Polyvalent ammonium salt compound, composition for forming silicon-containing resist underlayer film, and patterning method

Abstract

To provide a composition for forming a silicon-containing resist underlayer film capable of forming a silicon-containing resist underlayer film that has an appropriate etching rate and can improve LWR and CDU in an ultra-fine pattern in a multilayer resist method, a polyvalent ammonium salt compound contained in the composition, and a patterning method using the composition.SOLUTION: A polyvalent ammonium salt compound has two or more ammonium ions per molecule, the polyvalent ammonium salt compound being represented by the following general formula (A-1).SELECTED DRAWING: None

Description

[Technical Field]

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

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

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

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

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

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

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

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

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

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

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

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

[0013] The present invention has been made to solve the above-mentioned problems, and provides a polyvalent ammonium salt compound having two or more ammonium ions in one molecule, characterized in that the polyvalent ammonium salt compound is represented by the following general formula (A-1): [ka] (In the formula, R1 is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and may contain one or more nitrogen atoms; R2, R3, R4, R5, R6, and R7 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and may contain one or more nitrogen atoms. In addition, any two or more selected from R1, R2, R3, R4, R5, R6, and R7 may bond to each other to form a ring together with the nitrogen atom in the formula. A - represents an organic or inorganic anion that serves as a counter ion of the ammonium cation, excluding bistrifluoromethanesulfonylimide; and n is an integer of 2 to 10.

[0014] When such a polyvalent ammonium salt compound is added to a composition for forming a silicon-containing resist underlayer film, it functions as a curing catalyst and can promote its thermal curing. Furthermore, since the compound of the present invention is polyvalent, when added to a composition for forming a silicon-containing resist underlayer film, it exhibits higher reactivity than monovalent ammonium salt compounds, thereby suppressing material diffusion into the resist upper layer film and enabling the formation of a strong silicon-containing resist underlayer film with good LWR and CDU properties. Furthermore, when the composition for forming a silicon-containing resist underlayer film to which the polyvalent ammonium salt compound of the present invention is added is added, a silicon-containing resist underlayer film with a good etching rate can be formed due to the effect of silicon atoms.

[0015] In addition, in the present invention, - is preferably formate, acetate, propionate, butyrate, hexanoate, benzoate, t-butylbenzoate, trichloroacetate, trifluoroacetate, 2-hydroxy-2,2-bis(trifluoromethyl)acetate, trimethylacetate, pentafluoropropionate, methanesulfonate, butanesulfonate, benzenesulfonate, toluenesulfonate, trifluoromethanesulfonate, methylsulfate ion, chloride ion, bromide ion, iodide ion, fluoride ion, cyanide ion, nitrate ion, nitrite ion, or hydroxide ion.

[0016] A - When is the above-mentioned specific anion, the effects of the present invention are more fully exhibited.

[0017] In the present invention, the polyvalent ammonium salt compound is preferably represented by the following general formula (B-1), (B-2), (B-3), or (B-4): [ka] (R in the formula 11 , R 12 , R 13 and R 14A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.) [ka] (R in the formula 21 , R 22 , R 23 , R 24 , R 25 and R 26 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.) [ka] (R in the formula 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R 37 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.) [ka] (R in the formula 41 , R 42 , and R 43 R are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 and R 53A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.)

[0018] Such polyvalent ammonium salt compounds can more effectively exhibit the effects of the present invention.

[0019] The present invention also provides a composition for forming a silicon-containing resist underlayer film, which contains the polyvalent ammonium salt compound described above and a thermally crosslinkable polysiloxane.

[0020] Such a composition for forming a silicon-containing resist underlayer film can form a silicon-containing resist underlayer film in a multilayer resist method, which has an appropriate etching rate and can improve LWR and CDU in an ultrafine pattern.

[0021] In the present invention, the thermally crosslinkable polysiloxane preferably contains one or more of a repeating unit represented by the following general formula (Sx-1), a repeating unit represented by the following general formula (Sx-2), and a partial structure represented by the following general formula (Sx-3): [ka] [ka] [ka] (In the formula, R 1 , R 2 and R 3 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different.

[0022] When the thermally crosslinkable polysiloxane contains the above-mentioned specific structure, the effects of the present invention are more fully exhibited.

[0023] The composition for forming a silicon-containing resist underlayer film of the present invention preferably further contains an acid generator.

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

[0025] In this case, the acid generator is preferably a photoacid generator that generates an acid by the action of high-energy rays.

[0026] This allows for appropriate adjustment of the pattern shape, exposure sensitivity, etc. of the resist top layer film while minimizing deterioration of other performances, and may also be effective in reducing residues derived from the resist top layer film.

[0027] The present invention also provides a method for forming a pattern on a workpiece, comprising the steps of: 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 composition for forming a silicon-containing resist underlayer film described above; forming a resist upper layer film on the silicon-containing resist underlayer film using a resist upper layer film composition comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a step of transferring the pattern to the silicon-containing resist underlayer film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; a step of transferring the pattern to the organic film by etching using the silicon-containing resist underlayer film to which the pattern has been transferred as a mask; a step of transferring the pattern to the workpiece by etching using the organic film to which the pattern has been transferred as a mask; The present invention provides a pattern formation method comprising the steps of:

[0028] The present invention also provides a method for forming a pattern on a workpiece, comprising the steps of: forming a hard mask on a workpiece by a CVD method; forming a silicon-containing resist underlayer film on the hard mask using the composition for forming a silicon-containing resist underlayer film described above; forming a resist upper layer film on the silicon-containing resist underlayer film using a resist upper layer film composition comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a step of transferring the pattern to the silicon-containing resist underlayer film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the hard mask by dry etching using the silicon-containing resist underlayer film to which the pattern has been transferred as a mask; transferring the pattern to the workpiece by dry etching using the hard mask to which the pattern has been transferred as a mask; The present invention provides a pattern formation method comprising the steps of:

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

[0030] In the present invention, the method for forming a circuit pattern on the resist upper layer film is preferably photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0031] When the circuit pattern is formed on the resist upper layer film by the above-mentioned specific method, the effects of the present invention are more fully exhibited.

[0032] In addition, in the present invention, the workpiece may be a semiconductor device substrate, or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film formed thereon.

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

[0034] Furthermore, in the present invention, it is preferable to use, as the metal, silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

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

[0036] As described above, the polyvalent ammonium salt compound of the present invention, when added to a composition for forming a silicon-containing resist underlayer film containing a thermally crosslinkable polysiloxane as a curing catalyst, not only can form an ultrafine upper layer resist pattern with good LWR and CDU, but also has excellent dry etching selectivity with respect to the resist upper layer film and the organic film or hard mask, allowing for high yields of semiconductor device patterns to be formed on substrates. Furthermore, since the formed silicon-containing resist underlayer film exhibits high etching selectivity with respect to organic materials, the formed upper layer resist pattern can be transferred sequentially to the silicon-containing resist underlayer film and the organic film or hard mask using a dry etching process. Furthermore, since the formed silicon-containing resist underlayer film has a sufficient etching rate, the silicon-containing resist underlayer film remaining after patterning is easily removed, and defects due to residues are unlikely to occur, making it particularly useful for forming fine patterns. DETAILED DESCRIPTION OF THE INVENTION

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

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

[0039] That is, the present invention relates to a polyvalent ammonium salt compound having two or more ammonium ions in one molecule, which is represented by the following general formula (A-1). [ka] (In the formula, R1 is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and may contain one or more nitrogen atoms; R2, R3, R4, R5, R6, and R7 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and may contain one or more nitrogen atoms. In addition, any two or more selected from R1, R2, R3, R4, R5, R6, and R7 may bond to each other to form a ring together with the nitrogen atom in the formula. A - represents an organic or inorganic anion that serves as a counter ion of the ammonium cation, excluding bistrifluoromethanesulfonylimide; and n is an integer of 2 to 10.

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

[0041] <Silicon-containing resist underlayer film forming composition> The composition for forming a silicon-containing resist underlayer film of the present invention contains a polyvalent ammonium salt compound represented by the following general formula (A-1) and a thermally crosslinkable polysiloxane. In addition, it may contain other optional components. Hereinafter, each component contained in the composition for forming a silicon-containing resist underlayer film of the present invention will be described in detail.

[0042] <Polyvalent ammonium salt compounds> The polyvalent ammonium salt compound of the present invention is a polyvalent ammonium salt compound represented by the following general formula (A-1), and can be used as a curing catalyst. [ka] (In the formula, R1 is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and may contain one or more nitrogen atoms; R2, R3, R4, R5, R6, and R7 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and may contain one or more nitrogen atoms. In addition, any two or more selected from R1, R2, R3, R4, R5, R6, and R7 may bond to each other to form a ring together with the nitrogen atom in the formula. A - represents an organic or inorganic anion that serves as a counter ion of the ammonium cation, excluding bistrifluoromethanesulfonylimide; and n is an integer of 2 to 10.

[0043] [Polyvalent ammonium salt compound represented by general formula (A-1)] The polyvalent ammonium salt compound of the present invention, when added to a composition for forming a silicon-containing resist underlayer film, functions as a curing catalyst and promotes thermal curing. During curing, the compound is more reactive than monovalent ammonium salt compounds, thereby suppressing diffusion into the upper layer resist, providing a robust composition for forming a silicon-containing resist underlayer film that contributes to improving LWR and CDU. Furthermore, the formed silicon-containing resist underlayer film is believed to have an etching rate sufficient for processing because it has an appropriate composition and structure.

[0044] In the present specification, a film formed below a resist top layer film is called a bottom layer film, and includes what are called resist bottom layer films and silicon-containing resist intermediate films.

[0045] In the general formula (A-1), R1 is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent and may contain one or more nitrogen atoms, and R2, R3, R4, R5, R6, and R7 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent and may contain one or more nitrogen atoms. Specific examples of the aromatic group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. Examples of the substituent that may be substituted include a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, a heteroaromatic group, an alkoxy group, a hydroxyl group, an ester group, a carbonyl group, an amino group, a halogen group, a sulfide group, a carboxy group, a sulfo group, an amido group, an imido group, a cyano group, an aldehyde group, an imino group, a urea group, a carbamate group, a carbonate group, a nitro group, a sulfonyl group, and a combination of these groups. In addition, any two or more selected from R1, R2, R3, R4, R5, R6, and R7 may be bonded to each other to form a ring together with the nitrogen atom in the formula.

[0046] In order to more effectively demonstrate the effects of the present invention, the polyvalent ammonium salt compound may be represented by the following general formula (B-1), (B-2), (B-3) or (B-4): [ka] (R in the formula 11 , R 12 , R 13 and R 14 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.) [ka] (R in the formula 21 , R 22 , R 23 , R 24 , R 25 and R 26 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.) [ka] (R in the formula 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R 37 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and may be the same or different. - is the same as above.) [ka] (R in the formula 41 , R 42 , and R 43R are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 and R 53 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.)

[0047] In the above general formula (B-1), R 11 , R 12 , R 13 and R 14 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. Specific examples of aromatic groups having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. - represents an organic or inorganic anion that serves as a counterion to the ammonium cation. Examples of the substituent that may be present include a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, a heteroaromatic group, an alkoxy group, a hydroxyl group, an ester group, a carbonyl group, an amino group, a halogen group, a sulfide group, a carboxy group, a sulfo group, an amido group, an imido group, a cyano group, an aldehyde group, an imino group, a urea group, a carbamate group, a carbonate group, a nitro group, a sulfonyl group, and a combination of these groups. To more effectively demonstrate the effects of the present invention, a phenyl group, a naphthyl group, a furanyl group, a thiophenyl group, a pyrrolyl group, or a pyridinyl group is preferred, and a phenyl group or a naphthyl group is more preferred.

[0048] In the above general formula (B-2), R 21 , R 22 , R 23 , R24 , R 25 and R 26 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. Specific examples of aromatic groups having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. - represents an organic or inorganic anion that serves as a counterion to the ammonium cation. Examples of the substituent that may be present include a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, a heteroaromatic group, an alkoxy group, a hydroxyl group, an ester group, a carbonyl group, an amino group, a halogen group, a sulfide group, a carboxy group, a sulfo group, an amido group, an imido group, a cyano group, an aldehyde group, an imino group, a urea group, a carbamate group, a carbonate group, a nitro group, a sulfonyl group, and a combination of these groups. To more effectively demonstrate the effects of the present invention, a phenyl group, a naphthyl group, a furanyl group, a thiophenyl group, a pyrrolyl group, or a pyridinyl group is preferred, and a phenyl group or a naphthyl group is more preferred.

[0049] In the above general formula (B-3), R 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R 37 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. Specific examples of aromatic groups having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. -represents an organic or inorganic anion that serves as a counterion to the ammonium cation. Examples of the substituent that may be present include a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, a heteroaromatic group, an alkoxy group, a hydroxyl group, an ester group, a carbonyl group, an amino group, a halogen group, a sulfide group, a carboxy group, a sulfo group, an amido group, an imido group, a cyano group, an aldehyde group, an imino group, a urea group, a carbamate group, a carbonate group, a nitro group, a sulfonyl group, and a combination of these groups. To more effectively demonstrate the effects of the present invention, a phenyl group, a naphthyl group, a furanyl group, a thiophenyl group, a pyrrolyl group, or a pyridinyl group is preferred, and a phenyl group or a naphthyl group is more preferred.

[0050] In the above general formula (B-4), R 41 , R 42 , and R 43 R are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 and R 53 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. Specific examples of aromatic groups having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. -represents an organic or inorganic anion that serves as a counterion to the ammonium cation. Examples of the substituent that may be present include a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, a heteroaromatic group, an alkoxy group, a hydroxyl group, an ester group, a carbonyl group, an amino group, a halogen group, a sulfide group, a carboxy group, a sulfo group, an amido group, an imido group, a cyano group, an aldehyde group, an imino group, a urea group, a carbamate group, a carbonate group, a nitro group, a sulfonyl group, and a combination of these groups. To more effectively demonstrate the effects of the present invention, a phenyl group, a naphthyl group, a furanyl group, a thiophenyl group, a pyrrolyl group, or a pyridinyl group is preferred, and a phenyl group or a naphthyl group is more preferred.

[0051] In the above general formulae (B-1), (B-2), (B-3) and (B-4), A - indicates an organic or inorganic anion that serves as a counterion to the ammonium cation. Specific examples of organic anions include formate, acetate, propionate, butyrate, hexanoate, benzoate, t-butylbenzoate, trichloroacetate, trifluoroacetate, 2-hydroxy-2,2-bis(trifluoromethyl)acetate, trimethylacetate, pentafluoropropionate, methanesulfonate, butanesulfonate, benzenesulfonate, toluenesulfonate, trifluoromethanesulfonate, and methyl sulfate ions. Specific examples of inorganic anions include chloride ions, bromide ions, iodide ions, fluoride ions, cyanide ions, nitrate ions, nitrite ions, and hydroxide ions. Of these anions, chloride ions, iodide ions, fluoride ions, nitrate ions, nitrite ions, and hydroxide ions are preferred, with chloride ions and nitrate ions being more preferred.

[0052] In the present invention, the polyvalent ammonium salt compound represented by the general formula (A-1) may be used alone or in combination of two or more. The amount of the polyvalent ammonium salt compound represented by the general formula (A-1) to be blended is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane (Sx) described below.

[0053] More specific examples of the polyvalent ammonium salt compound represented by the general formula (A-1) include, but are not limited to, the following compounds.

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [Thermal crosslinkable polysiloxane] The composition for forming a silicon-containing resist underlayer film of the present invention contains one or more polyvalent ammonium salt compounds represented by the above general formula (A-1), as well as a thermally crosslinkable polysiloxane.

[0059] The thermally crosslinkable polysiloxane (Sx) used in the present invention preferably contains one or more of a repeating unit represented by the following general formula (Sx-1), a repeating unit represented by the following general formula (Sx-2), and a partial structure represented by the following general formula (Sx-3). [ka] [ka] [ka] (In the formula, R 1 , R 2 , and R 3 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different.

[0060] The thermally crosslinkable polysiloxane (Sx) can be produced, for example, by hydrolyzing and condensing the following hydrolyzable monomer (Sm).

[0061] Specific examples of the hydrolyzable monomer (Sm) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrippropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Oxysilane, vinyl tripropoxysilane, vinyl triisopropoxysilane, propyl trimethoxysilane, propyl triethoxysilane, propyl tripropoxysilane, propyl triisopropoxysilane, isopropyl trimethoxysilane, isopropyl triethoxysilane, isopropyl tripropoxysilane, isopropyl triisopropoxysilane, butyl trimethoxysilane, butyl triethoxysilane, butyl tripropoxysilane, butyl triisopropoxysilane, isobutyl trimethoxysilane, isobutyl triethoxysilane Silane, isobutyl tripropoxysilane, isobutyl triisopropoxysilane, sec-butyl trimethoxysilane, sec-butyl triethoxysilane, sec-butyl tripropoxysilane, sec-butyl triisopropoxysilane, t-butyl trimethoxysilane, t-butyl triethoxysilane, t-butyl tripropoxysilane, t-butyl triisopropoxysilane, allyl trimethoxysilane, allyl triethoxysilane, allyl tripropoxysilane, allyl triisopropoxysilane, cyclopropyl trimethoxysilane, Cyclopropyltriethoxysilane, cyclopropyltripropoxysilane, cyclopropyltriisopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyltrippropoxysilane, cyclobutyltriisopropoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltrippropoxysilane, cyclopentyltriisopropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrippropoxysilane,Cyclohexyltriisopropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltrippropoxysilane, bicycloheptenyltriisopropoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyltrippropoxysilane, bicycloheptyltriisopropoxysilane anisyltriisopropoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyltripropoxysilane, adamantyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrippropoxysilane, phenyltriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltrippropoxysilane, benzyltriisopropoxysilane, anisyltrimethoxysilane, anisyltriethoxysilane, anisyltrippropoxysilane, anisyl Triisopropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltrippropoxysilane, tolyltriisopropoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltrippropoxysilane, phenethyltriisopropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltrippropoxysilane, naphthyltriisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane,Dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, dipropyldiisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxy Silane, dibutyldiisopropoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldipropoxysilane, di-sec-butyldiisopropoxysilane, di-t-butyldimethoxysilane, di-t-butyldiethoxysilane, di-t-butyldipropoxysilane, di-t-butyldiisopropoxysilane, dicyclopropyldimethoxysilane, dicyclopropyldiethoxysilane, dicyclopropyldipropoxysilane, dicyclopropyldiisopropoxysilane, dicyclobutyldimethoxysilane, dicyclopropyl Dicyclobutyldiethoxysilane, dicyclobutyldipropoxysilane, dicyclobutyldiisopropoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentyldipropoxysilane, dicyclopentyldiisopropoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane, dicyclohexyldiisopropoxysilane, dicyclohexenyldimethoxysilane, dicyclohexenyldiethoxysilane, dicyclohexenyldipropoxysilane, dicyclo Hexenyl diisopropoxysilane, dicyclohexenyl ethyl dimethoxysilane, dicyclohexenyl ethyl diethoxysilane, dicyclohexenyl ethyl dipropoxysilane, dicyclohexenyl ethyl diisopropoxysilane, dicyclooctyl dimethoxysilane, dicyclooctyl diethoxysilane, dicyclooctyl dipropoxysilane, dicyclooctyl diisopropoxysilane, dicyclopentadienyl propyl dimethoxysilane, dicyclopentadienyl propyl diethoxysilane, dicyclopentadienyl propyl dipropoxysilane,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, diadamantyldi Examples include isopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethylbenzylmethoxysilane, dimethylbenzylethoxysilane, dimethylphenethylmethoxysilane, and dimethylphenethylethoxysilane.

[0062] Preferred examples of the above compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, and cyclohexenyltrimethoxysilane. Examples of such silane include cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, and dimethylphenethylmethoxysilane.

[0063] Above R 1 , R 2 , and R 3 Another example of the organic group represented by formula (Sm-R) is 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 an ether bond, an ester bond, an alkoxy group, a hydroxy group, etc. Examples of such an organic group include those represented by the following general formula (Sm-R):

[0064] (P-Q1-(S1) v1 -Q2-) u -(T)v2 -Q3-(S2) v3 -Q4- (Sm-R) In the general formula (Sm-R), P represents a hydrogen atom, a cyclic ether group, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or an alkylcarbonyl group having 2 to 6 carbon atoms; and Q1, Q2, Q3, and Q4 each independently represent -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 (however, 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, and T is a divalent group consisting of a divalent atom other than carbon, an alicyclic ring, an aromatic ring, or a heterocyclic ring.)

[0065] Examples of T that may contain a heteroatom such as an oxygen atom include an alicyclic ring, an aromatic ring, and a heterocyclic ring. The bonding positions of T to Q2 and Q3 are not particularly limited, but can be appropriately selected in consideration of reactivity due to steric factors, the availability of commercially available reagents used in the reaction, and the like.

[0066] [ka]

[0067] 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) include the following: In the following formula, (Si) is written to indicate the bonding site with Si.

[0068] [ka]

[0069] [ka]

[0070] Also, R 1 , R 2 , and R 3 As examples of the organic group, an organic group containing a silicon-silicon bond can also be used. Specific examples include the following: [ka]

[0071] Also, R 1 , R 2 , and R 3 Examples of the organic group include organic groups having a protecting group that is decomposed by an acid. Specific examples include the organic groups listed in paragraphs (0043) to (0048) of JP-A No. 2013-167669 and the organic groups obtained from silicon compounds listed in paragraph (0056) of JP-A No. 2013-224279.

[0072] Furthermore, R 1 , R 2 , and R 3 As an example of the organic group, an organic group having a fluorine atom can also be used. Specific examples include organic groups obtained from silicon compounds described in paragraphs (0059) to (0065) of JP-A No. 2012-53253.

[0073] The hydrolyzable monomer (Sm) has one, two or three hydrolyzable groups such as chlorine, bromine, iodine, acetoxy, methoxy, ethoxy, propoxy or butoxy groups bonded to the silicon atom represented by (Si) in the partial structure.

[0074] [Method for synthesizing thermally crosslinkable polysiloxane (Sx)] (Synthesis method 1: acid catalyst) The thermally crosslinkable polysiloxane (Sx) used in the present invention can be produced by hydrolyzing and condensing one or a mixture of two or more hydrolyzable monomers (Sm) in the presence of an acid catalyst.

[0075] Examples of the acid catalyst used in this case include organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid, as well as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid. The amount of the catalyst used is preferably 1×10 relative to 1 mole of the monomer. -6 ~10 moles, more preferably 1 x 10 -5 ~5 mol, more preferably 1 × 10 -4 ~1 mole.

[0076] When obtaining a thermally crosslinkable polysiloxane (Sx) from these monomers by hydrolysis and condensation, the amount of water added is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, and even more preferably 0.1 to 30 mol per mol of hydrolyzable substituent bonded to the monomer. If the amount is 100 mol or less, the apparatus used for the reaction can be made smaller and more economical. If the amount is 0.01 mol or more, the reaction proceeds sufficiently.

[0077] The operation method involves adding a monomer to an aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. A preferred method is to maintain the temperature at 5 to 80°C during the dropwise addition of the monomer, and then mature the mixture at 20 to 80°C.

[0078] Examples of organic solvents that can be added to the aqueous catalyst solution or that can be used to dilute the monomer include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, ethylene glycol, propylene glycol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and butanediol monoethyl ether. Preferred are propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, and mixtures thereof.

[0079] Among these organic solvents, water-soluble ones are preferred. Examples include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; polyhydric alcohols such as ethylene glycol and propylene glycol; polyhydric alcohol condensate derivatives such as butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, and ethylene glycol monopropyl ether; acetone, acetonitrile, and tetrahydrofuran. Among these, those having a boiling point of 100° C. or less are particularly preferred.

[0080] The amount of organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per mole of monomer. A smaller amount of organic solvent used allows for a smaller reaction vessel, which is more economical.

[0081] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture. At this time, the amount of alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used in the catalyst. This alkaline substance may be any substance that exhibits alkaline properties in water.

[0082] Subsequently, by-products such as alcohol produced in the hydrolysis-condensation reaction are preferably removed from the aqueous reaction mixture by vacuum removal or the like. The temperature to which the aqueous reaction mixture is heated depends on the types of organic solvent added and alcohol produced in the reaction, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum used here varies depending on the types of organic solvent and alcohol to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure. While it is difficult to accurately determine the amount of alcohol removed, it is desirable to remove approximately 80 mass% or more of the produced alcohol.

[0083] Next, the acid catalyst used in the hydrolysis and condensation may be removed from the aqueous reaction mixture. To remove the acid catalyst, water and the thermally crosslinkable polysiloxane solution are mixed, and the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used here is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0084] Furthermore, a mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent can be used. For example, a methanol-ethyl acetate mixture, an ethanol-ethyl acetate mixture, a 1-propanol-ethyl acetate mixture, a 2-propanol-ethyl acetate mixture, a butanediol monomethyl ether-ethyl acetate mixture, a propylene glycol monomethyl ether-ethyl acetate mixture, an ethylene glycol monomethyl ether-ethyl acetate mixture, a butanediol monoethyl ether-ethyl acetate mixture, a propylene glycol monoethyl ether-ethyl acetate mixture, an ethylene glycol monoethyl ether-ethyl acetate mixture, a butanediol monopropyl ether-ethyl acetate mixture, a propylene glycol monopropyl ether-ethyl acetate mixture, an ethylene glycol monopropyl ether-ethyl acetate mixture, a methanol-methyl isobutyl ketone mixture, an ethanol-methyl isobutyl ketone mixture, a 1-propanol-methyl isobutyl ketone mixture, a 2-propanol-methyl isobutyl ketone mixture, a propylene glycol monomethyl ether-methyl isobutyl ketone mixture, an ethylene glycol monomethyl ether-methyl isobutyl ketone mixture, ton mixture, propylene glycol monoethyl ether-methyl isobutyl ketone mixture, ethylene glycol monoethyl ether-methyl isobutyl ketone mixture, propylene glycol monopropyl ether-methyl isobutyl ketone mixture, ethylene glycol monopropyl ether-methyl isobutyl ketone mixture, methanol-cyclopentyl methyl ether mixture, ethanol-cyclopentyl methyl ether mixture, 1-propanol-cyclopentyl methyl ether mixture, 2-propanol-cyclopentyl methyl ether mixture, propylene glycol monomethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monomethyl ether-cyclopentyl methyl ether mixture, propylene glycol monoethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monoethyl ether-cyclopentyl methyl ether mixture, propylene glycol monopropyl ether-cyclopentyl methyl ether mixture, ethylene glycol monopropyl ether-cyclopentyl methyl ether mixture,Preferred combinations include, but are not limited to, a methanol-propylene glycol methyl ether acetate mixture, an ethanol-propylene glycol methyl ether acetate mixture, a 1-propanol-propylene glycol methyl ether acetate mixture, a 2-propanol-propylene glycol methyl ether acetate mixture, a propylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, an ethylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, a propylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, an ethylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, a propylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, and an ethylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture.

[0085] The mixing ratio of the water-soluble organic solvent to the poorly water-soluble organic solvent is selected as appropriate, but is preferably 0.1 to 1,000 parts by mass of the water-soluble organic solvent per 100 parts by mass of the poorly water-soluble organic solvent, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0086] Subsequently, the solution may be washed with neutral water. This water may be what is commonly called deionized water or ultrapure water. The amount of water used is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and even more preferably 0.1 to 5 L, per 1 L of the thermally crosslinkable polysiloxane solution. This washing method involves placing both solutions in the same container, stirring, and then leaving the solution to stand to separate the aqueous layer. Washing may be performed once or more, but washing 10 or more times will not provide the desired effect, so washing is preferably performed about 1 to 5 times.

[0087] Other methods for removing the acid catalyst include a method using an ion exchange resin and a method of neutralizing the acid catalyst with an epoxy compound such as ethylene oxide or propylene oxide and then removing the acid catalyst. These methods can be appropriately selected depending on the acid catalyst used in the reaction.

[0088] This water washing operation may cause a portion of the thermally crosslinkable polysiloxane to escape into the aqueous layer, thereby providing an effect substantially equivalent to that of the fractionation operation. Therefore, the number of water washes and the amount of washing water may be appropriately selected in consideration of the catalyst removal effect and the fractionation effect.

[0089] In both the thermally crosslinkable polysiloxane solution containing a residual acid catalyst and the thermally crosslinkable polysiloxane solution from which the acid catalyst has been removed, the desired thermally crosslinkable polysiloxane solution is obtained by adding a final solvent and performing solvent exchange under reduced pressure. The temperature for solvent exchange depends on the types of reaction solvent and extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum varies depending on the type of extraction solvent to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure.

[0090] In this case, the change in solvent may cause the thermally crosslinkable polysiloxane to become unstable. This occurs due to the compatibility between the final solvent and the thermally crosslinkable polysiloxane. To prevent this, a monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent, as described in paragraphs (0181) and (0182) of JP 2009-126940 A, may be added as a stabilizer. The amount added is preferably 0 to 25 parts by mass, more preferably 0 to 15 parts by mass, and even more preferably 0 to 5 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane in the solution before the solvent exchange. However, if added, 0.5 parts by mass or more is preferred. If necessary, the solvent exchange operation may be performed by adding a monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent to the solution before the solvent exchange.

[0091] The thermally crosslinkable polysiloxane is preferably kept in a solution state of an appropriate concentration. The concentration at this time is preferably 0.1 to 20% by mass. At such a concentration, further condensation reaction does not proceed, and the polysiloxane does not change to a state in which it cannot be redissolved in an organic solvent. Furthermore, the amount of solvent required is reduced, which is economical and preferable.

[0092] The final solvent to be added to the thermally crosslinkable polysiloxane solution is preferably an alcohol-based solvent, and particularly preferably a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, or butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, or diacetone alcohol is preferred.

[0093] If these solvents are the main component, it is also possible to add a non-alcoholic solvent as an auxiliary solvent, such as acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, or cyclopentyl methyl ether.

[0094] Another reaction procedure using an acid catalyst is to add water or a water-containing organic solvent to a monomer or an organic solution of the monomer to initiate the hydrolysis reaction. The catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. A preferred method involves heating the mixture to 10 to 50°C during the dropwise addition of water, and then raising the temperature to 20 to 80°C for aging.

[0095] When an organic solvent is used, it is preferably a water-soluble one, and examples thereof include polyhydric alcohol condensate derivatives such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, and mixtures thereof.

[0096] The amount of organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per mole of monomer. A smaller amount of organic solvent used allows for a smaller reaction vessel, which is more economical. The aqueous reaction mixture obtained can be post-treated in the same manner as described above to obtain a thermally crosslinkable polysiloxane.

[0097] (Synthesis method 2: Alkaline catalyst) The thermally crosslinkable polysiloxane (Sx) can be produced by hydrolyzing and condensing one or a mixture of two or more hydrolyzable monomers (Sm) in the presence of an alkali catalyst. Examples of the alkali catalyst used here include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclocyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. The amount of catalyst used is preferably 1 × 10 per mole of monomer. -6 mol to 10 mol, more preferably 1×10 -5 mol to 5 mol, more preferably 1×10 -4 mol to 1 mol.

[0098] When obtaining a thermally crosslinkable polysiloxane from the above monomers by hydrolysis and condensation, the amount of water added is preferably 0.1 to 50 moles per mole of hydrolyzable substituent bonded to the monomer. If the amount is 50 moles or less, the equipment used for the reaction can be small and economical. If the amount is 0.1 mole or more, the reaction proceeds sufficiently.

[0099] The operation method involves adding a monomer to an aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. A preferred method is to maintain the temperature at 5 to 80°C during the dropwise addition of the monomer, and then mature the mixture at 20 to 80°C.

[0100] As the organic solvent that can be added to the aqueous alkali catalyst solution or that can dilute the monomer, the same organic solvents as those exemplified as those that can be added to the aqueous acid catalyst solution are preferably used. The amount of organic solvent used is preferably 0 to 1,000 ml per mole of monomer, in order to carry out the reaction economically.

[0101] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture. At this time, the amount of the acidic substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the alkaline substance used in the catalyst. This acidic substance may be any substance that is acidic in water.

[0102] Subsequently, by-products such as alcohol produced in the hydrolysis-condensation reaction are preferably removed from the aqueous reaction mixture by vacuum removal or the like. The temperature to which the aqueous reaction mixture is heated depends on the type of organic solvent added and the type of alcohol produced in the reaction, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum used here varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure. While it is difficult to accurately determine the amount of alcohol removed, it is desirable to remove approximately 80 mass% or more of the produced alcohol.

[0103] Next, to remove the catalyst used in the hydrolysis and condensation, the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used here is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0104] Furthermore, it is also possible to use a mixture of a water-soluble organic solvent and a slightly water-soluble organic solvent.

[0105] Specific examples of the organic solvent used when removing the alkali catalyst include the organic solvents specifically exemplified above as those used when removing the acid catalyst, and mixtures of water-soluble organic solvents and poorly water-soluble organic solvents.

[0106] The mixing ratio of the water-soluble organic solvent to the poorly water-soluble organic solvent is appropriately selected, but is preferably 0.1 to 1,000 parts by mass of the water-soluble organic solvent per 100 parts by mass of the poorly water-soluble organic solvent, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0107] The mixture is then washed with neutral water. This water may be what is commonly called deionized water or ultrapure water. The amount of water used is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and even more preferably 0.1 to 5 L per 1 L of the thermally crosslinkable polysiloxane solution. This washing method involves placing both components in the same container, stirring, and then allowing the mixture to stand to separate the aqueous layer. Washing may be performed once or more, but washing more than 10 times will not provide the desired effect, so washing is preferably performed about 1 to 5 times.

[0108] The final solvent is added to the washed thermally crosslinkable polysiloxane solution, and solvent exchange is performed under reduced pressure to obtain the desired thermally crosslinkable polysiloxane solution. The temperature for solvent exchange depends on the type of extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum varies depending on the type of extraction solvent to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure.

[0109] The final solvent to be added to the thermally crosslinkable polysiloxane solution is preferably an alcohol-based solvent, and particularly preferably a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, or dipropylene glycol.Specifically, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, or diacetone alcohol is preferred.

[0110] Another reaction procedure using an alkali catalyst involves adding water or a water-containing organic solvent to a monomer or an organic solution of the monomer to initiate the hydrolysis reaction. The catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. A preferred method involves heating the mixture to 10 to 50°C during the dropwise addition of water, and then raising the temperature to 20 to 80°C for aging.

[0111] The organic solvent that can be used as the organic solution of the monomer or the aqueous organic solvent is preferably a water-soluble one, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, polyhydric alcohol condensate derivatives such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, and mixtures thereof.

[0112] The molecular weight of the thermally crosslinkable polysiloxane obtained by synthesis method 1 or 2 can be adjusted not only by the selection of monomers but also by controlling the reaction conditions during polymerization, but a weight-average molecular weight of 100,000 or less prevents the generation of foreign matter or coating spots, so it is preferable to use one of 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. Note that the data regarding the weight-average molecular weight above was measured by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an eluent, and polystyrene as a standard substance, and the molecular weight was expressed in terms of polystyrene.

[0113] The physical properties of the thermally crosslinkable polysiloxane used in the present invention vary depending on the type of acid or alkali catalyst used during hydrolysis and condensation and the reaction conditions, and therefore can be appropriately selected depending on the desired performance of the resist underlayer film.

[0114] Furthermore, a polysiloxane derivative produced from a mixture of one or more hydrolyzable monomers (Sm) and a hydrolyzable metal compound represented by the following general formula (Mm) under the conditions using the acid or alkali catalyst can be used as a component of a composition for forming a resist underlayer film. U(OR 7 ) m7 (OR 8 ) m8 (Mm) (In the general formula (Mm), R 7 , and R 8 are each independently an organic group having 1 to 30 carbon atoms, m7 + m8 is the same as the valence determined by the type of U, m7 and m8 are integers of 0 or more, and U is an element of Group III, IV, or V of the periodic table, excluding carbon and silicon.

[0115] Examples of the hydrolyzable metal compound represented by the general formula (Mm) used in this case include the following: When U is boron, examples of the hydrolyzable metal compound represented by the general formula (Mm) include boron methoxide, boron ethoxide, boron propoxide, boron butoxide, boron amyloxide, boron hexyloxide, boron cyclopentoxide, boron cyclohexyloxide, boron allyloxide, boron phenoxide, boron methoxyethoxide, boric acid, and boron oxide.

[0116] When U is aluminum, examples of the hydrolyzable metal compound represented by the general formula (Mm) include aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, aluminum amyloxide, aluminum hexyloxide, aluminum cyclopentoxide, aluminum cyclohexyloxide, aluminum allyloxide, aluminum phenoxide, aluminum methoxyethoxide, aluminum ethoxyethoxide, aluminum dipropoxyethyl acetoacetate, aluminum dibutoxyethyl acetoacetate, aluminum propoxybisethyl acetoacetate, aluminum butoxybisethyl acetoacetate, aluminum 2,4-pentanedionate, and aluminum 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0117] When U is gallium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include gallium methoxide, gallium ethoxide, gallium propoxide, gallium butoxide, gallium amyloxide, gallium hexyloxide, gallium cyclopentoxide, gallium cyclohexyloxide, gallium allyloxide, gallium phenoxide, gallium methoxyethoxide, gallium ethoxyethoxide, gallium dipropoxyethyl acetoacetate, gallium dibutoxyethyl acetoacetate, gallium propoxybisethyl acetoacetate, gallium butoxybisethyl acetoacetate, gallium 2,4-pentanedionate, and gallium 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0118] When U is yttrium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include yttrium methoxide, yttrium ethoxide, yttrium propoxide, yttrium butoxide, yttrium amyloxide, yttrium hexyloxide, yttrium cyclopentoxide, yttrium cyclohexyloxide, yttrium allyloxide, yttrium phenoxide, yttrium methoxyethoxide, yttrium ethoxyethoxide, yttrium dipropoxyethyl acetoacetate, yttrium dibutoxyethyl acetoacetate, yttrium propoxybisethyl acetoacetate, yttrium butoxybisethyl acetoacetate, yttrium 2,4-pentanedionate, and yttrium 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0119] When U is germanium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include germanium methoxide, germanium ethoxide, germanium propoxide, germanium butoxide, germanium amyloxide, germanium hexyloxide, germanium cyclopentoxide, germanium cyclohexyloxide, germanium allyloxide, germanium phenoxide, germanium methoxyethoxide, and germanium ethoxyethoxide.

[0120] When U is titanium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, titanium amyloxide, titanium hexyloxide, titanium cyclopentoxide, titanium cyclohexyloxide, titanium allyloxide, titanium phenoxide, titanium methoxyethoxide, titanium ethoxyethoxide, titanium dipropoxybisethylacetoacetate, titanium dibutoxybisethylacetoacetate, titanium dipropoxybis2,4-pentanedionate, and titanium dibutoxybis2,4-pentanedionate.

[0121] When U is hafnium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include hafnium methoxide, hafnium ethoxide, hafnium propoxide, hafnium butoxide, hafnium amyloxide, hafnium hexyloxide, hafnium cyclopentoxide, hafnium cyclohexyloxide, hafnium allyloxide, hafnium phenoxide, hafnium methoxyethoxide, hafnium ethoxyethoxide, hafnium dipropoxybisethylacetoacetate, hafnium dibutoxybisethylacetoacetate, hafnium dipropoxybis 2,4-pentanedionate, and hafnium dibutoxybis 2,4-pentanedionate.

[0122] When U is tin, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxytin, ethoxytin, propoxytin, butoxytin, phenoxytin, methoxyethoxytin, ethoxyethoxytin, tin 2,4-pentanedionate, and tin 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0123] When U is arsenic, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxy arsenic, ethoxy arsenic, propoxy arsenic, butoxy arsenic, and phenoxy arsenic.

[0124] When U is antimony, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxyantimony, ethoxyantimony, propoxyantimony, butoxyantimony, phenoxyantimony, antimony acetate, and antimony propionate.

[0125] When U is niobium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxy niobium, ethoxy niobium, propoxy niobium, butoxy niobium, and phenoxy niobium.

[0126] When U is tantalum, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxytantalum, ethoxytantalum, propoxytantalum, butoxytantalum, and phenoxytantalum.

[0127] When U is bismuth, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxybismuth, ethoxybismuth, propoxybismuth, butoxybismuth, and phenoxybismuth.

[0128] When U is phosphorus, examples of the hydrolyzable metal compound represented by the general formula (Mm) include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, and diphosphorus pentoxide.

[0129] When U is vanadium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include vanadium oxide bis(2,4-pentanedionate), vanadium 2,4-pentanedionate, vanadium tributoxide oxide, and vanadium tripropoxide oxide.

[0130] When U is zirconium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxyzirconium, ethoxyzirconium, propoxyzirconium, butoxyzirconium, phenoxyzirconium, zirconium dibutoxide bis(2,4-pentanedionate), and zirconium dipropoxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate).

[0131] In the composition for forming a silicon-containing resist underlayer film of the present invention, the blend amount of the thermally crosslinkable polysiloxane (Sx) is preferably, for example, 0.1 to 10% by mass relative to the solvent.

[0132] [Acid generator] The silicon-containing resist underlayer film-forming composition of the present invention preferably further contains an acid generator. One or more types of acid generators can be blended. Any acid generator that functions as an acid precursor, such as a thermal acid generator, a photoacid generator, or an acid multiplier, can be used. However, in the present invention, the acid generator is preferably a photoacid generator that generates an acid upon the action of high-energy rays. More preferably, the acid generator to be blended is a sulfonium salt that generates an acid upon the action of high-energy rays. More specifically, examples include, but are not limited to, the materials described in paragraphs

[0160] to

[0179] of JP 2009-126940 A. The amount of acid generator blended is preferably 0 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane (Sx).

[0133] [Other ingredients] (Crosslinking catalyst) The composition for forming a silicon-containing resist underlayer film of the present invention may contain, in addition to the polyvalent ammonium salt compound represented by the general formula (A-1), another crosslinking catalyst (Xc). Examples of the crosslinking catalyst (Xc) that can be added include compounds represented by the following general formula (Xc0): L a H b A (Xc0) (In general formula (Xc0), L represents lithium, sodium, potassium, rubidium, cesium, sulfonium, iodonium, phosphonium, or ammonium; A represents a non-nucleophilic counter ion; a represents an integer of 1 or greater; b represents 0 or an integer of 1 or greater; and a+b represents the valence of the non-nucleophilic counter ion.)

[0134] Specific examples of the crosslinking catalyst (Xc) used in the present invention as a compound represented by general formula (Xc0) include sulfonium salts of the following general formula (Xc-1), iodonium salts of (Xc-2), phosphonium salts of (Xc-3), and ammonium salts and alkali metal salts of (Xc-4).

[0135] Examples of the sulfonium salt (Xc-1), iodonium salt (Xc-2), phosphonium salt (Xc-3), and ammonium salt (Xc-4) are as follows:

[0136] [ka] [ka] (In the formula, R 204 , R 205 , R 206 , and R 207 represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group or the like. 205 and R 206 may form a ring, and when a ring is formed, R 205 , R 206 A represents an alkylene group having 1 to 6 carbon atoms. - represents a non-nucleophilic counter ion. 208 , R 209 , R 210 , and R 211 is R 204 , R 205 , R 206 , and R 207 R is the same as R, but may also be a hydrogen atom. 208 and R 209 , or R 208 and R 209 and R 210 may form a ring, and when a ring is formed, R 208 and R 209 , and R 208 and R 209 and R 210 represents an alkylene group having 3 to 10 carbon atoms.

[0137] Above R 204 , R 205 , R206 , R 207 , R 208 , R 209 , R 210 , and R 211may be the same or different, and specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl. Examples of alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Examples of oxoalkyl groups include 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl. Examples of the oxoalkenyl group include a 2-oxopropenyl group, a 2-oxobutenyl group, a 2-oxohexenyl group, a 2-oxocyclopentenyl group, and a 2-oxocyclohexenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, etc., alkoxyphenyl groups such as p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, and m-tert-butoxyphenyl group, alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group, alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group, alkoxynaphthyl groups such as methoxynaphthyl group and ethoxynaphthyl group, dialkylnaphthyl groups such as dimethylnaphthyl group and diethylnaphthyl group, and dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group, etc. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. Examples of the aryloxoalkyl group include 2-aryl-2-oxoethyl groups such as a 2-phenyl-2-oxoethyl group, a 2-(1-naphthyl)-2-oxoethyl group, and a 2-(2-naphthyl)-2-oxoethyl group.

[0138] A in (Xc-1) to (Xc-4) above - Non-nucleophilic counter ions of the above include hydroxide ion, formate ion, acetate ion, propionate ion, butanoate ion, pentanoate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleate ion, linolenate ion, benzoate ion, phthalate ion, isophthalate ion, terephthalate ion, salicylate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, trichloroacetate ion, fluorine ion, chloride ion, bromide ion, iodide ion, nitrate ion, Examples of the ion include monovalent ions such as nitrite ion, chlorate ion, bromate ion, methanesulfonate ion, paratoluenesulfonate ion, and monomethylsulfate ion; 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, citraconic acid ion, citrate ion, carbonate ion, and sulfate ion.

[0139] Examples of alkali metal salts include monovalent salts such as hydroxide, formate, acetate, propionate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, oleate, stearate, linoleate, linolenate, benzoate, phthalate, isophthalate, terephthalate, salicylate, trifluoroacetate, monochloroacetate, dichloroacetate, and trichloroacetate; monovalent or divalent oxalate; malonate, methylmalonate, ethylmalonate, propylmalonate, butylmalonate, dimethylmalonate, diethylmalonate, succinate, methylsuccinate, glutarate, adipate, itaconate, maleate, fumarate, citraconate, citrate, and carbonate of lithium, sodium, potassium, cesium, magnesium, and calcium.

[0140] Specifically, examples of the sulfonium salt (Xc-1) include triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionate, triphenylsulfonium butanoate, triphenylsulfonium benzoate, triphenylsulfonium phthalate, triphenylsulfonium isophthalate, triphenylsulfonium terephthalate, triphenylsulfonium salicylate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium monochloroacetate, triphenylsulfonium dichloroacetate, triphenylsulfonium trichloroacetate, triphenylsulfonium hydroxide, triphenylsulfonium nitrate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium oxalate, triphenylsulfonium malonate, triphenylsulfonium methylmalonate, ethylenediamine, ethylenediamine, ethylenediamine, ethylenediamine, ethylenediamine, ethylenediamine Examples of the alkyl esters include triphenylsulfonium ethylmalonate, triphenylsulfonium propylmalonate, triphenylsulfonium butylmalonate, triphenylsulfonium dimethylmalonate, triphenylsulfonium diethylmalonate, triphenylsulfonium succinate, triphenylsulfonium methylsuccinate, triphenylsulfonium glutarate, triphenylsulfonium adipate, triphenylsulfonium itaconate, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylsulfonium citraconic acid, triphenylsulfonium citrate, triphenylsulfonium carbonate, bistriphenylsulfonium oxalate, bistriphenylsulfonium maleate, bistriphenylsulfonium fumarate, bistriphenylsulfonium citraconic acid, bistriphenylsulfonium citrate, and bistriphenylsulfonium carbonate.

[0141] Specific examples of the iodonium salt (Xc-2) include diphenyliodonium formate, diphenyliodonium acetate, diphenyliodonium propionate, diphenyliodonium butanoate, diphenyliodonium benzoate, diphenyliodonium phthalate, diphenyliodonium isophthalate, diphenyliodonium terephthalate, diphenyliodonium salicylate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium monochloroacetate, diphenyliodonium dichloroacetate, diphenyliodonium trichloroacetate, diphenyliodonium hydroxide, Examples of the diphenyliodonium carbonate include bisdiphenyliodonium oxalate, bisdiphenyliodonium maleate, bisdiphenyliodonium fumarate, bisdiphenyliodonium citraconic acid, bisdiphenyliodonium citrate, and bisdiphenyliodonium carbonate.

[0142] Specific examples of the phosphonium salt (Xc-3) include tetraethylphosphonium formate, tetraethylphosphonium acetate, tetraethylphosphonium propionate, tetraethylphosphonium butanoate, tetraethylphosphonium benzoate, tetraethylphosphonium phthalate, tetraethylphosphonium isophthalate, tetraethylphosphonium terephthalate, tetraethylphosphonium salicylate, tetraethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoroacetate, tetraethylphosphonium monochloroacetate, tetraethylphosphonium dichloroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium hydroxide, tetraethylphosphonium nitrate, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetraethylphosphonium oxalate, tetraethylphosphonium maleate, tetraethylphosphonium fumarate, tetraethylphosphonium citraconic acid, tetraethylphosphonium citrate, tetraethylphosphonium carbonate, bistetraethylphosphonium oxalate, bistetraethylphosphonium maleate, thiaminyl phosphonium, bistetraethylphosphonium fumarate, bistetraethylphosphonium citraconic acid, bistetraethylphosphonium citrate, bistetraethylphosphonium carbonate, tetraphenylphosphonium formate, tetraphenylphosphonium acetate, tetraphenylphosphonium propionate, tetraphenylphosphonium butanoate, tetraphenylphosphonium benzoate, tetraphenylphosphonium phthalate, tetraphenylphosphonium isophthalate, tetraphenylphosphonium terephthalate, tetraphenylphosphonium salicylate, tetraphenylphosphonium trifluoromethanesulfonate, tetraphenylphosphonium trifluoroacetate, tetraphenylphosphonium monochloroacetate, tetraphenylphosphonium dichloroacetate, tetraphenylphosphonium trichloroacetate, tetraphenylphosphonium hydroxide, tetraphenylphosphonium nitrate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium oxalate, tetraphenylphosphonium maleate, tetraphenylphosphonium fumarate,Examples of such tetraphenylphosphonium compounds include tetraphenylphosphonium citrate, tetraphenylphosphonium carbonate, bistetraphenylphosphonium oxalate, bistetraphenylphosphonium maleate, bistetraphenylphosphonium fumarate, bistetraphenylphosphonium citraconic acid, bistetraphenylphosphonium citrate, and bistetraphenylphosphonium carbonate.

[0143] On the other hand, specific examples of the ammonium salt (Xc-4) include tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butanoate, tetramethylammonium benzoate, tetramethylammonium phthalate, tetramethylammonium isophthalate, tetramethylammonium terephthalate, tetramethylammonium salicylate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium monochloroacetate, tetramethylammonium dichloroacetate, tetramethylammonium trichloroacetate, tetramethylammonium hydroxide, tetramethylammonium nitrate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium monomethylsulfate, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium maleate, tetramethylammonium fumarate, tetramethylammonium citraconate, tetramethylammonium citrate, and tetramethylammonium carbonate. ammonium, bistetramethylammonium oxalate, bistetramethylammonium malonate, bistetramethylammonium maleate, bistetramethylammonium fumarate, bistetramethylammonium citraconate, bistetramethylammonium citrate, bistetramethylammonium carbonate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butanoate, tetraethylammonium benzoate, tetraethylammonium phthalate, tetraethylammonium isophthalate, tetraethylammonium terephthalate, tetraethylammonium salicylate, tetraethylammonium trifluoromethanesulfonate, tetraethylammonium trifluoroacetate, tetraethylammonium monochloroacetate, tetraethylammonium dichloroacetate, tetraethylammonium trichloroacetate, tetraethylammonium hydroxide, tetraethylammonium nitrate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium monomethylsulfate,Tetraethylammonium oxalate, tetraethylammonium malonate, tetraethylammonium maleate, tetraethylammonium fumarate, tetraethylammonium citraconate, tetraethylammonium citrate, tetraethylammonium carbonate, bistetraethylammonium oxalate, bistetraethylammonium malonate, bistetraethylammonium maleate, bistetraethylammonium fumarate, bistetraethylammonium citraconate, bistetraethylammonium citrate, bistetraethylammonium carbonate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butanoate, tetrapropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dipropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dipropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dipropylammonium benzoate, tetra ...benzoate, Tetrapropylammonium dichloroacetate, tetrapropylammonium trichloroacetate, tetrapropylammonium hydroxide, tetrapropylammonium nitrate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrapropylammonium monomethylsulfate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium maleate, tetrapropylammonium fumarate, tetrapropylammonium citraconate, tetrapropylammonium citrate, tetrapropylammonium carbonate, bistetrapropylammonium oxalate, bistetrapropylammonium malonate, bistetrapropylammonium maleate, bistetrapropylammonium fumarate, bistetrapropylammonium citraconate, bistetrapropylammonium citrate, bistetrapropylammonium carbonate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butanoate, tetrabutylammonium benzoate,Examples of the ammonium nitrate include tetrabutylammonium phthalate, tetrabutylammonium isophthalate, tetrabutylammonium terephthalate, tetrabutylammonium salicylate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluoroacetate, tetrabutylammonium monochloroacetate, tetrabutylammonium dichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, tetrabutylammonium nitrate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium methanesulfonate, tetrabutylammonium monomethylsulfate, tetrabutylammonium oxalate, tetrabutylammonium malonate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citraconate, tetrabutylammonium citrate, tetrabutylammonium carbonate, bistetrabutylammonium oxalate, bistetrabutylammonium malonate, bistetrabutylammonium maleate, bistetrabutylammonium fumarate, bistetrabutylammonium citraconate, bistetrabutylammonium citrate, and bistetrabutylammonium carbonate.

[0144] Examples of alkali metal salts include lithium formate, lithium acetate, lithium propionate, lithium butanoate, lithium benzoate, lithium phthalate, lithium isophthalate, lithium terephthalate, lithium salicylate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium monochloroacetate, lithium dichloroacetate, lithium trichloroacetate, lithium hydroxide, lithium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium methanesulfonate, lithium hydrogen oxalate, lithium hydrogen malonate, lithium hydrogen maleate, Lithium hydrogen fumarate, lithium hydrogen citraconic acid, lithium hydrogen citrate, lithium hydrogen carbonate, lithium oxalate, lithium malonate, lithium maleate, lithium fumarate, lithium citraconic acid, lithium citrate, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butanoate, sodium benzoate, sodium phthalate, sodium isophthalate, sodium terephthalate, sodium salicylate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, Sodium dichloroacetate, sodium trichloroacetate, sodium hydroxide, sodium nitrate, sodium chloride, sodium bromide, sodium iodide, sodium methanesulfonate, sodium hydrogen oxalate, sodium hydrogen malonate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium hydrogen citraconate, sodium hydrogen citrate, sodium bicarbonate, sodium oxalate, sodium malonate, sodium maleate, sodium fumarate, sodium citraconate, sodium citrate, sodium carbonate, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium benzoate, potassium phthalate, potassium isophthalate, potassium terephthalate, potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, potassium trichloroacetate, potassium hydroxide, potassium nitrate, potassium chloride, potassium bromide, potassium iodide, potassium methanesulfonate, potassium hydrogen oxalate, potassium hydrogen malonate, potassium hydrogen maleate, potassium hydrogen fumarate, potassium hydrogen citraconate,Examples include potassium hydrogen citrate, potassium hydrogen carbonate, potassium oxalate, potassium malonate, potassium maleate, potassium fumarate, potassium citraconate, potassium citrate, and potassium carbonate.

[0145] In the present invention, a polysiloxane (Xc-10) having an ammonium salt, a sulfonium salt, a phosphonium salt, or an iodonium salt as part of its structure may be blended as the crosslinking catalyst (Xc) in the composition for forming a resist underlayer film.

[0146] As a raw material used to produce (Xc-10) used here, a compound represented by the following general formula (Xm) can be used. R 1A A1 R 2A A2 R 3A A3 Si(OR 0A ) (4-A1-A2-A3) (Xm) (In the general formula (Xm), R 0A is a hydrocarbon group having 1 to 6 carbon atoms, and R 1A , R 2A , and R 3A At least one of these is an organic group having an ammonium salt, a sulfonium salt, a phosphonium salt, or an iodonium salt, and the other is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. A1, A2, and A3 are 0 or 1, and 1≦A1+A2+A3≦3.

[0147] where R 0A Examples of such alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and a phenyl group.

[0148] Examples of Xm include compounds represented by the following general formula (Xm-1), which are hydrolyzable silicon compounds having a sulfonium salt as part of their structure. [ka]

[0149] (In general formula (Xm-1), R SA1 , and R SA2 represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, or the like. SA1 and R SA2 may form a ring together with the sulfur atom to which they are attached, and when they form a ring, R SA1 , and R SA2 R represents an alkylene group having 1 to 6 carbon atoms. SA3 represents a linear, branched, or cyclic alkylene or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like.

[0150] In the above general formula (Xm-1), (Si) is written to indicate the bonding site with Si.

[0151] X -Examples include hydroxide ion, fluorine ion, chloride ion, bromide ion, iodide ion, formate ion, acetate ion, propionate ion, butanoate ion, pentanoate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleate ion, linolenate ion, benzoate ion, p-methylbenzoate ion, p-butylbenzoate ion, phthalate ion, isophthalate ion, terephthalate ion, salicylate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, trichloroacetate ion, Examples of the ion include nitrate ion, chlorate ion, perchlorate ion, bromate ion, iodate ion, methanesulfonate ion, benzenesulfonate ion, toluenesulfonate ion, monomethylsulfate ion, hydrogen sulfate ion, oxalate ion, malonate ion, methylmalonate ion, ethylmalonate ion, propylmalonate ion, butylmalonate ion, dimethylmalonate ion, diethylmalonate ion, succinate ion, methylsuccinate ion, glutarate ion, adipate ion, itaconate ion, maleate ion, fumarate ion, citraconic acid ion, citrate ion, and carbonate ion.

[0152] Specific examples of the cation moiety of the compound represented by the above general formula (Xm-1) include the following ions. [ka]

[0153] As Xm, for example, a compound represented by the following general formula (Xm-2) can be exemplified as a hydrolyzable silicon compound having an iodonium salt as part of its structure. [ka] (In the general formula (Xm-2), R IA1R represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, or the like. IA2 represents a linear, branched, or cyclic alkylene or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like.

[0154] In the general formula (Xm-2), (Si) is used to indicate the bonding site with Si. - is as described above.

[0155] Specific examples of the cation moiety of the compound represented by the above general formula (Xm-2) include the following ions.

[0156] [ka]

[0157] Examples of Xm include compounds represented by the following general formula (Xm-3), which are hydrolyzable silicon compounds having a phosphonium salt as part of their structure. [ka] (In general formula (Xm-3), R PA1 , R PA2 , and R PA3represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, or the like. PA1 and R PA2 may form a ring together with the phosphorus atom to which they are attached, and when they form a ring, R PA1 , and R PA2 R represents an alkylene group having 1 to 6 carbon atoms. PA4 is a linear, branched, or cyclic alkylene or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like.

[0158] In the general formula (Xm-3), (Si) is used to indicate the bonding site with Si. - is as described above.

[0159] Specific examples of the cation moiety of the compound represented by the above general formula (Xm-3) include the following ions.

[0160] [ka]

[0161] [ka]

[0162] As Xm, for example, a hydrolyzable silicon compound having an ammonium salt as part of its structure, such as a compound represented by the following general formula (Xm-4), can be mentioned. [ka] (In general formula (Xm-4), R NA1 , R NA2 , and R NA3 each represents a hydrogen atom, a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like. NA1 and R NA2 may form a ring together with the nitrogen atom to which they are attached, and when they form a ring, R NA1 , and R NA2 R represents an alkylene group having 1 to 6 carbon atoms, or a nitrogen-containing heterocyclic ring, or a heteroaromatic ring. NA4 R represents a linear, branched, or cyclic alkylene or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like. NA1 and R NA2 , or R NA1 and R NA4 When a ring structure is formed and an unsaturated nitrogen is contained, n N3 = 0, otherwise n N3 =1.)

[0163] In the general formula (Xm-4), (Si) is used to indicate the bonding site with Si. - is as described above.

[0164] Specific examples of the cation moiety of the compound represented by the above general formula (Xm-4) include the following ions.

[0165] [ka]

[0166]

change

[0167]

change

[0168]

change

[0169]

change

[0170]

change

[0171]

change

[0172]

change

[0173]

change

[0174]

change

[0175]

change

[0176]

change

[0177] [ka]

[0178] To produce (Xc-10), the hydrolyzable silicon compound used together with (Xm-1), (Xm-2), (Xm-3), and (Xm-4) can be, for example, the hydrolyzable monomer (Sm). A hydrolyzable metal compound (Mm) represented by the general formula (Mm) may also be added.

[0179] One or more of the monomers (Xm-1), (Xm-2), (Xm-3), and (Xm-4) shown above, one or more of (Sm), and if necessary, one or more of (Mm), can be selected and mixed before or during the reaction to form (Xc-10). The reaction conditions may be the same as those used in the synthesis of the thermally crosslinkable polysiloxane (Sx).

[0180] The molecular weight of the resulting crosslinking catalyst (Xc-10) can be adjusted not only by selecting the monomer but also by controlling the reaction conditions during polymerization, but a weight-average molecular weight of 100,000 or less prevents the generation of foreign matter or coating spots, so it is preferable to use one of 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. Note that the data regarding the weight-average molecular weight above was measured by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an eluent, and polystyrene as a standard substance, and the molecular weight was expressed in terms of polystyrene.

[0181] The crosslinking catalysts (Xc-1), (Xc-2), (Xc-3), (Xc-4), and (Xc-10) can be used alone or in combination of two or more. The amount of the crosslinking catalyst added is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, per 100 parts by mass of the base polymer (the thermally crosslinkable polysiloxane (Sx) obtained by the above method).

[0182] (organic acid) 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 or higher organic acid having 1 to 30 carbon atoms. Examples of the acid to be added in this case include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and citric acid. Particularly preferred are oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid, etc. Furthermore, to maintain stability, two or more acids may be mixed and used. The amount of organic acid added is preferably 0.001 to 25 parts by mass, more preferably 0.01 to 15 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of silicon contained in the composition for forming a silicon-containing resist underlayer film of the present invention.

[0183] Alternatively, the organic acid may be added so that the pH of the composition for forming a silicon-containing resist underlayer film of the present invention is preferably 0≦pH≦7, more preferably 0.3≦pH≦6.5, and even more preferably 0.5≦pH≦6.

[0184] (water) In the present invention, water may be added to the composition for forming a silicon-containing resist underlayer film. Addition of water hydrates the polysiloxane compound in the composition for forming a silicon-containing resist underlayer film of the present invention, thereby improving lithography performance. The water content in the solvent component of the composition for forming a silicon-containing resist underlayer film of the present invention is preferably greater than 0% by mass and less than 50% by mass, particularly preferably 0.3 to 30% by mass, and even more preferably 0.5 to 20% by mass. When the amount of water added is less than 50% by mass, the uniformity of the silicon-containing resist underlayer film is improved and repellency does not occur. On the other hand, when the amount of water added is greater than 0% by mass, the lithography performance is improved.

[0185] The amount of the total solvent including water used is preferably 100 to 100,000 parts by mass, and particularly preferably 200 to 50,000 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane that is the base polymer.

[0186] (stabilizer) Furthermore, in the present invention, a stabilizer can be added to the composition for forming a silicon-containing resist underlayer film. A monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent can be added as a stabilizer. In particular, the addition of a stabilizer described in paragraphs

[0181] and

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

[0187] (surfactant) Furthermore, in the present invention, if necessary, a surfactant can be added to the composition for forming a silicon-containing resist underlayer film. Specifically, the materials described in paragraph

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

[0188] (High boiling point solvent) Furthermore, in the present invention, a high boiling point solvent having a boiling point of 180° C. or higher can be added to the composition as needed. Examples of such high boiling point solvents include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, gamma butyrolactone, tripropylene glycol monomethyl ether, and diacetone alcohol. Examples of the high-boiling point solvent include ethanol, n-nonyl acetate, ethylene glycol monoethyl ether acetate, 1,2-diacetoxyethane, 1-acetoxy-2-methoxyethane, 1,2-diacetoxypropane, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, etc. The amount of the high-boiling point solvent to be blended is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, based on the solvent components.

[0189] [Pattern formation method] One of the pattern formation methods of the present invention is a method for forming a pattern on a workpiece, comprising the steps of: 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 composition for forming a silicon-containing resist underlayer film described above; forming a resist upper layer film on the silicon-containing resist underlayer film using a resist upper layer film composition comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a step of transferring the pattern to the silicon-containing resist underlayer film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; a step of transferring the pattern to the organic film by etching using the silicon-containing resist underlayer film to which the pattern has been transferred as a mask; a step of transferring the pattern to the workpiece by etching using the organic film to which the pattern has been transferred as a mask; This is a pattern formation method (the so-called "multilayer resist method") that includes the steps of:

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

[0191] One of the pattern formation methods of the present invention is a method for forming a pattern on a workpiece, comprising the steps of: forming a silicon-containing resist underlayer film on a workpiece using the composition for forming a silicon-containing resist underlayer film described above; forming a resist upper layer film on the silicon-containing resist underlayer film using a resist upper layer film composition comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a step of transferring the pattern to the silicon-containing resist underlayer film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the workpiece by dry etching using the silicon-containing resist underlayer film to which the pattern has been transferred as a mask; The pattern forming method includes the steps of:

[0192] The pattern obtained by incorporating the polyvalent ammonium salt compound of the present invention into the composition for forming a silicon-containing resist underlayer film can form a fine pattern on a substrate with excellent LWR and CDU by optimizing the combination of a hard mask and an organic film, as described above. Furthermore, since the silicon-containing resist underlayer film remaining after pattern formation can be easily removed by etching or the like, residues that cause defects can be suppressed, and substrate damage due to excessive etching conditions can also be prevented.

[0193] In the positive pattern formation method, a photoresist film (resist upper layer film) is formed, heat-treated, exposed to light, and then typically developed with an alkaline developer to obtain a positive resist pattern. It is also preferable to perform post-exposure baking (PEB) after exposure.

[0194] As the alkaline developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) or the like can be used.

[0195] The method for forming a circuit pattern on the resist upper layer film is preferably a pattern forming method using photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0196] The workpiece is preferably a semiconductor device substrate, or a semiconductor device substrate having any of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, and a metal oxynitride film formed thereon.

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

[0198] The present invention will be specifically explained below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these descriptions. In the following examples, % indicates mass %, and the molecular weight Mw is the weight average molecular weight in terms of polystyrene measured by GPC using tetrahydrofuran as an elution solvent. Furthermore, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0199] [Synthesis Example 1-1] A mixture of 30.6 g of compound (101), 38.1 g of compound (102), and 5.9 g of compound (110) (molar ratio: 40 / 50 / 10) was added 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 maintained at 40°C for 12 hours to allow hydrolysis and condensation. After completion of the reaction, 600 g of propylene glycol monoethyl ether (PGEE) was added, and the water and by-product alcohol used in the 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 polystyrene-equivalent molecular weight of polysiloxane compound 1 was measured and found to be Mw = 2,900.

[0200] [Synthesis Example 1-2] to [Synthesis Example 1-18] were carried out using the monomers shown in Table 1 under the same conditions as in [Synthesis Example 1-1], and the target products were obtained as polysiloxane compounds 2 to 18, respectively.

[0201] [Table 1] PhSi(OCH3)3...Compound (100) CH3Si(OCH3)3...Compound (101) Si(OCH3)4...Compound (102)

[0202] [ka]

[0203] [Synthesis example of crosslinking catalyst] [Synthesis Example 2-1] Synthesis of Compound A' [ka] 25 g of compound A was dissolved in 40 g of water. This solution was added dropwise over 30 minutes to 650 g of 7% aqueous nitric acid solution cooled to 0°C. After aging at room temperature for 24 hours, the solution was dried under reduced pressure at 50°C to obtain 57 g of the target compound A' as a white solid.

[0204] [Synthesis Example 2-2] Synthesis of Compound A'' [ka] 10 g of compound A and 40.4 g of potassium carbonate were dissolved in 200 mL of ethanol, and 41 g of methyl iodide was added dropwise to the solution at room temperature over 30 minutes. After aging at room temperature for 24 hours, the resulting reaction solution was filtered and dried under reduced pressure to obtain 8.7 g of the target compound A'' as a white solid.

[0205] [Synthesis Example 2-3] to [Synthesis Example 2-7] were carried out using the raw materials shown in Table 2 under the same conditions as in Synthesis Example 2-1, and the target products were obtained in each case. In addition, Synthesis Example 2-8 to Synthesis Example 2-13 were carried out using the raw materials and alkylating agents shown in Table 3 under the same conditions as in Synthesis Example 2-2, and the target products were obtained in each case. [Table 2] [Table 3]

[0206] [Reaction raw materials] [ka]

[0207] [Object] [ka]

[0208] [Comparative Synthesis Example 1-1] Synthesis of sulfonium salt-containing polysiloxane compound R A mixture of 61.3 g of compound (101) and 24.4 g of compound (120) was added to a mixture of 120 g of methanol, 0.1 g of 10% nitric acid, and 60 g of deionized water, and the mixture was maintained at 40°C for 12 hours to allow hydrolysis and condensation. After completion of the reaction, 300 g of propylene glycol monoethyl ether (PGEE) was added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure, yielding 250 g of a PGEE solution of sulfonium salt-containing polysiloxane compound R (compound concentration 20%). The polystyrene-equivalent molecular weight of polysiloxane compound R was measured and found to be Mw = 2,000.

[0209] [Examples 1-1 to 1-58 and Comparative Examples 1-1 to 1-4] Polysiloxane compounds 1 to 18 obtained in the above synthesis examples, a polyvalent ammonium salt compound represented by the above general formula (A-1) as a crosslinking catalyst or a comparative crosslinking catalyst, an acid, a photoacid generator (PAG-1 to 7 listed in Table 7), a solvent, and water were mixed in the proportions shown in Tables 4 to 6, and filtered through a 0.1 μm fluororesin filter to prepare silicon-containing underlayer film-forming composition solutions, designated Sol. 1 to 62, respectively.

[0210] [Table 4]

[0211] [Table 5]

[0212] [Table 6]

[0213] The crosslinking catalysts used were as follows: XL-1...Compound (A') XL-2...Compound (A'') XL-3...Compound (B') XL-4...Compound (C') XL-5...Compound (D') XL-6...Compound (E') XL-7...Compound (F') XL-8...Compound (A''') XL-9...Compound (B'') XL-10...Compound (C'') XL-11...Compound (D'') XL-12...Compound (E'') XL-13...Compound (F'') XL-14 Triphenylsulfonium nitrate XL-15 Tetramethylammonium Nitrate XL-16 Tetraoctylammonium Nitrate XL-17: Sulfonium salt-containing polysiloxane compound (R)

[0214] The solvents used were as follows: PGEE: Propylene glycol monoethyl ether PGME: Propylene glycol monomethyl ether GBL: Gamma Butyrolactone DAA: Diacetone alcohol

[0215] [Table 7]

[0216] (EUV patterning test) Sol. 1 to 62, which are compositions for forming silicon-containing resist underlayer films, were spin-coated onto a silicon wafer and heated at 220° C. for 60 seconds to prepare Films 1 to 62, which are silicon-containing resist underlayer films with a thickness of 25 nm.

[0217] Next, a resist material containing the following components dissolved in the proportions shown in Table 8 was spin-coated onto Films 1 to 62 and pre-baked for 60 seconds at 105°C using a hot plate to produce a 60nm thick resist top layer film. This was then exposed using an ASML EUV scanner NXE3300 (NA 0.33, σ 0.9 / 0.6, quadruple-pole illumination, wafer dimensions with a 46nm pitch and a hole pattern mask with a +20% bias), subjected to PEB on a hot plate at 100°C for 60 seconds, and developed for 30 seconds in a 2.38% by mass TMAH aqueous solution to obtain a hole pattern with a dimension of 23nm. Using a critical dimension SEM (CG5000) manufactured by Hitachi High-Technologies Corporation, the exposure dose when holes were formed with a dimension of 23 nm was measured and used as the sensitivity. The dimensions of 50 holes were also measured and the dimension variation (CDU, 3σ) was calculated. The results are shown in Tables 9 and 10.

[0218] The polymer, quencher, sensitizer, surfactant and organic solvent used as the resist material are as follows:

[0219] [ka]

[0220] [ka]

[0221] [ka]

[0222] Surfactant: 3M FC-4430 PGMEA: Propylene glycol monomethyl ether acetate CyHO: Cyclohexanone PGME: Propylene glycol monomethyl ether

[0223] [Table 8]

[0224] (Silicon-containing resist underlayer film etching test) Sol. 1 to 62, which are compositions for forming silicon-containing resist underlayer films, were spin-coated onto a silicon wafer and heated at 220° C. for 60 seconds to prepare Films 1 to 62, which are silicon-containing resist underlayer films with a thickness of 25 nm. These silicon-containing resist underlayer films were subjected to an etching test under the following etching conditions.

[0225] Etching test using CHF3 / CF4 gas Equipment: Tokyo Electron Ltd. dry etching equipment Telius SP Etching test: Chamber pressure 10Pa Upper / Lower RF Power 200W / 100W CHF3 gas flow rate 50ml / min CF4 gas flow rate 50ml / min N2 gas flow rate 100 ml / min Processing time: 20 seconds

[0226] [Table 9]

[0227] [Table 10]

[0228] As shown in Comparative Examples 1-1 to 1-4 in Tables 9 and 10, Films 59 to 62, which did not use the polyvalent ammonium salt compound of the present invention represented by the general formula (A-1) as a crosslinking catalyst, were found to have deteriorated CDU or insufficient etching rates. On the other hand, as shown in Examples 1-1 to 1-58, Films 1 to 58, which used the polyvalent ammonium salt compound of the present invention represented by the general formula (A-1) as a crosslinking catalyst, were found to have improved CDU and sufficient etching rates because the reactivity of the silicon polymer was increased due to the polyvalent nature of the crosslinking catalyst, allowing the formation of a strong film that suppresses diffusion into the upper layer resist.

[0229] [Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-4] (ArF patterning test) A 200 nm thick spin-on carbon film ODL-102 (carbon content 89% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was formed on a silicon wafer. Silicon-containing resist underlayer film-forming compositions Sols. 1 to 5, 11 to 13, 28 to 30, 51 to 54, and 59 to 62 were applied onto the spin-on carbon film and heated at 220°C for 60 seconds to produce 20 nm thick silicon-containing resist underlayer films Films 1 to 5, 11 to 13, 28 to 30, 51 to 54, and 59 to 62.

[0230] Next, a positive development ArF resist solution (PR-1) shown in Table 11 was applied onto the silicon-containing resist underlayer film and baked at 110°C for 60 seconds to form a photoresist film with a thickness of 100 nm. Further, an immersion protective film material (TC-1) shown in Table 12 was applied onto the photoresist film and baked at 90°C for 60 seconds to form a protective film with a thickness of 50 nm. These were then exposed using an ArF immersion exposure system (ASML XT-1900i, NA 1.35, σ 0.97 / 0.77, 35° dipole polarized illumination), baked at 100°C for 60 seconds (PEB), and developed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, yielding a 40 nm 1:1 positive line-and-space pattern. The LWR was observed using a Hitachi High-Technologies Corporation CG5000 electron microscope. The results are shown in Table 13.

[0231] [Table 11]

[0232] ArF resist polymer 1 [molecular weight (Mw) = 7,800, dispersity (Mw / Mn) = 1.78]: [ka]

[0233] Acid generator: PAG-A [ka]

[0234] Base: Quencher [ka]

[0235] Surfactant: 3M FC-4430

[0236] Protective film polymer [molecular weight (Mw) = 8,800, dispersity (Mw / Mn) = 1.69]

[0237] [ka]

[0238] [Table 12]

[0239] [Table 13]

[0240] As shown in Examples 2-1 to 2-15 in Table 13, Films 1 to 5, 11 to 13, 28 to 30, and 51 to 54, which used the polyvalent ammonium salt compound of the present invention represented by the general formula (A-1) as a crosslinking catalyst, formed strong films due to the effect of the highly reactive crosslinking catalyst, thereby suppressing diffusion into the upper layer resist and improving LWR.On the other hand, as shown in Comparative Examples 2-1 to 2-4, Films 59 to 62, which did not use the polyvalent ammonium salt compound of the present invention, showed inferior LWR.

[0241] The present specification includes the following aspects. [1]: A polyvalent ammonium salt compound having two or more ammonium ions in one molecule, characterized in that it is represented by the following general formula (A-1): [ka] (In the formula, R1 is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and may contain one or more nitrogen atoms; R2, R3, R4, R5, R6, and R7 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and may contain one or more nitrogen atoms. In addition, any two or more selected from R1, R2, R3, R4, R5, R6, and R7 may bond to each other to form a ring together with the nitrogen atom in the formula. A - represents an organic or inorganic anion that serves as a counter ion of the ammonium cation, excluding bistrifluoromethanesulfonylimide; and n is an integer of 2 to 10. [2]: The above A -is formate, acetate, propionate, butyrate, hexanoate, benzoate, t-butylbenzoate, trichloroacetate, trifluoroacetate, 2-hydroxy-2,2-bis(trifluoromethyl)acetate, trimethylacetate, pentafluoropropionate, methanesulfonate, butanesulfonate, benzenesulfonate, toluenesulfonate, trifluoromethanesulfonate, methylsulfate ion, chloride ion, bromide ion, iodide ion, fluoride ion, cyanide ion, nitrate ion, nitrite ion, or hydroxide ion. [3]: The polyvalent ammonium salt compound according to [1] or [2] above, characterized in that the polyvalent ammonium salt compound is represented by the following general formula (B-1), the following general formula (B-2), the following general formula (B-3) or the following general formula (B-4): [ka] (R in the formula 11 , R 12 , R 13 and R 14 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.) [ka] (R in the formula 21 , R 22 , R 23 , R 24 , R 25 and R 26 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.) [ka] (R in the formula 31 , R32 , R 33 , R 34 , R 35 , R 36 and R 37 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.) [ka] (R in the formula 41 , R 42 , and R 43 R are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 and R 53 A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. - is the same as above.) [4]: A composition for forming a silicon-containing resist underlayer film, comprising any one of the polyvalent ammonium salt compounds [1] to [3] above, and a thermally crosslinkable polysiloxane. [5]: The composition for forming a silicon-containing resist underlayer film according to [4] above, wherein the thermally crosslinkable polysiloxane 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): [ka] [ka] [ka] (In the formula, R 1 , R 2 and R 3 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different. [6]: The composition for forming a silicon-containing resist underlayer film according to [4] or [5] above, further comprising an acid generator. [7]: The composition for forming a silicon-containing resist underlayer film according to the above [6], wherein the acid generator is a photoacid generator that generates an acid by the action of high-energy rays. [8]: A method for forming a pattern on a workpiece, comprising: 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 a composition for forming a silicon-containing resist underlayer film according to any one of [4] to [7] above; forming a resist upper layer film on the silicon-containing resist underlayer film using a resist upper layer film composition comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a step of transferring the pattern to the silicon-containing resist underlayer film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; a step of transferring the pattern to the organic film by etching using the silicon-containing resist underlayer film to which the pattern has been transferred as a mask; a step of transferring the pattern to the workpiece by etching using the organic film to which the pattern has been transferred as a mask; A pattern forming method comprising the steps of: [9]: A method for forming a pattern on a workpiece, comprising: forming a hard mask on a workpiece by a CVD method; forming a silicon-containing resist underlayer film on the hard mask using any one of the compositions for forming a silicon-containing resist underlayer film described in [4] to [7] above; forming a resist upper layer film on the silicon-containing resist underlayer film using a resist upper layer film composition comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a step of transferring the pattern to the silicon-containing resist underlayer film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the hard mask by dry etching using the silicon-containing resist underlayer film to which the pattern has been transferred as a mask; transferring the pattern to the workpiece by dry etching using the hard mask to which the pattern has been transferred as a mask; A pattern forming method comprising the steps of:

[10] : The pattern forming method according to [8] or [9] above, characterized in that a circuit pattern is formed on the resist upper layer film by using photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing using an electron beam, nanoimprinting, or a combination thereof.

[11] : The pattern formation method according to any one of [8] to

[10] above, characterized in that the workpiece is a semiconductor device substrate, or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film formed thereon.

[12] : The pattern formation method according to

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

[0242] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A polyvalent ammonium salt compound having two or more ammonium ions in one molecule, characterized in that it is represented by the following general formula (A-1): 【Chemical 1】 (In the formula, R １ represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent and which may contain one or more nitrogen atoms, and R ２ , R ３ , R ４ , R ５ , R ６ and R ７ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and may contain one or more nitrogen atoms. １ , R ２ , R ３ , R ４ , R ５ , R ６ and R ７ Any two or more selected from may be bonded to each other to form a ring together with the nitrogen atom in the formula. － represents an organic or inorganic anion that serves as a counter ion of the ammonium cation, excluding bistrifluoromethanesulfonylimide; and n is an integer of 2 to 10.

2. The above A － is formate, acetate, propionate, butyrate, hexanoate, benzoate, t-butylbenzoate, trichloroacetate, trifluoroacetate, 2-hydroxy-2,2-bis(trifluoromethyl)acetate, trimethylacetate, pentafluoropropionate, methanesulfonate, butanesulfonate, benzenesulfonate, toluenesulfonate, trifluoromethanesulfonate, methylsulfate ion, chloride ion, bromide ion, iodide ion, fluoride ion, cyanide ion, nitrate ion, nitrite ion, or hydroxide ion.

3. The polyvalent ammonium salt compound according to claim 1, characterized in that the polyvalent ammonium salt compound is represented by the following general formula (B-1), the following general formula (B-2), the following general formula (B-3), or the following general formula (B-4): 【Chemistry 2】 (R in the formula １１ , R １２ , R １３ and R １４ A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. － is the same as above.) 【Chemistry 3】 (R in the formula ２１ , R ２２ , R ２３ , R ２４ , R ２５ and R ２６ A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. － is the same as above.) 【Chemistry 4】 (R in the formula ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ and R ３７ A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. － is the same as above.) 【Chemistry 5】 (R in the formula ４１ , R ４２ , and R ４３ R are each independently a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. ４４ , R ４５ , R ４６ , R ４７ , R ４８ , R ４９ , R ５０ , R ５１ , R ５２ and R ５３ A each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. － is the same as above.)

4. A composition for forming a silicon-containing resist underlayer film, comprising the polyvalent ammonium salt compound according to any one of claims 1 to 3 and a thermally crosslinkable polysiloxane.

5. 5. The composition for forming a silicon-containing resist underlayer film according to claim 4, wherein the thermally crosslinkable polysiloxane comprises 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): 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 (In the formula, R １ , R ２ and R ３ are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different.

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

7. 7. The composition for forming a silicon-containing resist underlayer film according to claim 6, wherein the acid generator is a photoacid generator that generates an acid by the action of high-energy rays.

8. A method for forming a pattern on a workpiece, comprising: 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 composition for forming a silicon-containing resist underlayer film according to claim 4; forming a resist upper layer film on the silicon-containing resist underlayer film using a resist upper layer film composition comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a step of transferring the pattern to the silicon-containing resist underlayer film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; a step of transferring the pattern to the organic film by etching using the silicon-containing resist underlayer film to which the pattern has been transferred as a mask; a step of transferring the pattern to the workpiece by etching using the organic film to which the pattern has been transferred as a mask; A pattern forming method comprising the steps of:

9. A method for forming a pattern on a workpiece, comprising: forming a hard mask on a workpiece by a CVD method; forming a silicon-containing resist underlayer film on the hard mask using the composition for forming a silicon-containing resist underlayer film according to claim 4; forming a resist upper layer film on the silicon-containing resist underlayer film using a resist upper layer film composition comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a step of transferring the pattern to the silicon-containing resist underlayer film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the hard mask by dry etching using the silicon-containing resist underlayer film to which the pattern has been transferred as a mask; transferring the pattern to the workpiece by dry etching using the hard mask to which the pattern has been transferred as a mask; A pattern forming method comprising the steps of:

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

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

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

13. 10. The pattern forming method according to claim 9, wherein the workpiece is a semiconductor device substrate, or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film formed thereon.

14. 13. The pattern formation method according to claim 12, wherein the metal 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.

15. 14. The pattern formation method according to claim 13, wherein the metal 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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