diacetoxypropane, diethylene glycol monomethyl acetate, diethylene glycol monoethyl acetate, diethylene glycol mono-n-butyl acetate, propylene glycol monomethyl acetate, propylene glycol monopropyl acetate, propylene glycol monobutyl acetate, dipropylene glycol monomethyl acetate, dipropylene glycol monoethyl acetate, etc.

[0279] [Pattern Formation Method]

[0280] A pattern forming method among the pattern forming methods of the present invention (the so-called "multilayer resist method") is characterized in that it includes the following steps: forming an organic film on a workpiece using a coating type organic film material, forming a silicon-containing resist underlayer film on the above-mentioned organic film using the above-mentioned silicon-containing resist underlayer film forming composition of the present invention, forming a resist upper layer film using a resist upper layer film composition composed of a photoresist composition on the above-mentioned silicon-containing resist underlayer film, forming a circuit pattern on the above-mentioned resist upper layer film, using the above-mentioned resist upper layer film with the circuit pattern formed as a mask and transferring the pattern to the above-mentioned silicon-containing resist underlayer film by etching, using the above-mentioned silicon-containing resist underlayer film with the pattern transferred as a mask and transferring the pattern to the organic film by etching, and using the above-mentioned organic film with the pattern transferred as a mask and transferring the pattern to the above-mentioned workpiece by etching.

[0281] Another pattern forming method of the pattern forming method of the present invention (the so-called "multilayer resist method") is characterized in that it includes the following steps: forming a hard mask with carbon as the main component on the workpiece by using the CVD method, forming a silicon-containing resist underlayer film using the silicon-containing resist underlayer film forming composition of the present invention on the above-mentioned hard mask, forming a resist upper film using a resist upper film composition composed of a photoresist composition on the above-mentioned silicon-containing resist underlayer film, forming a circuit pattern on the above-mentioned resist upper film, using the above-mentioned resist upper film with the circuit pattern formed as a mask and transferring the pattern to the above-mentioned silicon-containing resist underlayer film by etching, using the above-mentioned silicon-containing resist underlayer film with the pattern transferred as a mask and transferring the pattern to the above-mentioned hard mask by dry etching, and using the above-mentioned hard mask with the pattern transferred as a mask and transferring the pattern to the above-mentioned workpiece by dry etching.

[0282] When the silicon-containing resist underlayer film-forming composition of the present invention is used to form a pattern, by optimizing the combination of the hard mask and the organic film as described above, an ultrafine pattern formed by the photoresist can be formed on a substrate in a manner that suppresses pattern collapse and has a good shape. In addition, the silicon-containing resist underlayer film remaining after pattern formation can be easily removed by etching, etc., so that residues that cause defects can be suppressed, and damage to the substrate caused by excessive etching conditions can be prevented.

[0283] Thus, the pattern forming method of the present invention can suppress the pattern collapse of the resist upper film and form a good pattern shape. In addition, the pattern transfer to the silicon-containing resist lower film by dry etching is excellent, and the silicon-containing resist lower film remaining after patterning is easily removed, and defects caused by residues are not easily generated, so it is a practical pattern forming method especially for the formation of fine patterns.

[0284] In addition, in the positive patterning method, after the photoresist film is formed and heated, exposure is performed, and alkali development is usually performed using an alkali developer to obtain a positive resist pattern. In addition, after exposure, post-exposure baking (PEB) is preferably performed.

[0285] As the alkaline developer, a tetramethylammonium hydroxide (TMAH) aqueous solution or the like can be used.

[0286] The patterning in the step of forming a circuit pattern on the resist upper film is preferably performed by optical lithography with a wavelength of 10 nm to 300 nm, direct writing using an electron beam, nanoimprinting, or a combination thereof.

[0287] The object to be processed is preferably a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film or a metal oxide nitride film.

[0288] When the above-mentioned workpiece is in this state, the effect of the present invention is more fully exerted.

[0289] The metal constituting the above-mentioned processed body is preferably silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt or an alloy thereof.

[0290] When the metal constituting the above-mentioned object to be processed is the above-mentioned specific metal, the effect of the present invention is more fully exerted.

[0291] [Example]

[0292] Hereinafter, the present invention will be specifically described with reference to synthesis examples, embodiments and comparative examples, but the present invention is not limited to these descriptions. In addition, in the following examples, % represents mass %, and molecular weight Mw is a weight average molecular weight obtained by GPC measurement and calculated as polystyrene.

[0293] [Synthesis example 1]

[0294] A mixture of 30.6 g of compound (101), 38.1 g of compound (102) and 5.9 g of compound (110) was added to a mixture of 120 g of methanol, 0.1 g of 10% nitric acid and 60 g of deionized water, and the mixture was kept at 40°C for 12 hours to allow hydrolysis and condensation to proceed. After the reaction was completed, 600 g of propylene glycol ethyl ether (PGEE) was added, and the water and by-product alcohol used for hydrolysis and condensation were distilled off under reduced pressure to obtain 440 g of a PGEE solution of polysiloxane compound 1 (compound concentration 10%). The molecular weight of polysiloxane compound 1 was measured as Mw = 2,900 in terms of polystyrene.

[0295] [Synthesis Examples 2 to 16]

[0296] [Synthesis Example 2] to [Synthesis Example 16] were carried out under the same conditions as in Synthesis Example 1 using the monomers shown in Table 1 to obtain the target products.

[0297] [Table 1]

[0298]

[0299]

[0300] The compounds used in Examples and Comparative Examples are shown below.

[0301] PhSi(OCH3)3…Compound (100)

[0302] CH3Si(OCH3)3…Compound (101)

[0303] Si(OCH3)4…Compounds (102)

[0304] [Chemistry 42]

[0305]

[0306] [Synthesis Example of Cross-linking Catalyst]

[0307] A mixture of 61.3 g of compound (101) and 12.9 g of compound (117) was added to a mixture of 120 g of methanol, 0.1 g of 10% nitric acid and 60 g of deionized water, and the mixture was kept at 40°C for 12 hours to allow hydrolysis and condensation to proceed. After the reaction, 300 g of propylene glycol ethyl ether (PGEE) was added, and the water and by-product alcohol used for hydrolysis and condensation were distilled off under reduced pressure to obtain 250 g of a PGEE solution of polysiloxane compound 17 containing an ammonium salt (compound concentration 20%). The molecular weight of polysiloxane compound 17 in terms of polystyrene was measured to be Mw=1,500.

[0308] [Examples, Comparative Examples]

[0309] The polysiloxane compounds 1 to 16 obtained in the above synthesis examples, the quaternary ammonium salt represented by the above general formula (A-1) as a crosslinking catalyst or a crosslinking catalyst as a comparison, a photoacid generator (PAG-1 to 7 described in Table 7), an acid, a solvent, and water were mixed in the proportions shown in Tables 2 to 6, and filtered using a 0.1 μm fluororesin filter to prepare silicon-containing lower film-forming composition solutions, which are solutions 1 to 96 respectively.

[0310] [Table 2]

[0311]

[0312]

[0313]

[0314] [Table 3]

[0315]

[0316]

[0317] [Table 4]

[0318]

[0319]

[0320]

[0321] [Table 5]

[0322]

[0323]

[0324]

[0325] [Table 6]

[0326]

[0327] The cross-linking catalyst used is as follows.

[0328] XL-1…Trimethylphenylammonium hydroxide

[0329] XL-2…Trimethylphenylammonium nitrate

[0330] XL-3…Triethylphenylammonium iodide

[0331] XL-4…Benzyldimethylphenylammonium chloride

[0332] XL-5…Dimethyldiphenylammonium chloride

[0333] XL-6…3-(Trifluoromethyl)phenyltrimethylammonium hydroxide

[0334] XL-7~17…refer to the following formula

[0335] XL-18…Tetramethylammonium nitrate

[0336] XL-19…Tetraoctylammonium nitrate

[0337] XL-20…Trimethylsulfonium iodide

[0338] XL-21··Polysiloxane compound containing ammonium salt 17

[0339] [Chemistry 43]

[0340]

[0341] The solvents used are as follows.

[0342] PGEE…Propylene glycol ethyl ether

[0343] PGME…Propylene glycol methyl ether

[0344] GBL...γ-Butyrolactone

[0345] DAA…Diacetone alcohol

[0346] [Table 7]

[0347]

[0348] (EUV patterning test)

[0349] On a silicon wafer, silicon-containing resist underlayer film forming composition solutions 1 to 96 were spin-coated on a silicon substrate and heated at 220° C. for 60 seconds to obtain silicon-containing films 1 to 96 (polysiloxane resist underlayer films) having a film thickness of 25 nm.

[0350] Then, a resist material prepared by dissolving the following components in the ratio of Table 8 was spin-coated on films 1 to 96, and pre-baked at 105° C. for 60 seconds using a hot plate to obtain a resist film with a film thickness of 35 nm. It was exposed using an EUV scanning exposure machine NXE3300 manufactured by ASML (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, L / S pattern with a size of 36 nm pitch on the wafer), and PEB was performed on a hot plate at 100° C. for 60 seconds, and then developed with a 2.38 mass % TMAH aqueous solution for 30 seconds to obtain a line pattern with a size of 18 nm.

[0351] The line size was measured using a length-measuring SEM (CG5000) manufactured by Hitachi High-Technologies Co., Ltd., and was evaluated as good when no pattern collapse was observed at a line width of 15 nm, and was evaluated as poor when pattern collapse was observed. In addition, the cross-sectional shape was observed using an electron microscope (S-4800) manufactured by Hitachi High-Technologies Co., Ltd., and was evaluated as good when no tailing shape was observed, and was evaluated as poor when a clear tailing shape was observed.

[0352] The polymer, quencher, sensitizer, surfactant and organic solvent used are as follows.

[0353] [Chemistry 44]

[0354]

[0355] [Chemistry 45]

[0356]

[0357] Surfactant: FC-4430 manufactured by 3M

[0358] PGMEA: Propylene glycol monomethyl ether acetate

[0359] CyHO: Cyclohexanone

[0360] PGME: Propylene glycol monomethyl ether

[0361] [Table 8]

[0362]

[0363] (Coating film etching test)

[0364] The resist underlayer film forming composition solutions 1 to 96 containing silicon were spin-coated on a silicon wafer and heated at 220° C. for 60 seconds to form silicon-containing films 1 to 96 having a film thickness of 25 nm on a silicon substrate.

[0365] These films were subjected to etching tests under the following etching conditions.

[0366] If the dry etching rate is 44 nm / min or more under the following conditions, it can be said that the etching rate is sufficient.

[0367] Etching test using CHF3 / CF4 gas

[0368] Equipment: Telius SP dry etching equipment manufactured by Tokyo Electron Co., Ltd.

[0369] Etching test:

[0370]

[0371] The results of the above tests are shown in Tables 9 to 11.

[0372] [Table 9]

[0373]

[0374]

[0375]

[0376] [Table 10]

[0377]

[0378]

[0379]

[0380] [Table 11]

[0381]

[0382] As shown in Tables 9 to 11, in Examples 1-1 to 1-92 using the quaternary ammonium salt (XL-1 to XL-17) represented by the above-mentioned general formula (A-1) of the present invention as a crosslinking catalyst, the effect of suppressing pattern collapse and good pattern shape were observed, and it was confirmed that there was a sufficient etching rate.

[0383] On the other hand, in Comparative Examples 1-1, 1-3, and 1-4, which used salts (XL-18 to XL-21) different from the quaternary ammonium salt represented by the general formula (A-1) as crosslinking catalysts, pattern collapse was observed at a line width of 15 nm, and in Comparative Examples 1-2, 1-3, and 1-4, a clear tailing shape was observed. In addition, in Comparative Examples 1-2 and 1-4, it was confirmed that the etching rate was insufficient.

[0384] It was confirmed that the quaternary ammonium salts (XL-1 to XL-17) represented by the general formula (A-1) of the present invention, when used as a crosslinking catalyst, have a superior effect of suppressing pattern collapse and a good pattern forming effect as compared to the prior art, and have a sufficient etching rate.

[0385] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same configuration and exhibiting the same functions and effects as the technical concept described in the claims of the present invention are intended to be included in the technical scope of the present invention.

Claims

1. A silicon-containing resist underlayer film-forming composition, characterized in that At least Contains: one or more quaternary ammonium salts represented by the following formula, and Thermally cross-linkable polysiloxane (Sx); 2. The silicon-containing resist underlayer film-forming composition according to claim 1, wherein The heat-crosslinkable polysiloxane (Sx) contains at least one 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); In the formula, R 1 , R 2 , R 3 They are respectively monovalent organic groups having 1 to 30 carbon atoms and may be the same or different. 3 . The silicon-containing resist underlayer film forming composition according to claim 1 , further comprising an acid generator.

4. The silicon-containing resist underlayer film-forming composition according to claim 3, wherein The acid generator is a sulfonium salt and is a photoacid generator that generates an acid by the action of high-energy rays.

5. A pattern forming method, characterized by comprising the following steps: The organic film is formed on the workpiece using a coating type organic film material. forming a silicon-containing resist underlayer film on the organic film using the silicon-containing resist underlayer film-forming composition according to any one of claims 1 to 4, forming a resist upper layer film on the resist lower layer film containing silicon using a resist upper layer film composition composed of a photoresist composition, forming a circuit pattern on the resist upper film, Using the resist upper layer film having the circuit pattern formed thereon as a mask and transferring the pattern to the resist lower layer film containing silicon by etching, Transferring the pattern to the organic film by etching using the silicon-containing resist underlayer film having the transferred pattern as a mask, and The pattern is transferred to the object to be processed by etching using the organic film to which the pattern is transferred as a mask.

6. A pattern forming method, characterized by comprising the following steps: A hard mask mainly composed of carbon is formed on the workpiece by CVD. forming a resist underlayer film containing silicon on the hard mask using the resist underlayer film forming composition containing silicon according to any one of claims 1 to 4, forming a resist upper layer film on the resist lower layer film containing silicon using a resist upper layer film composition composed of a photoresist composition, forming a circuit pattern on the resist upper film, Using the resist upper layer film having the circuit pattern formed thereon as a mask and transferring the pattern to the resist lower layer film containing silicon by etching, Using the silicon-containing resist underlayer film having the transferred pattern as a mask, the hard mask is subjected to pattern transfer by dry etching, and The pattern is transferred to the workpiece by dry etching using the hard mask to which the pattern is transferred as a mask.

7. The pattern forming method according to claim 5 or 6, wherein: The pattern formation in the step of forming a circuit pattern on the resist upper layer film is pattern formation using optical lithography with a wavelength of 10 nm to 300 nm, direct writing using an electron beam, nanoimprinting, or a combination thereof.

8. The pattern forming method according to claim 5 or 6, wherein: The object to be processed is a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film or a metal oxide nitride film.

9. The pattern forming method according to claim 5 or 6, wherein: The metal constituting the processed object is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt or an alloy thereof.

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