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

Abstract

To provide a composition for forming a silicon-containing underlay film of a resist including a heat-curable silicon-containing material for improving sensibility, LWR, and resolution of an upper layer resist, and further contributing to prevention of pattern collapse in photolithography using a high energy ray, and a pattern formation method using the composition for forming a silicon-containing underlay film of a resist.SOLUTION: A composition for forming a silicon-containing underlay film of a resist having a non-condensation reacting-organic group reacting with a radical chemical species including a condensation reaction type heat curable silicon-containing material (Sx), which is a polysiloxane, includes more than 0 and 70 mol% or less of any one or more of a repeating unit represented by general formula (Sx-4), and a repeating unit represented by general formula (Sx-5) where an organic group remains unreacted even after thermosetting reaction of the polysiloxane resin.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a silicon-containing resist underlayer film formation composition and a pattern formation method. [Background technology]

[0002] With the expansion of the IoT market, there is an increasing demand for higher integration, higher speed, and lower power consumption in LSIs, leading to rapid miniaturization of pattern rules. Logic devices, in particular, are driving this miniaturization. As cutting-edge miniaturization technology, mass production of 10nm node devices is underway using double, triple, and quadruple patterning in ArF immersion lithography, and research is progressing on 7nm node devices using next-generation 13.5nm extreme ultraviolet (EUV) lithography.

[0003] In EUV lithography, chemically amplified resist compositions can be applied, and line patterns with line widths of 20 nm or less can be formed. However, when polymer-based resist compositions used in ArF lithography are used in EUV lithography, the large molecular size of the base polymer they contain results in roughness on the pattern surface, making pattern control difficult. Therefore, various low-molecular-weight materials have been proposed.

[0004] Molecular resist compositions are resist compositions mainly composed of low-molecular-weight compounds and do not contain the base polymers used in polymer-based resist compositions. Molecular resist compositions are expected to be one of the effective measures for forming fine patterns. For example, molecular resist compositions containing sulfonium salts provide a resist film that exhibits high sensitivity, excellent resolution and LWR, and are extremely effective for precise microfabrication (Patent Document 1). Although the molecular size of the molecular resist composition is smaller than that of polymer materials, thus improving roughness is expected. However, molecular resist compositions using the chemical amplification mechanism have not yet achieved satisfactory performance because it is difficult to control the diffusion of reactive species. Furthermore, in EUV resist compositions, it is necessary to achieve not only roughness but also high sensitivity and high resolution simultaneously, and further improvements are required.

[0005] On the other hand, one factor that makes material development for EUV lithography difficult is the need to precisely form line patterns with extremely fine line widths as miniaturization progresses. When miniaturization is performed while keeping the thickness of the photoresist film the same, i.e., when the pattern width is reduced, the resolution performance of the photoresist film decreases. Furthermore, when attempting to develop the photoresist film with a developer, the aspect ratio becomes too large, resulting in the problem of pattern collapse.

[0006] One method to solve these problems is to form a silicon-containing resist underlayer film between the substrate and the photoresist film, which has excellent adhesion to the photoresist film (Patent Document 2). Although Patent Document 2 describes a multilayer resist method using the above-mentioned silicon-containing resist underlayer film, it does not mention molecular resists at all.

[0007] Furthermore, while curing a film with crosslinkable organic groups is a known technique (Patent Documents 3 and 4), when the film is sufficiently cured by heating or other means, the crosslinkable organic groups do not remain intact. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2022-055315 [Patent Document 2] Japanese Patent Publication No. 2012-237975 [Patent Document 3] Japanese Patent Publication No. 2017-97240 [Patent Document 4] International Publication No. 2019 / 124514 [Overview of the project] [Problems that the invention aims to solve]

[0009] The present invention has been made in view of the above circumstances, and aims to provide a resist underlayer film formation composition containing a thermosetting silicon-containing material that improves the sensitivity, LWR, and resolution of the upper layer resist in photolithography using high-energy rays, and further contributes to preventing pattern collapse, as well as a pattern formation method using the resist underlayer film formation composition. [Means for solving the problem]

[0010] To solve the above problems, the present invention provides a silicon-containing resist underlayer film forming composition comprising a condensation reaction type thermosetting silicon-containing material (Sx) which is a polysiloxane resin, wherein the material (Sx) has non-condensation reactive organic groups that react with radical chemical species generated by irradiation with high-energy rays, and contains in the resin in an amount greater than 0 and less than 70 mol% of either a repeating unit represented by the following general formula (Sx-4) or a repeating unit represented by the following general formula (Sx-5), and the organic groups remain unreacted even after the thermosetting reaction of the polysiloxane resin. [ka] (In the formula, R 4 (This is a non-aromatic substituent that may contain a hydrogen atom, a hydroxyl group, or a monovalent heteroatom having 1 to 30 carbon atoms.)

[0011] For such a composition for forming a silicon-containing resist underlayer film, the sensitivity, LWR, and resolution of the upper-layer resist can be improved, and furthermore, pattern collapse such as line patterns can be prevented.

[0012] In the present invention, the polysiloxane resin of the material (Sx) contains any one or more of a repeating unit represented by the following general formula (Sx-1), a repeating unit represented by the following general formula (Sx-2), and a partial structure represented by the following general formula (Sx-3), and these repeating units are contained in the resin in an amount of 30 to 99 mol%, and any one or more of the repeating unit represented by the above general formula (Sx-4) or the repeating unit represented by the above general formula (Sx-5) are contained in the resin in an amount of 1 to 70 mol%. Further, it preferably contains a crosslinking catalyst (Xc) for siloxane polymerization, an alcohol-based organic solvent, and water.

Chemical formula

[0013] For such a composition for forming a silicon-containing resist underlayer film, the sensitivity, LWR, and resolution of the upper-layer resist become better, and pattern collapse can be prevented.

[0014] Further, the organic groups R 1 , R 2 and R 3 can be organic groups represented by the following general formula R 5 or R 6 .

Chemical formula

[0015] By combining such crosslinking groups with the thermosetting silicon-containing material of the present invention, it is possible to obtain a resist underlayer film that contributes to preventing pattern collapse of the upper resist layer.

[0016] Furthermore, the organic group R 5 However, the following general formula R 8 The organic group is represented by the organic group R 6 However, the following general formula R 9 It can be an organic group represented by . [ka] (In the formula, L 2 R is a divalent organic group having 1-10 carbon atoms that may contain an oxygen atom, 10 is a hydrogen atom or a monovalent organic group with 1-5 carbon atoms. * represents the linkage with a silicon atom.

[0017] Such crosslinking groups allow the effects of the present invention to be more fully realized.

[0018] Furthermore, the siloxane polymerization crosslinking catalyst can be a sulfonium salt, iodonium salt, phosphonium salt, ammonium salt, or a polysiloxane or alkali metal salt having these as part of its structure.

[0019] When such a crosslinking catalyst is combined with the thermosetting silicon-containing material of the present invention, the crosslinking catalyst can promote the formation of siloxane bonds when the condensation reaction type thermosetting polysiloxane hardens, thereby enabling the formation of a high-density crosslinked silicon-containing resist underlayer film.

[0020] Furthermore, the silicon-containing resist underlayer film formation composition of the present invention is A step of forming a resist underlayer film using the silicon-containing resist underlayer film formation composition, It is preferable that this method be used in a pattern forming method comprising the step of forming a resist upper film using a resist upper film composition containing a compound having polymerizable functional groups on the resist lower film.

[0021] The silicon-containing resist underlayer film formation composition exhibits a good effect in suppressing pattern deformation when used together with a resist upper layer film composition containing a compound having polymerizable functional groups.

[0022] Furthermore, the present invention includes the step of forming a resist underlayer film on a workpiece or a film formed on a workpiece using the silicon-containing resist underlayer film forming composition described above, A step of forming a resist upper layer film using a resist upper layer film composition containing a compound having polymerizable functional groups on the resist lower layer film, Pattern formation including the step of forming a circuit pattern on the resist upper layer film. method The silicon-containing resist underlayer film forming composition is heated and cured to form the resist underlayer film, The present invention provides a pattern formation method characterized by forming the circuit pattern and causing crosslinking between the resist underlayer and the resist upper layer by irradiation with high-energy rays.

[0023] Furthermore, the present invention includes the step of forming an organic film on a workpiece using a coating-type organic film material, A step of forming a resist underlayer on the organic film using the silicon-containing resist underlayer formation composition, A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern onto an organic film by etching, using the resist underlayer film on which the pattern has been transferred as a mask. The present invention provides a pattern forming method characterized by including the step of transferring the pattern to a workpiece by etching, using the organic film on which the pattern has been transferred as a mask.

[0024] Furthermore, the present invention includes a step of forming an organic hard mask mainly composed of carbon on a workpiece by CVD, The steps include forming a resist underlayer film on the organic hard mask using the silicon-containing resist underlayer film forming composition, A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern onto the organic hard mask by dry etching, using the resist underlayer film on which the pattern has been transferred as a mask. The present invention provides a pattern forming method characterized by including the step of transferring the pattern to a workpiece by dry etching using the organic hard mask on which the pattern has been transferred as a mask.

[0025] Furthermore, the present invention includes the step of forming an organic film on a workpiece using a coating-type organic film material, A step of forming an inorganic hard mask interlayer on the organic film by CVD or ALD, The process involves forming a resist underlayer on the inorganic interlayer using the silicon-containing resist underlayer formation composition described above, A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern to the inorganic interlayer by etching, using the resist underlayer film on which the circuit pattern is formed as a mask, A step of transferring the pattern onto an organic film by etching, using the inorganic interfilm on which the pattern has been transferred as a mask, The present invention provides a pattern forming method characterized by including the step of transferring the pattern to a workpiece by etching, using the organic film on which the pattern has been transferred as a mask.

[0026] Furthermore, the present invention includes a step of forming an organic hard mask mainly composed of carbon on a workpiece by CVD, The process involves forming an inorganic hard mask interlayer on the aforementioned organic hard mask by CVD or ALD, The process involves forming a resist underlayer on the inorganic interlayer using the silicon-containing resist underlayer formation composition described above, A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern to the inorganic interlayer by etching, using the resist underlayer film on which the circuit pattern is formed as a mask, A step of transferring the pattern by etching onto the organic hard mask mainly composed of carbon, using the inorganic interfilm on which the pattern has been transferred as a mask, The present invention provides a pattern forming method characterized by including the step of transferring the pattern to a workpiece by etching, using the organic hard mask on which the pattern has been transferred as a mask.

[0027] When the silicon-containing resist underlayer film formation composition of the present invention is used in the multilayer resist method described above, it is not only possible to form an upper resist pattern with good LWR and sensitivity, but also to crosslink the silicon-containing resist underlayer film with the upper resist (photoresist film) to create a strong adhesion, thereby suppressing pattern collapse and enabling the formation of semiconductor device patterns on the substrate with a high yield.

[0028] In the pattern formation method described above, the pattern formation on the resist upper film can be achieved by photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0029] After pattern formation under conditions tailored to such a photoresist film, suitable negative or positive resist patterns can be obtained by performing necessary processing.

[0030] Furthermore, in the pattern formation method described above, the workpiece can be a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film.

[0031] The pattern forming method of the present invention allows for the formation of highly accurate patterns on a substrate (film) without causing size conversion differences when forming an organic underlayer film or an organic hard mask on the workpiece.

[0032] Furthermore, in the pattern forming method described above, the metal constituting the workpiece may be silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or alloys thereof.

[0033] By using a workpiece made of such metal, negative and positive patterns can be transferred to the workpiece with high precision through accurate etching. [Effects of the Invention]

[0034] The silicon-containing resist underlayer film formation composition of the present invention can improve the sensitivity, LWR, and resolution of the upper resist and further suppress pattern deformation in photolithography using high-energy beams, particularly electron beam (EB) lithography and EUV lithography. Furthermore, the composition of the present invention not only enables the formation of an upper resist pattern with excellent LWR and pattern deformation prevention, but also provides high etching selectivity with organic materials (organic underlayer film, organic hard mask), allowing the formed photoresist pattern to be sequentially transferred to a silicon-containing resist underlayer film, an organic underlayer film, or a CVD organic hard mask using a dry etching process. Moreover, the composition of the present invention can use a molecular resist as the upper resist, and in this case as well, it can improve the sensitivity, LWR, and resolution of the resist and further suppress pattern deformation. Furthermore, in recent semiconductor device manufacturing processes, which are becoming increasingly miniaturized, multiple exposure processes are frequently used, and preventing LWR and pattern deformation in the developed pattern has a significant impact on device performance. Therefore, improving LWR and pattern deformation prevention is important. By using the silicon-containing resist underlayer film formation composition of the present invention, it is possible to form an upper resist pattern with excellent LWR and pattern deformation prevention. In addition, since the silicon-containing resist underlayer film formation composition of the present invention has a good dry etching selectivity ratio, even when the silicon-containing resist underlayer film is used as a dry etching mask, deformation of the upper resist pattern during dry etching is suppressed, and it is possible to transfer it to the substrate with high precision while maintaining excellent LWR and CDU. [Brief explanation of the drawing]

[0035] [Figure 1] This is a flowchart illustrating the pattern formation method of the present invention. [Modes for carrying out the invention]

[0036] As described above, there was a need for the development of a resist underlayer film formation composition that would enable the formation of an upper resist pattern with excellent resistance to LWR and pattern collapse.

[0037] To meet the above requirements, the inventors focused on a method for bringing a photoresist film and a silicon-containing resist underlayer film into close contact by combining a photoresist film having crosslinkable organic groups with a silicon-containing resist underlayer film having crosslinkable organic groups and crosslinking the films together.

[0038] While curing films with crosslinkable organic groups is a known technique, achieving the above-mentioned interlayer crosslinking technology requires that crosslinkable organic groups remain in the silicon-containing resist underlying film even after curing treatment such as heating. Therefore, it has been difficult to achieve both sufficient film curing and the preservation of crosslinkable organic groups with conventional techniques.

[0039] As a result of diligent research to achieve the above objective, the present inventors have discovered that a resist underlayer film formation composition containing a thermosetting silicon-containing material having a non-condensation reactive organic group that reacts with radical chemical species generated by irradiation with high-energy rays (such as electron beams) improves the sensitivity, LWR, and resolution of the resist film, provides a resist film that prevents line pattern collapse, and is extremely effective for precise microfabrication, leading to the present invention.

[0040] In other words, the present invention relates to a silicon-containing resist underlayer film formation composition comprising a condensation reaction type thermosetting silicon-containing material (Sx) which is a polysiloxane resin, wherein the material (Sx) has non-condensation reactive organic groups that react with radical chemical species generated by irradiation with high-energy rays, and contains in the resin in an amount greater than 0 and less than 70 mol% of either a repeating unit represented by the following general formula (Sx-4) or a repeating unit represented by the following general formula (Sx-5), and the organic groups remain unreacted even after the thermosetting reaction of the polysiloxane resin. [ka] (In the formula, R 4 (This is a non-aromatic substituent that may contain a hydrogen atom, a hydroxyl group, or a monovalent heteroatom having 1 to 30 carbon atoms.)

[0041] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0042] [Silicon-containing composition for forming a resist underlayer film] The silicon-containing resist underlayer film formation composition of the present invention is a silicon-containing resist underlayer film formation composition comprising a condensation reaction type thermosetting silicon-containing material (Sx) which is a polysiloxane resin, wherein the material (Sx) has non-condensation reactive organic groups that react with radical chemical species generated by irradiation with high-energy rays, and contains one or more repeating units represented by the general formula (Sx-4) or the general formula (Sx-5) in the resin in an amount greater than 0 and less than 70 mol%, and the organic groups remain unreacted even after the thermosetting reaction of the polysiloxane resin.

[0043] [Condensation reaction type thermosetting silicon-containing material] The condensation-type thermosetting silicon-containing material (Sx) of the present invention has non-condensation-reactive organic groups that react with radical chemical species generated by irradiation with high-energy rays, and contains in the resin in an amount greater than 0 and less than 70 mol% of either the repeating unit represented by the following general formula (Sx-4) or the repeating unit represented by the following general formula (Sx-5), and the organic groups remain unreacted even after the thermosetting reaction of the polysiloxane resin. [ka] (In the formula, R 4 (This is a non-aromatic substituent that may contain a hydrogen atom, a hydroxyl group, or a monovalent heteroatom having 1 to 30 carbon atoms.)

[0044] The condensation reaction type thermosetting silicon-containing material of the present invention hardens through a condensation reaction of the siloxane portion of the repeating units of the polysiloxane resin. The molecular chains of polysiloxane resins are sealed at their ends by hydroxyl groups (silanols) and / or hydrolyzable alkoxy groups bonded to silicon atoms derived from the raw materials. These molecular chain ends undergo hydrolysis and condensation reactions due to heat, leading to a curing (crosslinking) reaction. The condensation reaction can be accelerated by crosslinking catalysts or heating, as described later. Examples of condensation-reactive functional groups include hydroxyl groups bonded to silicon atoms, hydrolyzable alkoxy groups, and ring-opening polymerization functional groups such as epoxy groups and oxetanyl groups.

[0045] On the other hand, non-condensation reactivity refers to the property of not undergoing a condensation reaction even when crosslinked or heated. In the present invention, the material has a non-condensation reactive organic group that reacts with radical chemical species, and the organic group remains unreacted even after the thermosetting reaction of the polysiloxane resin. Preferred non-condensation reactive organic groups are non-condensation reactive organic groups having one or more polymerizable double bonds, or non-condensation reactive organic groups that react with radical chemical species generated by irradiation with high-energy rays. Specifically, examples include vinyl groups, isopropenyl groups, allyl groups, (meth)acryloyl groups, 3,3,3-trifluoro-2-propenyl groups, and 5-norbornene-2-yl groups. Among these, (meth)acryloyl groups are preferred.

[0046] In this invention, "remaining unreacted even after the thermosetting reaction" means that the non-condensation reactive organic group remains in the film even after the curing (crosslinking) reaction has progressed due to heating. The presence of the non-condensation reactive organic group in the film can be confirmed, for example, by measuring the organic group using nuclear magnetic resonance spectroscopy or infrared spectroscopy.

[0047] In this invention, high-energy rays are not particularly limited as long as they generate radical chemical species in organic groups or the like through their action, but they are suitable for use in the exposure of resist films. Examples of such high-energy rays include ultraviolet rays, far ultraviolet rays, electron beams (EB), extreme ultraviolet rays (EUV) with wavelengths of 3 to 15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation.

[0048] R 4 This is a non-aromatic substituent that may contain a hydrogen atom, a hydroxyl group, or a monovalent heteroatom having 1 to 30 carbon atoms, and examples include a linear, branched, or cyclic monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms. Among these, a linear alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group is particularly preferred.

[0049] In the present invention, it is preferable that the polysiloxane resin of the material (Sx) contains one or more of the repeating units represented by the following general formula (Sx-1), the repeating units represented by the following general formula (Sx-2), and the substructures represented by the following general formula (Sx-3), with these repeating units present in 30 to 99 mol% of the resin, and that one or more of the repeating units represented by the above general formula (Sx-4) or the repeating units represented by the above general formula (Sx-5) present in 1 to 70 mol% of the resin. [ka] (In the formula, R 1 R is a non-condensation reactive organic group having one or more polymerizable double bonds, or a non-condensation reactive organic group that reacts with radical chemical species generated by irradiation with high-energy rays, 2 , R 3 R is independent 1 It is the same as, or a non-aromatic substituent that may contain a hydrogen atom, a hydroxyl group, or a monovalent heteroatom having 1 to 30 carbon atoms. 4 (As stated above.)

[0050] In this case, the silicon-containing resist underlayer film forming composition of the present invention may further contain a siloxane polymerization crosslinking catalyst (Xc), an alcohol-based organic solvent, and water.

[0051] Furthermore, the organic group R 1 , R 2 and R 3 However, the following general formula R 5 or R 6 It can be an organic group represented by . [ka] (In the formula, L 1 R is a divalent organic group with 1-15 carbon atoms that may contain an oxygen atom, Ar is an aromatic ring with 6-14 carbon atoms, and * represents the linkage with a silicon atom. 7 R is a hydrogen atom or a monovalent organic group with 1-5 carbon atoms. 1 , R 2 and R 3They may be the same or different from each other.

[0052] Furthermore, the organic group R 5 However, the following general formula R 8 The organic group is represented by the organic group R 6 However, the following general formula R 9 It is preferable that the organic group is represented by . [ka] (In the formula, L 2 R is a divalent organic group having 1-10 carbon atoms that may contain an oxygen atom, 10 is a hydrogen atom or a monovalent organic group with 1-5 carbon atoms. * represents the linkage with a silicon atom.

[0053] By combining such crosslinking groups with the thermosetting silicon-containing material of the present invention, it is possible to obtain a resist underlayer film that contributes to preventing pattern collapse of the upper resist layer.

[0054] The silicon-containing resist underlayer film forming composition of the present invention contains one or more of the repeating units represented by the following general formula (Sx-1), the repeating units represented by the following general formula (Sx-2), and the substructures represented by the following general formula (Sx-3), and can contain one or more of the repeating units represented by the following general formula (Sx-4) or the repeating units represented by the following general formula (Sx-5) in the resin at an amount of 1 to 70 mol%. [ka] (In the formula, R 1 , R 2 , R 3 and R 4 (As stated above.)

[0055] The silicon-containing resist underlayer film forming composition of the present invention has a polysiloxane resin material (Sx) which has non-condensation reactive organic groups that react with radical chemical species generated by irradiation with high-energy rays, and contains one or more repeating units represented by the general formula (Sx-4) or the general formula (Sx-5) in the resin in an amount greater than 0 and less than 70 mol%, and the organic groups remain unreacted even after the thermosetting reaction of the polysiloxane resin. For this reason, when a resist composition containing polymerizable functional groups, for example, a molecular resist composition containing a sulfonium salt represented by the following formula (1A) or (2A) and an organic solvent, and not containing a base polymer, is used as a resist upper layer film composition to form a resist upper layer film on the silicon-containing resist underlayer film, the silicon-containing resist underlayer film with polymerizable groups and the molecular resist film (resist upper layer film) with polymerizable groups crosslink (radical polymerization) in the exposed area, exhibiting excellent effects such as improved adhesion and prevention of molecular resist collapse. [ka] (In the formula, n is an integer between 1 and 3.) A 1 This is a hydrocarbyl group having 2 to 20 carbon atoms that contains a polymerizable functional group, and this hydrocarbyl group may contain a heteroatom. A 2 It contains polymerizable functional groups, Ar 1B It is a group that forms an alicyclic ring with 4 to 20 carbon atoms together with the two carbon atoms inside, and the alicyclic ring may contain heteroatoms. Ar 1A This is an arylene group having 6 to 20 carbon atoms, and the arylene group may have some or all of the hydrogen atoms on its aromatic ring substituted with a hydrocarbyl group having 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms. 1B This is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and this trivalent aromatic hydrocarbon group may have some or all of the hydrogen atoms on its aromatic ring substituted with a hydrocarbyl group having 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms. 2This is an aryl group having 6 to 20 carbon atoms, and this aryl group may have some or all of the hydrogen atoms on its aromatic ring substituted with a hydrocarbyl group having 1 to 20 carbon atoms, which may contain halogen atoms or heteroatoms. Also, two Ar 1A , two Ar 1B , two Ar 2 Ar 1A and Ar 2 to, or Ar 1B and Ar 2 These may bond with each other to form a ring with the sulfur atom to which they are bonded. X - This is the pair anion. Note that the above symbols apply only in the above formula.

[0056] The silicon-containing resist underlayer film forming composition of the present invention contains the above-mentioned non-condensation reactive organic group, which remains unreacted even after the thermal curing of the polysiloxane resin. This organic group acts as a crosslinking group, crosslinking with the above-mentioned molecular resist during exposure to produce the above-mentioned effect.

[0057] The aforementioned R 1 The group is not particularly limited as long as it is a non-condensation reactive organic group that reacts with radical chemical species generated by irradiation with high-energy beams such as electron beams. Examples of such condensation reaction type thermosetting silicon-containing materials (Sx) include the following. In the following formulas, (Si) is included to indicate the bonding site with Si (the same applies below). [ka]

[0058] The hydrolyzable monomer (Sm) used as a raw material for forming the structure of the present invention has the above structure on silicon, and on the other hand, has one, two or three hydrolyzable groups such as chlorine, bromine, iodine, acetoxy group, methoxy group, ethoxy group, propoxy group or butoxy group, and if present, R 2 , R 3One or more types of materials containing a hydrogen atom or a monovalent organic group with 1 to 30 carbon atoms can be used.

[0059] The above R 2 , R 3 Examples of organic groups represented by include methyl, ethyl, vinyl, propyl, cyclopropyl, butyl, cyclobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, cyclohexenyl, cyclopentylmethyl, heptyl, cyclohexylmethyl, cyclohexenylmethyl, bicyclo[2,2,1]heptyl, octyl, cyclooctyl, cyclohexylethyl, decyl, adamantyl, and dodecyl, which may be the same or different.

[0060] The above R 2 , R 3 Another example of an organic group represented by this formula 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 ether bonds, ester bonds, alkoxy groups, hydroxyl groups, etc. An example of this is the one represented by the following general formula (Sm-R).

[0061] (P-Q1-(S1) v1 -Q2-) u -(T) v2 -Q3-(S2) v3 -Q4(Sm-R) (In the general formula (Sm-R), P is a hydrogen atom, a cyclic ether group, a hydroxyl group, a carbon 1-4 alkoxy group, a carbon 1-6 alkylcarbonyloxy group, or a carbon 1-6 alkylcarbonyl group, and Q1, Q2, Q3, and Q4 are each independently -C q H (2q-p) P p-(In the formula, P is the same as above, p is an integer from 0 to 3, and q is an integer from 0 to 10 (where q=0 indicates a single bond).), u is an integer from 0 to 3, and S1 and S2 independently represent -O-, -CO-, -OCO-, -COO-, or -OCOO-. v1, v2, and v3 independently represent 0 or 1. Along with these, T is a divalent group consisting of a divalent atom other than carbon or an alicyclic ring.) Examples of alicyclic rings that may contain heteroatoms such as oxygen atoms as T are shown below. The positions in T where Q2 and Q3 are bonded are not particularly limited, but can be appropriately selected considering factors such as reactivity due to steric factors and the availability of commercially available reagents used in the reaction.

[0062] [ka]

[0063] Preferred examples of organic groups having one or more carbon-oxygen single or carbon-oxygen double bonds in the general formula (Sm-R) include the following:

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] Also, R 2 , R 3 Examples of organic groups include those containing silicon-silicon bonds. Specifically, the following can be cited.

[0068] [ka]

[0069] Furthermore, R 2 , R 3 As an example of an organic group, an organic group having a fluorine atom can also be used. Specifically, examples include organic groups obtained from silicon compounds as shown in paragraphs (0059) to (0065) of Japanese Patent Publication No. 2012-53253.

[0070] The above hydrolyzable monomer (Sm) has one, two, or three hydrolyzable groups such as chlorine, bromine, iodine, acetoxy group, methoxy group, ethoxy group, propoxy group, or butoxy group bonded to the silicon element indicated by (Si) in the above substructure.

[0071] Furthermore, the silicon-containing material (Sx) of the present invention can be produced by hydrolysis condensation of a mixture containing the following hydrolyzable monomer (Sm).

[0072] Specifically, hydrolyzable monomers (Sm) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, vinyltri Toxysilane, vinyl tripropoxysilane, vinyl triisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltriisopropoxysilane, isopropyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltriisopropoxysilane, sec-butyltrimethoxysilane, sec-butyl Riethoxysilane, sec-butyltripropoxysilane, sec-butyltriisopropoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltripropoxysilane, t-butyltriisopropoxysilane, cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane, cyclopropyltripropoxysilane, cyclopropyltriisopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyltripropoxysilane, cyclobutyltriisopropoxysilane Sisilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltripropoxysilane, cyclopentyltriisopropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, cyclohexyltriisopropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane, cyclohexenylethyltrimethoxysilane,Cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, bicycloheptenyl Dimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltripropoxysilane, bicycloheptenyltriisopropoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyltripropoxysilane, bicycloheptyltriisopropoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyltripropoxysilane, adamantyltriisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimeth Xysilane, methylethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, dipropyldiisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, dibutyldimethoxysilane, di Butyldiethoxysilane, dibutyldipropoxysilane, dibutyldiisopropoxysilane, disec-butyldimethoxysilane, disec-butyldiethoxysilane, disec-butyldipropoxysilane, disec-butyldiisopropoxysilane, dit-butyldimethoxysilane, dit-butyldiethoxysilane, dit-butyldipropoxysilane, dit-butyldiisopropoxysilane, dicyclopropyldimethoxysilane, dicyclopropyldiethoxysilane, dicyclopropyldipropoxysilane, dicyclopropyldiisopropoxysilane,Dicyclobutyldimethoxysilane, dicyclobutyldiethoxysilane, dicyclobutyldipropoxysilane, dicyclobutyldiisopropoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentyldipropoxysilane, dicyclopentyldiisopropoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane, dicyclohexyldiisopropoxysilane, di Chlohexenyldimethoxysilane, dicyclohexenyldiethoxysilane, dicyclohexenyldipropoxysilane, dicyclohexenyldiisopropoxysilane, dicyclohexenylethyldimethoxysilane, dicyclohexenylethyldiethoxysilane, dicyclohexenylethyldipropoxysilane, dicyclohexenylethyldiisopropoxysilane, dicyclooctyldimethoxysilane, dicyclooctyldiethoxysilane, dicyclooctyldipropoxysilane, di Cyclooctyl diisopropoxysilane, dicyclopentadienylpropyl dimethoxysilane, dicyclopentadienylpropyl diethoxysilane, dicyclopentadienylpropyl dipropoxysilane, dicyclopentadienylpropyl diisopropoxysilane, bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis(bicycloheptenyl)dipropoxysilane, bis(bicycloheptenyl)diisopropoxysilane, bis(bi Examples include cycloheptyl)dimethoxysilane, bis(bicycloheptyl)diethoxysilane, bis(bicycloheptyl)dipropoxysilane, bis(bicycloheptyl)diisopropoxysilane, diadamantyldimethoxysilane, diadamantyldiethoxysilane, diadamantyldipropoxysilane, diadamantyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, etc.

[0073] Preferably, the above compounds are tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxy Examples include sisilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, etc.

[0074] [Method for synthesizing thermosetting silicon-containing materials (Sx)] (Synthesis method 1: acid catalyst) The thermosetting silicon-containing material of the present invention (Sx: hereinafter also referred to as thermosetting polysiloxane) can be produced by hydrolysis condensation of one or more hydrolyzable monomers (Sm) (hereinafter also simply referred to as "monomers") in the presence of an acid catalyst.

[0075] Examples of acid catalysts used in this process include organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid, and inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid. The amount of catalyst used is 1 × 10⁻¹⁶ per mole of monomer. -6 ~10 moles, preferably 1 × 10⁻⁶ moles -5 ~5 moles, comfortable 1 × 10⁻⁶ -4 It is approximately 1 mole.

[0076] When obtaining thermosetting polysiloxanes from these monomers by hydrolysis condensation, it is preferable to add 0.01 to 100 moles of water per mole of hydrolyzable substituents attached to the monomer, more preferably 0.05 to 50 moles, and even more preferably 0.1 to 30 moles. If the amount is 100 moles or less, the apparatus used for the reaction can be made smaller and more economical.

[0077] The procedure 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 beforehand, or both may be done. The reaction temperature is 0 to 100°C, preferably 5 to 80°C. It is preferable to maintain the temperature at 5 to 80°C when adding the monomer dropwise, and then allow it to mature at 20 to 80°C.

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

[0079] Among these 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. Of these, those with a boiling point of 100°C or lower are particularly preferred.

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

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

[0082] Next, it is preferable to remove by-products such as alcohol produced by the hydrolysis condensation reaction from the reaction mixture by vacuum removal or the like. The temperature at which the reaction mixture is heated depends on the type of organic solvent added and the type of alcohol produced by 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 at this time varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condensing device, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and even more preferably 50 kPa or less in absolute pressure. It is difficult to know the exact amount of alcohol removed at this time, but it is desirable that approximately 80% or more by mass of the produced alcohol is removed.

[0083] Next, the acid catalyst used in the hydrolysis condensation may be removed from the reaction mixture. As a method for removing the acid catalyst, water and a thermosetting polysiloxane solution are mixed, and the thermosetting polysiloxane is extracted with an organic solvent. The organic solvent used at this time is preferably one that can dissolve the thermosetting polysiloxane and separates into two layers when mixed with water. Examples 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, it is also possible to use mixtures of water-soluble organic solvents and water-insoluble organic solvents. For example, methanol-ethyl acetate mixture, ethanol-ethyl acetate mixture, 1-propanol-ethyl acetate mixture, 2-propanol-ethyl acetate mixture, butanediol monomethyl ether-ethyl acetate mixture, propylene glycol monomethyl ether-ethyl acetate mixture, ethylene glycol monomethyl ether-ethyl acetate mixture, butanediol monoethyl ether-ethyl acetate mixture, propylene glycol monoethyl ether-ethyl acetate mixture, ethylene glycol monoethyl ether-ethyl acetate mixture, butanediol monopropyl ether-ethyl acetate mixture, propylene glycol monopropyl ether-ethyl acetate mixture, ethylene glycol monopropyl ether-ethyl acetate mixture, methanol-methyl isobutyl ketone mixture, ethanol-methyl isobutyl ketone mixture, 1-propanol-methyl isobutyl ketone mixture, 2-propanol-methyl isobutyl ketone mixture, propylene glycol monomethyl ether-methyl isobutyl ketone mixture, ethylene glycol monomethyl ether-methyl isobutyl ketone 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 monoethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monoethyl ether-cyclopentyl methyl ether mixture, propylene glycol monopropyl ether-cyclopentyl methyl ether mixture, ethylene glycol monopropyl ether-cyclopentyl methyl ether mixture,Methanol-propylene glycol methyl ether acetate mixtures, ethanol-propylene glycol methyl ether acetate mixtures, 1-propanol-propylene glycol methyl ether acetate mixtures, 2-propanol-propylene glycol methyl ether acetate mixtures, propylene glycol monomethyl ether-propylene glycol methyl ether acetate mixtures, ethylene glycol monomethyl ether-propylene glycol methyl ether acetate mixtures, propylene glycol monoethyl ether-propylene glycol methyl ether acetate mixtures, ethylene glycol monoethyl ether-propylene glycol methyl ether acetate mixtures, propylene glycol monopropyl ether-propylene glycol methyl ether acetate mixtures, ethylene glycol monopropyl ether-propylene glycol methyl ether acetate mixtures, etc. are preferred, but the combinations are not limited to these.

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

[0086] Next, the mixture may be washed with neutral water. This water can be what is commonly called deionized water or ultrapure water. The amount of water used is 0.01 to 100 L, preferably 0.05 to 50 L, and more preferably 0.1 to 5 L, per 1 L of thermosetting polysiloxane solution. This washing method involves placing both solutions in the same container, stirring them, and then letting them stand to separate the aqueous layer. One or more washes are sufficient, but washing more than 10 times will not yield the desired results, so 1 to 5 washes are preferable.

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

[0088] During this rinsing process, some of the thermosetting polysiloxane escapes into the aqueous layer, and in some cases, an effect equivalent to fractionation can be achieved. Therefore, the number of rinses and the amount of washing water should be appropriately selected considering the catalyst removal effect and the fractionation effect.

[0089] At this time, the thermosetting polysiloxane may become unstable due to the change in solvent. This occurs due to the compatibility between the final solvent and the thermosetting polysiloxane. To prevent this, a monovalent or divalent or higher alcohol having a cyclic ether as a substituent, as described in paragraphs (0181) to (0182) of Japanese Patent Publication No. 2009-126940, may be added as a stabilizer. The amount to be added is 0 to 25 parts by mass, preferably 0 to 15 parts by mass, more preferably 0 to 5 parts by mass, per 100 parts by mass of thermosetting polysiloxane in the solution before solvent exchange, but if added, 0.5 parts by mass or more is preferable. If necessary, a monovalent or divalent or higher alcohol having a cyclic ether as a substituent may be added to the solution before solvent exchange and the solvent exchange operation may be performed.

[0090] Thermosetting polysiloxanes, when concentrated beyond a certain concentration, undergo further condensation reactions and may become irresolvable in organic solvents. Therefore, it is preferable to maintain them in a solution of an appropriate concentration. Conversely, if the solution is too dilute, the amount of solvent becomes excessive. Therefore, maintaining a solution of an appropriate concentration is economical and preferable. The preferred concentration at this time is 0.1 to 20% by mass.

[0091] Preferred final solvents to be added to thermosetting polysiloxane solutions are alcohol-based organic solvents, with particular preference being monoalkyl ether derivatives such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, and diacetone alcohol are preferred.

[0092] If these solvents are the main components, it is also possible to add non-alcoholic organic solvents as auxiliary solvents. Examples of such auxiliary solvents include acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, and cyclopentyl methyl ether.

[0093] Another reaction procedure using an acid catalyst involves adding water or an aqueous organic solvent to a monomer or an organic solution of a monomer to initiate the hydrolysis reaction. The catalyst may be added to the monomer or the organic solution of a monomer, or it may be added to the water or aqueous organic solvent beforehand. The reaction temperature is 0 to 100°C, preferably 10 to 80°C. A preferred method involves heating to 10 to 50°C when adding water dropwise, and then raising the temperature to 20 to 80°C for aging.

[0094] When using organic solvents, water-soluble ones are preferred, 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 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 Examples include polyhydric alcohol condensate derivatives and mixtures thereof.

[0095] The amount of organic solvent used is preferably 0 to 1,000 ml, and particularly preferably 0 to 500 ml, per mole of monomer. Using less organic solvent allows for a smaller reaction vessel, which is more economical. The resulting reaction mixture can be post-treated in the same manner as described above to obtain a thermosetting polysiloxane.

[0096] (Synthesis method 2: Alkaline catalyst) Furthermore, thermosetting silicon-containing materials (Sx: thermosetting polysiloxanes) can be produced by hydrolysis condensation of one or more hydrolyzable monomers (Sm) in the presence of an alkaline catalyst. Examples of alkaline catalysts used in this case include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclocyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. The amount of catalyst used is 1 × 10⁻⁶ per mole of silicon monomer. -6 Moles ~ 10 moles, preferably 1 × 10 -5 Moles ~5 moles, comfortable 1 × 10 -4 Moles is approximately equal to 1 mole.

[0097] When obtaining a thermosetting polysiloxane from the above monomers by hydrolysis condensation, it is preferable to add 0.1 to 50 moles of water per mole of hydrolyzable substituents attached to the monomer. If the amount is 50 moles or less, the apparatus used for the reaction can be made smaller and more economical.

[0098] The procedure 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 beforehand, or both may be done. The reaction temperature is 0 to 100°C, preferably 5 to 80°C. It is preferable to maintain the temperature at 5 to 80°C when adding the monomer dropwise, and then allow it to mature at 20 to 80°C.

[0099] As organic solvents that can be added to the alkaline catalyst aqueous solution or used to dilute the monomer, those similar to the organic solvents exemplified as those that can be added to the acid catalyst aqueous solution are preferably used. Furthermore, 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.

[0100] Subsequently, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous solution of the reaction mixture. At this time, the amount of acidic substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the alkaline substance used in the catalyst. Any substance that exhibits acidity in water can be used as this acidic substance. good.

[0101] Next, it is preferable to remove by-products such as alcohol produced by the hydrolysis condensation reaction from the reaction mixture by vacuum removal or the like. The temperature at which the reaction mixture is heated depends on the type of alcohol produced by the reaction with the added organic solvent, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum at this time varies depending on the type of organic solvent and alcohol to be removed, the exhaust system, the condensing system, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and even more preferably 50 kPa or less in absolute pressure. It is difficult to know the exact amount of alcohol removed at this time, but it is desirable that approximately 80% or more by mass of the produced alcohol is removed.

[0102] Next, to remove the catalyst used in hydrolysis condensation, the thermosetting polysiloxane is extracted with an organic solvent. The organic solvent used is preferably one that can dissolve the thermosetting polysiloxane and separates into two layers when mixed with water. Examples 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.

[0103] Next, to remove the alkaline catalyst used in hydrolysis condensation, the thermosetting polysiloxane is extracted with an organic solvent. The organic solvent used is preferably one that can dissolve the thermosetting polysiloxane and separates into two layers when mixed with water. Furthermore, a mixture of a water-soluble organic solvent and a water-insoluble organic solvent can also be used.

[0104] Specific examples of organic solvents used to remove alkaline catalysts include the same organic solvents mentioned above as examples used to remove acid catalysts, as well as mixtures of water-soluble organic solvents and water-repellent organic solvents.

[0105] The mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent is selected as appropriate, but is preferably 0.1 to 1,000 parts by mass of the water-soluble organic solvent, more preferably 1 to 500 parts by mass, and more preferably 2 to 100 parts by mass of the water-soluble organic solvent per 100 parts by mass of the water-insoluble organic solvent.

[0106] Next, wash with neutral water. This water can be what is commonly called deionized water or ultrapure water. The amount of water should be 0.01 to 100 L, preferably 0.05 to 50 L, and more preferably 0.1 to 5 L, per 1 L of thermosetting polysiloxane solution. To wash, put both in the same container, stir, and then let it stand to separate the aqueous layer. One or more washes are sufficient, but washing more than 10 times will not yield sufficient results, so preferably 1 to 5 washes are recommended.

[0107] The final solvent is added to the washed thermosetting polysiloxane solution, and the solvent is exchanged under reduced pressure to obtain the desired thermosetting polysiloxane solution. The temperature of the solvent exchange at this time depends on the type of extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of reduced pressure at this time varies depending on the type of extraction solvent to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and even more preferably 50 kPa or less in absolute pressure.

[0108] Preferred final solvents to be added to thermosetting polysiloxane solutions are alcohol-based solvents, with particular preference being monoalkyl ethers such as ethylene glycol, diethylene glycol, and triethylene glycol, and monoalkyl ethers such as propylene glycol and dipropylene glycol. Specifically, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, and diacetone alcohol are preferred.

[0109] Organic solvents that can be used as organic solutions or aqueous organic solvents for monomers are preferably water-soluble, including methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether. acetate Examples include polyhydric alcohol condensate derivatives and mixtures thereof.

[0110] The molecular weight of the thermosetting polysiloxane obtained by the above synthesis method 1 or 2 can be adjusted not only by selecting monomers but also by controlling the reaction conditions during polymerization. However, it is preferable to use a weight-average molecular weight (Mw) of 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. Using a weight-average molecular weight of 100,000 or less prevents the generation of foreign matter and uneven coating. The above data regarding weight-average molecular weight was obtained by gel permeation chromatography (GPC) using radioisotopes (RI) as the detector and tetrahydrofuran as the eluent, with polystyrene used as the standard substance, and the molecular weight expressed in terms of polystyrene equivalent.

[0111] The physical properties of the thermosetting polysiloxane used in this invention vary depending on the type of acid or alkali catalyst used during hydrolysis condensation and the reaction conditions. Therefore, it can be appropriately selected according to the desired performance of the resist underlayer film.

[0112] The thermosetting silicon-containing material (Sx) can be produced under conditions using an acid or an alkali catalyst for a hydrolyzable monomer. Furthermore, a polysiloxane derivative produced under conditions using the above-mentioned acid or alkali catalyst for a mixture of this monomer and a hydrolyzable metal compound represented by the following general formula (Mm) can be used as a component of a resist underlayer film composition. U(OR 7 ) m7 (OR 8 ) m8 (Mm) (In the formula, R 7 , R 8 are organic groups having 1 to 30 carbon atoms, m7 + m8 is the same number 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, Group IV, or Group V of the periodic table excluding carbon and silicon.)

[0113] Examples of the hydrolyzable metal compound (Mm) used at this time include the following. When U is boron, examples of the compound represented by the general formula (Mm) include borone methoxide, borone ethoxide, borone propoxide, borone butoxide, borone amyloxide, borone hexyloxide, borone cyclopentoxide, borone cyclohexyloxide, borone allyloxide, borone phenoxide, borone methoxyethoxide, boric acid, boron oxide, etc. as monomers.

[0114] When U is aluminum, examples of monomers represented by the general formula (Mm) include aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, aluminum amyloxide, aluminum hexyloxide, aluminum cyclopentoxide, aluminum cyclohexyloxide, aluminum alyloxide, aluminum phenoxide, aluminum methoxyethoxide, aluminum ethoxyethoxide, aluminum dipropoxyethyl acetate, aluminum dibutoxyethyl acetate, aluminum propoxybisethyl acetate, aluminum butoxybisethyl acetate, aluminum 2,4-pentanedione, and aluminum 2,2,6,6-tetramethyl-3,5-heptanedione.

[0115] When U is gallium, examples of monomers represented by the general formula (Mm) include gallium methoxide, gallium ethoxide, gallium propoxide, gallium butoxide, gallium amyloxide, gallium hexyloxide, gallium cyclopentoxide, gallium cyclohexyloxide, gallium alliloxide, gallium phenoxide, gallium methoxyethoxide, gallium ethoxyethoxide, gallium dipropoxyethyl acetate, gallium dibutoxyethyl acetate, gallium propoxybisethyl acetate, gallium butoxybisethyl acetate, gallium 2,4-pentanedione, and gallium 2,2,6,6-tetramethyl-3,5-heptanedione.

[0116] When U is yttrium, examples of monomers represented by the general formula (Mm) include yttrium methoxide, yttrium ethoxide, yttrium propoxide, yttrium butoxide, yttrium amyloxide, yttrium hexyloxide, yttrium cyclopentoxide, yttrium cyclohexyloxide, yttrium alliloxide, yttrium phenoxide, yttrium methoxyethoxide, yttrium ethoxyethoxide, yttrium dipropoxyethyl acetate, yttrium dibutoxyethyl acetate, yttrium propoxybisethyl acetate, yttrium butoxybisethyl acetate, yttrium 2,4-pentanedione, and yttrium 2,2,6,6-tetramethyl-3,5-heptanedione.

[0117] When U is germanium, examples of monomers represented by the general formula (Mm) include germanium methoxide, germanium ethoxide, germanium propoxide, germanium butoxide, germanium amyloxide, germanium hexyloxide, germanium cyclopentoxide, germanium cyclohexyloxide, germanium alliloxide, germanium phenoxide, germanium methoxyethoxide, and germanium ethoxyethoxide.

[0118] When U is titanium, examples of monomers represented by the general formula (Mm) include titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, titanium amyloxide, titanium hexyloxide, titanium cyclopentoxide, titanium cyclohexyloxide, titanium alyroxide, titanium phenoxide, titanium methoxyethoxide, titanium ethoxyethoxide, titanium dipropoxybis-ethyl acetate, titanium dibutoxybis-ethyl acetate, titanium dipropoxybis-2,4-pentanedione, and titanium dibutoxybis-2,4-pentanedione.

[0119] When U is hafnium, examples of monomers represented by the general formula (Mm) include hafnium methoxide, hafnium ethoxide, hafnium propoxide, hafnium butoxide, hafnium amyloxide, hafnium hexyloxide, hafnium cyclopentoxide, hafnium cyclohexyloxide, hafnium alliloxide, hafnium phenoxide, hafnium methoxyethoxide, hafnium ethoxyethoxide, hafnium dipropoxybis-ethylacetate, hafnium dibutoxybis-ethylacetate, hafnium dipropoxybis-2,4-pentanedione, and hafnium dibutoxybis-2,4-pentanedione.

[0120] When U is tin, examples of monomers that can be 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.

[0121] When U is arsenic, examples of monomers that can be represented by the general formula (Mm) include methoxyarsenic, ethoxyarsenic, propoxyarsenic, butoxyarsenic, and phenoxyarsenic.

[0122] When U is antimony, examples of monomers represented by the general formula (Mm) include methoxyantimony, ethoxyantimony, propoxyantimony, butoxyantimony, phenoxyantimony, antimony acetate, and antimony propionate.

[0123] When U is niobium, examples of monomers that can be represented by the general formula (Mm) include methoxyniobium, ethoxyniobium, propoxyniobium, butoxyniobium, and phenoxyniobium.

[0124] When U is tantalum, examples of monomers that can be represented by the general formula (Mm) include methoxytantalum, ethoxytantalum, propoxytantalum, butoxytantalum, and phenoxytantalum.

[0125] When U is bismuth, examples of monomers that can be represented by the general formula (Mm) include methoxybismuth, ethoxybismuth, propoxybismuth, butoxybismuth, and phenoxybismuth.

[0126] When U is phosphorus, examples of monomers represented by the general formula (Mm) include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, and phosphorus pentoxide.

[0127] When U is vanadium, examples of monomers that can be represented by the general formula (Mm) include vanadium oxide bis(2,4-pentanedione), vanadium 2,4-pentanedione, vanadium triputoxide oxide, and vanadium trippropoxide oxide.

[0128] When U is zirconium, examples of monomers that can be represented by the general formula (Mm) include methoxyzirconium, ethoxyzirconium, propoxyzirconium, butoxyzirconium, phenoxyzirconium, zirconium dibutoxide bis(2,4-pentanedione), and zirconium dipropoxide bis(2,2,6,6-tetramethyl-3,5-heptanedione).

[0129] [Crosslinking catalyst for siloxane polymerization] The silicon-containing resist underlayer film formation composition of the present invention comprises the above-mentioned condensation reaction type thermosetting silicon-containing material (Sx) in addition to a compound represented by the following general formula (Xc). In the following, this compound may also be referred to as a siloxane polymerization crosslinking catalyst or simply a crosslinking catalyst.

[0130] In the present invention, the crosslinking catalyst for siloxane polymerization can be a sulfonium salt, an iodonium salt, a phosphonium salt, an ammonium salt, a polysiloxane having these as a part of its structure, or an alkali metal salt.

[0131] As the crosslinking catalyst (Xc) for siloxane polymerization, compounds represented by the following general formula (Xc0) can be cited. L a H b A (Xc0) (In the formula, L is lithium, sodium, potassium, rubidium, cesium, sulfonium, iodonium, phosphonium or ammonium, A is a non-nucleophilic counter ion, a is an integer of 1 or more, b is 0 or an integer of 1 or more, and a + b is the valence of the non-nucleophilic counter ion.)

[0132] Specific examples of (Xc0) include sulfonium salts of the following general formula (Xc-1), iodonium salts of (Xc-2), phosphonium salts of (Xc-3), ammonium salts of (Xc-4), alkali metal salts, and the like.

[0133] Examples of the sulfonium salt (Xc-1), iodonium salt (Xc-2), and phosphonium salt (Xc-3) are as follows.

Chemical formula

[0134] Examples of the ammonium salt (Xc-4) are as follows.

Chemical formula

[0135] The above R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211These groups may be identical or different from each other. Specifically, examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups. Examples of alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl groups. Examples of oxoalkyl groups include 2-oxocyclopentyl and 2-oxocyclohexyl groups, and can also include 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl groups. Examples of aryl groups include phenyl groups, naphthyl groups, alkoxyphenyl groups such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert-butoxyphenyl, alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl, alkylnaphthyl groups such as methylnaphthyl and ethylnaphthyl, alkoxynaphthyl groups such as methoxynaphthyl and ethoxynaphthyl, dialkylnaphthyl groups such as dimethylnaphthyl and diethylnaphthyl, and dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl. Examples of aralkyl groups include benzyl, phenylethyl, and phenethyl groups. Examples of aryloxoalkyl groups include 2-phenyl-2-oxoethyl group, 2-(1-naphthyl)-2-oxoethyl group, 2-(2-naphthyl)-2-oxoethyl group, and other 2-aryl-2-oxoethyl groups.

[0136] A -Non-nucleophilic counterions 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, linolenicate ion, benzoate ion, phthalate ion, isophthalate ion, terephthalate ion, salicylate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, trichloroacetate ion, fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion, Examples include monovalent ions such as nitrite ions, chlorate ions, bromate ions, methanesulfonate ions, p-toluenesulfonate ions, and monomethylsulfate ions, as well as monovalent or divalent oxalate ions, malonate ions, methylmalonate ions, ethylmalonate ions, propylmalonate ions, butylmalonate ions, dimethylmalonate ions, diethylmalonate ions, succinate ions, methylsuccinate ions, glutarate ions, adipicate ions, itaconicate ions, maleate ions, fumarate ions, citraconate ions, citrate ions, carbonate ions, and sulfate ions.

[0137] Examples of alkali metal salts include hydroxylates, formates, acetates, propions, butanoates, pentanoates, hexanoates, heptanoates, octanates, nonanoates, decanoates, oleates, stearates, linoleates, linolenates, benzoates, phthalates, isophthalates, terephthalates, salicylates, trifluoroacetates, monochloroacetates, dichloroacetates, trichloroacetates, and other monovalent salts; monovalent or divalent oxalates, malonates, methylmalonates, ethylmalonates, propylmalonates, butylmalonates, dimethylmalonates, diethylmalonates, succinates, methylsuccinates, glutarates, adipines, itaconates, maleates, fumarates, citraconates, citrates, and carbonates.

[0138] Specifically, as sulfonium salts (Xc-1), we have 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, and Examples include triphenylsulfonium tylmalonate, triphenylsulfonium propylmalonate, triphenylsulfonium butylmalonate, triphenylsulfonium dimethylmalonate, triphenylsulfonium diethylmalonate, triphenylsulfonium succinate, triphenylsulfonium methylsuccinate, triphenylsulfonium glutarate, triphenylsulfonium adipicate, triphenylsulfonium itaconicate, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylsulfonium citrate, triphenylsulfonium citrate, triphenylsulfonium carbonate, bistriphenylsulfonium oxalate, bistriphenylsulfonium maleate, bistriphenylsulfonium fumarate, bistriphenylsulfonium citrate, bistriphenylsulfonium citrate, and bistriphenylsulfonium carbonate.

[0139] Furthermore, the iodonium salts (Xc-2) specifically 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, and diphenyliodonium hydroxide. Examples include nyliodonium, diphenyliodonium nitrate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide, diphenyliodonium oxalate, diphenyliodonium maleate, diphenyliodonium fumarate, diphenyliodonium citrate, diphenyliodonium citrate, diphenyliodonium carbonate, bisdiphenyliodonium oxalate, bisdiphenyliodonium maleate, bisdiphenyliodonium fumarate, bisdiphenyliodonium citrate, bisdiphenyliodonium citrate, and bisdiphenyliodonium carbonate.

[0140] Furthermore, specific examples of phosphonium salts (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 citrate, tetraethylphosphonium carbonate, bistetraethylphosphonium oxalate, and bistetraethylphosphonium maleate. Tylphosphonium, bistetraethylphosphonium fumarate, bistetraethylphosphonium citraconate, 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 include tetraphenylphosphonium citraconate, tetraphenylphosphonium citrate, tetraphenylphosphonium carbonate, bistetraphenylphosphonium oxalate, bistetraphenylphosphonium maleate, bistetraphenylphosphonium fumarate, bistetraphenylphosphonium citraconate, bistetraphenylphosphonium citrate, and bistetraphenylphosphonium carbonate.

[0141] On the other hand, specific examples of ammonium salts (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 monomethyl sulfate, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium maleate, tetramethylammonium fumarate, tetramethylammonium citrate, 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, dik Tetrapropylammonium 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,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, citra Bistetrabutylammonium ammonium citrate, bistetrabutylammonium ammonium carbonate, trimethylphenylammonium formate, trimethylphenylammonium acetate, trimethylphenylammonium propionate, trimethylphenylammonium butanoate, trimethylphenylammonium benzoate, trimethylphenylammonium phthalate, trimethylphenylammonium isophthalate, trimethylphenylammonium terephthalate, trimethylphenylammonium salicylate, trimethylphenylammonium trifluoromethanesulfonate, trimethylphenylammonium trifluoroacetate, trimethylphenylammonium monochloroacetate, trimethylphenylammonium dichloroacetate, trimethylphenylammonium trichloroacetate, trimethylphenylammonium hydroxide, trimethylphenylammonium nitrate, trimethylphenylammonium chloride, trimethylphenylammonium bromide, trimethylphenylammonium iodide, trimethylphenylammonium methanesulfonate, trimethylphenylammonium monomethylsulfateTrimethylphenylammonium oxalate, trimethylphenylammonium malonate, trimethylphenylammonium maleate, trimethylphenylammonium fumarate, trimethylphenylammonium citraconate, trimethylphenylammonium citrate, trimethylphenylammonium carbonate, bistrimethylphenylammonium oxalate, bistrimethylphenylammonium malonate, bistrimethylphenylammonium maleate, bistrimethylphenylammonium fumarate, bistrimethylphenylammonium citraconate, bistrimethylphenylammonium citrate, bistrimethylphenylammonium carbonate, triethylphenylammonium formate, triethylphenylammonium acetate, triethylphenylammonium propionate, triethylphenylammonium butanoate, triethylphenylammonium benzoate, triethylphenylammonium phthalate, triethylphenylammonium isophthalate, triethylphenylammonium terephthalate, triethylphenylammonium salicylate, triethylphenylammonium trifluoromethanesulfonate Bistriethylphenylammonium trifluoroacetate, triethylphenylammonium monochloroacetate, triethylphenylammonium dichloroacetate, triethylphenylammonium trichloroacetate, triethylphenylammonium hydroxide, triethylphenylammonium nitrate, triethylphenylammonium chloride, triethylphenylammonium bromide, triethylphenylammonium iodide, triethylphenylammonium methanesulfonate, triethylphenylammonium monomethylsulfate, triethylphenylammonium oxalate, triethylphenylammonium malonate, triethylphenylammonium maleate, triethylphenylammonium fumarate, triethylphenylammonium citrate, triethylphenylammonium citrate, triethylphenylammonium carbonate, bistriethylphenylammonium oxalate, bistriethylphenylammonium malonate, bistriethylphenylammonium maleate, bistriethylphenylammonium fumarate, bistriethylphenylammonium citrate,Bistriethylphenylammonium citrate, bistriethylphenylammonium carbonate, benzyldimethylphenylammonium formate, benzyldimethylphenylammonium acetate, benzyldimethylphenylammonium propionate, benzyldimethylphenylammonium butanoate, benzyldimethylphenylammonium benzoate, benzyldimethylphenylammonium phthalate, benzyldimethylphenylammonium isophthalate, benzyldimethylphenylammonium terephthalate, benzyldimethylphenylammonium salicylate, benzyldimethylphenylammonium trifluoromethanesulfonate, benzyldimethylphenylammonium trifluoroacetate, benzyldimethylphenylammonium monochloroacetate, benzyldimethylphenylammonium dichloroacetate, benzyldimethylphenylammonium trichloroacetate, benzyldimethylphenylammonium hydroxide, benzyldimethylphenylammonium nitrate, benzyldimethylphenylammonium chloride Examples include ammonium, benzyldimethylphenylammonium bromide, benzyldimethylphenylammonium iodide, benzyldimethylphenylammonium methanesulfonate, benzyldimethylphenylammonium monomethylsulfate, benzyldimethylphenylammonium oxalate, benzyldimethylphenylammonium malonate, benzyldimethylphenylammonium maleate, benzyldimethylphenylammonium fumarate, benzyldimethylphenylammonium citraconate, benzyldimethylphenylammonium citrate, benzyldimethylphenylammonium carbonate, bisbenzyldimethylphenylammonium oxalate, bisbenzyldimethylphenylammonium malonate, bisbenzyldimethylphenylammonium maleate, bisbenzyldimethylphenylammonium fumarate, bisbenzyldimethylphenylammonium citraconate, bisbenzyldimethylphenylammonium citrate, bisbenzyldimethylphenylammonium carbonate, etc.

[0142] 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 citraconate, lithium hydrogen citrate, lithium bicarbonate, lithium oxalate, lithium malonate, lithium maleate, lithium fumarate, lithium citraconate, 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 citrate, sodium bicarbonate, sodium oxalate, sodium malonate, sodium maleate, sodium fumarate, sodium citrate, 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 citrate,Examples include potassium biturethane, potassium bicarbonate, potassium oxalate, potassium malonate, potassium maleate, potassium fumarate, potassium citraconate, potassium citrate, and potassium carbonate.

[0143] In the present invention, examples of the curing catalyst (Xc) include thermosetting polysiloxane (Xc-10) having an ammonium salt, sulfonium salt, phosphonium salt, or iodonium salt as part of its structure.

[0144] The compound represented by the following general formula (Xm) can be used as a raw material for producing (Xc-10) used here. R 1A A1 R 2A A2 R 3A A3 Si(OR 0A ) (4-A1-A2-A3) (Xm) (In the formula, R 0A R is a hydrocarbon group having 1 to 6 carbon atoms. 1A , R 2A , R 3A Of these, at least one is an organic group having an ammonium salt, sulfonium salt, phosphonium salt, or 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. Here 、R 0A Examples of these groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, and phenyl group.

[0145] For example, as Xm, the following general formula (Xm-1) can be used as an example of a hydrolyzable silicon compound having a sulfonium salt as part of its structure. [ka]

[0146] (wherein R SA1 , R SA2 each 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 a part or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, an amino group, an alkylamino group, a halogen atom or the like. Also, R SA1 and R SA2 may form a ring together with the sulfur atom to which they are bonded, and when forming a ring, R SA1 , R SA2 each represents an alkylene group having 1 to 6 carbon atoms. R SA3 represents a linear, branched or cyclic alkylene group, alkenylene group, substituted or unsubstituted arylene group or aralkylene group having 1 to 20 carbon atoms, and a part or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, an amino group, an alkylamino group or the like. R SA1 , R SA2 , R SA3 may have an oxygen atom or a nitrogen atom in the middle of its chain or ring.)

[0147] In the above general formula (Xm-1), (Si) is described to indicate the bonding position with Si.

[0148] X -Examples include hydroxide ions, formate ions, acetate ions, propionate ions, butyrate ions, pentanoate ions, hexanoate ions, heptanoate ions, octanoate ions, nonanoate ions, decanoate ions, oleate ions, stearate ions, linoleate ions, linolenate ions, benzoate ions, p-methylbenzoate ions, p-t-butylbenzoate ions, phthalate ions, isophthalate ions, terephthalate ions, salicylate ions, trifluoroacetate ions, monochloroacetate ions, dichloroacetate ions, trichloroacetate ions, nitrate ions, chlorate ions, perchlorate ions, bromate ions, iodate ions, oxalate ions, malonate ions, methylmalonate ions, ethylmalonate ions, propylmalonate ions, butylmalonate ions, dimethylmalonate ions, diethylmalonate ions, succinate ions, methylsuccinate ions, glutarate ions, adipate ions, itaconate ions, maleate ions, fumarate ions, citraconate ions, citrate ions, carbonate ions, and the like.

[0149] Specific examples of the cation moiety of the compound represented by the general formula (Xm-1) include the following ions (X - is the same as defined above). [Chemical formula]

[0150] For example, a hydrolyzable silicon compound having an iodonium salt as part of its structure can be exemplified by the following general formula (Xm-2). <​​​​​​​​​R 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 of this group may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, etc. Also, R IA1 and R IA2 These may form a ring together with the nitrogen atom to which they bond, and if a ring is formed, R IA1 , R IA2 Each of these represents an alkylene group with 1 to 6 carbon atoms. IA2 R is a linear, branched, or cyclic alkylene group, alkenylene group, or substituted or unsubstituted arylene or aralkylene group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy groups, amino groups, alkylamino groups, etc. IA1 ~R IA2 It may have oxygen or nitrogen atoms in the middle of its chain or ring.

[0152] In the above general formula (Xm-2), (Si) is included to indicate the bonding site with Si. - This is as stated above.

[0153] The following ions are examples of the cation moiety of the compound represented by the above general formula (Xm-2): (X - (This is the same as above). [ka]

[0154] For example, the following general formula (Xm-3) can be used as an example of a hydrolyzable silicon compound having a phosphonium salt as part of its structure. [ka]

[0155] (In the formula, R PA1 , RPA2 , R PA3 Each of these groups 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 of these groups may be substituted with alkoxy groups, amino groups, alkylamino groups, halogen atoms, etc. Also, R PA1 and R PA2 These may form a ring together with the phosphorus atom to which they are bonded, and if a ring is formed, R PA1 , R PA2 Each of these represents an alkylene group with 1 to 6 carbon atoms. PA4 R is a linear, branched, or cyclic alkylene group, alkenylene group, or substituted or unsubstituted arylene or aralkylene group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy groups, amino groups, alkylamino groups, etc. PA1 ~R PA4 It may have oxygen or nitrogen atoms in the middle of its chain or ring.

[0156] In the above general formula (Xm-3), (Si) is included to indicate the bonding site with Si. - This is as stated above.

[0157] The following ions are examples of the cation moiety of the compound represented by the above general formula (Xm-3) (X - (This is the same as above).

[0158] [ka]

[0159] For example, the following general formula (Xm-4) can be used as an example of a hydrolyzable silicon compound having an ammonium salt as part of its structure. [ka]

[0160] (In the formula, R NA1 ), R NA2 ), R NA3 each represents 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 a part or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, an amino group, an alkylamino group, etc., and is a monovalent organic group. Also, R NA1 and R NA2 may form a ring together with the nitrogen atom to which they are attached. When forming a ring, R NA1 , R NA2 each represents an alkylene group having 1 to 6 carbon atoms or a cyclic heterocyclic ring or heteroaromatic ring containing nitrogen. R NA4 is a linear, branched or cyclic al tree ylene group, alkenylene group, a substituted or unsubstituted arylene group having 6 to 29 carbon atoms, and is a divalent organic group in which a part or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, an amino group, an alkylamino group, etc., and when R[[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​

[0163] [ka]

[0164] [ka]

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168] [ka]

[0169] (Organic solvents) The silicon-containing resist underlayer film forming composition of the present invention may contain a solvent. Preferred solvents are alcohol-based organic solvents, and more preferred are monoalkyl ether derivatives such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, and ethylene glycol monopropyl ether are preferred.

[0170] If these solvents are the main components, it is also possible to add non-alcoholic organic solvents as auxiliary solvents. Examples of such auxiliary solvents include acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, and cyclopentyl methyl ether.

[0171] (water) Water may be added to the silicon-containing resist underlayer film forming composition of the present invention. Adding water hydrates the polysiloxane compound in the composition, thereby improving lithography performance. The water content in the solvent component of the silicon-containing resist underlayer film forming composition of the present invention is preferably greater than 0% by mass and less than 50% by mass, more preferably 0.3 to 30% by mass, and even more preferably 0.5 to 20% by mass. When the water content is less than 50% by mass, the uniformity of the silicon-containing resist underlayer film is good and no repulsion occurs.

[0172] (High boiling point solvent) Furthermore, a high-boiling-point solvent with a boiling point of 180°C or higher may be added to the silicon-containing resist underlayer film forming composition of the present invention as needed. Examples of such high-boiling-point solvents include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecal, 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 include ethyl acetate, n-nonyl acetate, ethylene glycol monoethyl ether, 1,2-diacetoxyethane, 1-acetoxy-2-methoxyethane, 1,2-diacetoxypropane, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

[0173] The amount of the total solvent, including water, used is preferably 100 to 100,000 parts by mass, particularly 200 to 50,000 parts by mass, per 100 parts by mass of the polysiloxane compound, which is the base polymer.

[0174] [Other ingredients] (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 acids to be added include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, citric acid, and the like. Oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, and citric acid are particularly preferred. Furthermore, to maintain stability, two or more acids may be mixed and used. The amount added is 0.001 to 25 parts by mass, preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of silicon contained in the composition.

[0175] (Photoacid generator) In the present invention, a photoacid generator may be added to the composition. Specifically, as the photoacid generator used in the present invention, the materials described in paragraphs (0160) to (0179) of Japanese Patent Application Publication No. 2009-126940 can be added.

[0176] In addition, the present invention may include one or more compounds (photoacid generators) having an anionic part and a cation part represented by the following general formula (P-0) in one molecule. [ka] (Here, R 300 R is a divalent organic group substituted with one or more fluorine atoms. 301 and R 302 Each of these may be independently substituted with a heteroatom, or a heteroatom may be interposed, representing a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms. 303R represents a linear, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with heteroatoms or may have heteroatoms interposed. 301 and R 302 , or R 301 and R 303 L may bond with each other to form a ring together with the sulfur atoms in the formula. 304 This represents a linear, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with single bonds or heteroatoms, or may have heteroatoms interposed.

[0177] By combining such compounds (photoacid generators) with the thermosetting silicon-containing material of the present invention, it is possible to obtain a resist underlayer film that contributes to the rectangularization of the cross-sectional shape while maintaining the LWR of the upper resist.

[0178] In the above general formula (P-0), R 300 R is a divalent organic group substituted with one or more fluorine atoms. The above divalent organic group refers to, for example, a divalent hydrocarbon group such as a linear, branched, or cyclic alkylene group, alkenylene group, or arylene group having 1 to 20 carbon atoms. 300 Specifically, the following structure can be cited.

[0179] [ka]

[0180] In addition, in the above formula, (SO3 - ) is SO3 in the above general formula (P-0) - This was written to indicate the bonding site with the group. Also, (R 350 ) is the cation part in the above general formula (P-0) L 304 via R 300 This was included to indicate the connection point with the part that is connected to it.

[0181] R 301 and R 302Each of these groups may be independently substituted with a heteroatom, or a heteroatom may be interposed between them. These groups represent linear, branched, or cyclic monovalent hydrocarbon groups having 1 to 20 carbon atoms, such as alkyl groups, alkenyl groups, aryl groups, and aralkyl groups. 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 groups. Examples of alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl groups. Examples of oxoalkyl groups include 2-oxocyclopentyl group, 2-oxocyclohexyl group, 2-oxopropyl group, 2-oxoethyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, and 2-(4-methylcyclohexyl)-2-oxoethyl group. Examples of aryl groups include phenyl groups, naphthyl groups, thienyl groups, alkoxyphenyl groups such as 4-hydroxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4-tert-butoxyphenyl, and 3-tert-butoxyphenyl, alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-n-butylphenyl, and 2,4-dimethylphenyl, alkylnaphthyl groups such as methylnaphthyl and ethylnaphthyl, alkoxynaphthyl groups such as methoxynaphthyl, ethoxynaphthyl, n-propoxynaphthyl, and n-butoxynaphthyl, dialkylnaphthyl groups such as dimethylnaphthyl and diethylnaphthyl, and dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl. Examples of aralkyl groups include benzyl groups, 1-phenylethyl groups, and 2-phenylethyl groups.Examples of aryloxoalkyl groups include 2-phenyl-2-oxoethyl group, 2-(1-naphthyl)-2-oxoethyl group, 2-(2-naphthyl)-2-oxoethyl group, and other 2-aryl-2-oxoethyl groups. Also, R. 301 and R 302 These elements may bond with each other to form a ring with the sulfur atom in the formula, in which case the group shown in the following formula is an example.

[0182] [ka] (The dashed line indicates a connection.)

[0183] In the above general formula (P-0), R 303 R represents a linear, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with heteroatoms or may have heteroatoms interposed. 303 Specifically, these include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group. Examples include linear alkanediyl groups such as yl groups, tetradecane-1,14-diyl groups, pentadecane-1,15-diyl groups, hexadecane-1,16-diyl groups, and heptadecane-1,17-diyl groups; saturated cyclic hydrocarbon groups such as cyclopentanediyl groups, cyclohexanediyl groups, norbornanediyl groups, and adamantanediyl groups; and unsaturated cyclic hydrocarbon groups such as phenylene groups and naphthylene groups. Furthermore, some of the hydrogen atoms in these groups may be substituted with alkyl groups such as methyl groups, ethyl groups, propyl groups, n-butyl groups, and tert-butyl groups. Alternatively, they may be replaced with heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, resulting in the formation of hydroxyl groups, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, lactone rings, sultone rings, carboxylic acid anhydrides, haloalkyl groups, etc.301 and R 303 These elements may bond with each other to form a ring with the sulfur atom in the formula, in which case the group shown in the following formula is an example.

[0184] [ka] (The dashed line indicates a connection.)

[0185] In the above general formula (P-0), L 304 This represents a linear, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with single bonds or heteroatoms, or which may have heteroatoms interposed. 304 Specifically, these include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group. Examples include linear alkanediyl groups such as yl groups, tetradecane-1,14-diyl groups, pentadecane-1,15-diyl groups, hexadecane-1,16-diyl groups, and heptadecane-1,17-diyl groups; saturated cyclic hydrocarbon groups such as cyclopentanediyl groups, cyclohexanediyl groups, norbornanediyl groups, and adamantanediyl groups; and unsaturated cyclic hydrocarbon groups such as phenylene groups and naphthylene groups. Some of the hydrogen atoms of these groups may be substituted with alkyl groups such as methyl groups, ethyl groups, propyl groups, n-butyl groups, and tert-butyl groups. Alternatively, they may be replaced with heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, which may result in the formation of hydroxyl groups, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, lactone rings, sultone rings, carboxylic acid anhydrides, haloalkyl groups, etc.

[0186] The compound represented by the above general formula (P-0) (photoacid generator) is preferably represented by the following general formula (P-1). [ka] In the above general formula (P-1), X 305 , X 306 Each of these independently represents either a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but not all of them can be hydrogen atoms. 307 R represents an integer from 1 to 4. 301 , R 302 , R 303 and L 304 This is as stated above.

[0187] The photoacid generator represented by the above general formula (P-0) is more preferably represented by the following general formula (P-1-1). [ka]

[0188] In the above general formula (P-1-1), R 308 , R 309 and R 310 Each of these independently represents a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a hydrogen atom or a heteroatom. Specifically, this includes methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, norbornyl group, oxanorbornyl group, tricyclo[5.2.1.0 2,6Examples include decanyl groups and adamantyl groups. Some of the hydrogen atoms in these groups may be replaced by heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, or heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms may be interposed, resulting in the formation or interposition of hydroxyl groups, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, lactone rings, sultone rings, carboxylic acid anhydrides, haloalkyl groups, etc. Preferably, methyl groups, methoxy groups, tert-butyl groups, and tert-butoxy groups.

[0189] In the above general formula (P-1-1), n 308 and n 309 Each represents an integer from 0 to 5, preferably 0 or 1. 310 L represents an integer between 0 and 4, preferably 0 or 2. 304 , X 305 , X 306 , n 307 The details are as stated above.

[0190] The compound represented by the above general formula (P-0) (photoacid generator) is more preferably represented by the following general formula (P-1-2). [ka] In the above general formula (P-1-2), A 311 R represents a hydrogen atom or a trifluoromethyl group. 308 , R 309 , R 310 , n 308 , n 309 , n 310 , L 304 The details are as stated above.

[0191] More specifically, the photoacid generators represented by the above general formulas (P-0), (P-1), (P-1-1), and (P-1-2) include the structures shown below. However, the photoacid generators are not limited to these.

[0192] [ka]

[0193] [ka]

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] [ka]

[0198] The amount of compound represented by the above general formula (P-0) added is 0.001 to 40 parts by mass per 100 parts by mass of thermally crosslinkable polysiloxane, preferably 0.1 to 40 parts by mass, and more preferably 0.1 to 20 parts by mass. By adding such photoacid generators, the residue in the exposed areas of the upper resist can be reduced, and a small LWR pattern can be formed.

[0199] (Stabilizer) Furthermore, in the present invention, a stabilizer can be added to the composition. A monovalent or divalent or higher alcohol having a cyclic ether as a substituent can be added as a stabilizer. In particular, adding the stabilizer described in paragraphs (0181) to (0182) of Japanese Patent Application Publication No. 2009-126940 can improve the stability of the silicon-containing resist underlayer film forming composition. The amount of stabilizer added can be preferably 0.001 to 50 parts by mass, more preferably 0.01 to 40 parts by mass, per 100 parts by mass of thermally crosslinkable polysiloxane.

[0200] (Surfactants) Furthermore, in the present invention, surfactants can be added to the composition as needed. Specifically, materials described in paragraph (0185) of Japanese Patent Application Publication No. 2009-126940 can be added. The amount of surfactant added is preferably 0 to 10 parts by mass, and particularly preferably 0 to 5 parts by mass, per 100 parts by mass of thermally crosslinkable polysiloxane.

[0201] [Pattern formation method] The present invention provides a pattern formation method using the silicon-containing resist underlayer film formation composition described above. The embodiments thereof are shown below.

[0202] (I) A step of forming a resist underlayer film on a workpiece or a film formed on a workpiece using the silicon-containing resist underlayer film forming composition of the present invention, A step of forming a resist upper layer film using a resist upper layer film composition containing a compound having polymerizable functional groups on the resist lower layer film, Pattern formation including the step of forming a circuit pattern on the resist upper layer film. method The silicon-containing resist underlayer film forming composition is heated and cured to form the resist underlayer film, A pattern formation method characterized by forming the circuit pattern and causing crosslinking between the resist underlayer film and the resist upper layer film by irradiation with high-energy rays.

[0203] (II) A step of forming an organic film on a workpiece using a coating-type organic film material, A step of forming a resist underlayer on the aforementioned organic film using the silicon-containing resist underlayer forming composition of the present invention, A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern onto an organic film by etching, using the resist underlayer film on which the pattern has been transferred as a mask. A pattern forming method characterized by comprising the step of transferring the pattern to a workpiece by etching, using the organic film on which the pattern has been transferred as a mask.

[0204] (III) A step of forming an organic hard mask mainly composed of carbon on a workpiece by CVD, The steps include forming a resist underlayer film on the aforementioned organic hard mask using the silicon-containing resist underlayer film forming composition of the present invention, A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern onto the organic hard mask by dry etching, using the resist underlayer film on which the pattern has been transferred as a mask. A pattern forming method characterized by comprising the step of transferring the pattern to a workpiece by dry etching using the organic hard mask on which the pattern has been transferred as a mask.

[0205] (IV) A step of forming an organic film on a workpiece using a coating-type organic film material, A step of forming an inorganic hard mask interlayer on the organic film by CVD or ALD, A step of forming a resist underlayer on the inorganic interlayer using the silicon-containing resist underlayer forming composition of the present invention, A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern to the inorganic interlayer by etching, using the resist underlayer film on which the circuit pattern is formed as a mask, A step of transferring the pattern onto an organic film by etching, using the inorganic interfilm on which the pattern has been transferred as a mask, A pattern forming method characterized by comprising the step of transferring the pattern to a workpiece by etching, using the organic film on which the pattern has been transferred as a mask.

[0206] (V) A step of forming an organic hard mask mainly composed of carbon on a workpiece by CVD, The process involves forming an inorganic hard mask interlayer on the aforementioned organic hard mask by CVD or ALD, A step of forming a resist underlayer on the inorganic interlayer using the silicon-containing resist underlayer forming composition of the present invention, A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern to the inorganic interlayer by etching, using the resist underlayer film on which the circuit pattern is formed as a mask, A step of transferring the pattern by etching onto the organic hard mask mainly composed of carbon, using the inorganic interfilm on which the pattern has been transferred as a mask, A pattern forming method characterized by comprising the step of transferring the pattern to a workpiece by etching, using the organic hard mask on which the pattern has been transferred as a mask.

[0207] The above-mentioned organic hard mask and inorganic hard mask interlayer (inorganic interlayer) are not particularly limited and may be formed by known techniques. The following will explain the negative pattern formation method with examples, but the same method can be used for positive patterns by taking appropriate measures.

[0208] (Negative pattern formation method 1) The present invention provides a pattern formation method characterized by forming an organic underlayer film on a workpiece using a coating-type organic underlayer film material, forming a silicon-containing resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film forming composition of the present invention, forming a photoresist film on the silicon-containing resist underlayer film using the resist composition, exposing the photoresist film with EUV light after heat treatment, forming a negative pattern by dissolving the unexposed parts of the photoresist film with an alkaline developer, transferring the pattern to the silicon-containing resist underlayer film by dry etching using the photoresist film with the pattern formed on it as a mask, transferring the pattern to the organic underlayer film by dry etching using the silicon-containing resist underlayer film with the pattern transferred on it as a mask, and further transferring the pattern to the workpiece by dry etching using the organic underlayer film with the pattern transferred on it as a mask (a so-called "multilayer resist method"). The resist composition may be a chemically amplified resist composition.

[0209] (Negative pattern formation method 2) Furthermore, the present invention provides a pattern formation method characterized by forming an organic hard mask mainly composed of carbon on a workpiece by CVD, forming a silicon-containing resist underlayer film on the organic hard mask using the silicon-containing resist underlayer film forming composition of the present invention, forming a photoresist film on the silicon-containing resist underlayer film using the resist composition, exposing the photoresist film with EUV light after heat treatment, forming a negative pattern by dissolving the unexposed parts of the photoresist film with an alkaline developer, transferring the pattern to the silicon-containing resist underlayer film by dry etching using the photoresist film on which the pattern has been formed as a mask, transferring the pattern to the organic hard mask by dry etching using the silicon-containing resist underlayer film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by dry etching using the organic hard mask on which the pattern has been transferred as a mask (so-called "multilayer resist method"). The resist composition may be a chemically amplified resist composition.

[0210] When a pattern is formed using the silicon-containing resist underlayer film formation composition of the present invention, as described above, by optimizing the combination with CVD films and organic underlayer films, a pattern formed with photoresist can be formed on a substrate without causing size conversion differences.

[0211] In the negative-type pattern formation method, a photoresist film is formed, followed by heat treatment, exposure, and then alkaline development using an alkaline developer to obtain a negative-type resist pattern. It is also preferable to perform post-exposure baking (PEB) after exposure.

[0212] Furthermore, by exposing the photoresist film, the silicon-containing resist underlayer film and the resist upper layer film containing a polymerizable functional group crosslink each other through their polymerizable functional groups. This reaction causes the photoresist film and the silicon-containing resist underlayer film to adhere firmly, suppressing pattern deformation.

[0213] As the alkaline developer, tetramethylammonium hydroxide (TMAH) or the like can be used.

[0214] [Pattern formation method of the present invention using a three-layer resist method] The positive pattern formation method of the present invention using a three-layer resist method is as follows (see Figure 1). In this process, first, an organic underlayer film 2 is fabricated on the workpiece 1 by spin coating (Figure 1(IA)). Since this organic underlayer film 2 acts as a mask when etching the workpiece 1, it is desirable that it has high etching resistance and that it does not mix with the silicon-containing resist underlayer film of the upper layer. Therefore, it is desirable to crosslink it with heat or acid after it has been formed by spin coating.

[0215] A silicon-containing resist underlayer film 3 is formed on top of this by spin coating using the silicon-containing resist underlayer film formation composition of the present invention (Figure 1(IB)), and a photoresist film 4 is formed by spin coating (Figure 1(IC)).

[0216] The photoresist film 4 can be patterned according to a standard method by pattern exposure using a light source P appropriate to the photoresist film 4, such as KrF excimer laser light, ArF excimer laser light, F2 laser light, or EUV light, preferably by photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, and nanoimprinting, or a combination thereof (a mask 5 is used as needed). In the present invention, EUV light is most preferred (Figure 1(ID)), and after heat treatment under conditions tailored to each photoresist film (Figure 1(IE)), development is performed with an alkaline developer, and then rinsing is performed as needed to obtain a negative-type resist pattern 4a (Figure 1(IF)).

[0217] Next, using this resist pattern 4a as an etching mask, the photoresist film 4 is etched under dry etching conditions that result in a significantly higher etching rate of the silicon-containing resist underlayer film 3, such as dry etching using a fluorine-based gas plasma. As a result, a negative-type silicon-containing resist underlayer film pattern 3a can be obtained with almost no influence from pattern changes due to side etching of the resist film (Figure 1(IG)).

[0218] Next, the substrate having the negative-type silicon-containing resist underlayer pattern 3a onto which the negative-type resist pattern obtained above has been transferred is subjected to dry etching conditions that result in a significantly higher etching rate of the organic underlayer 2, such as reactive dry etching using an oxygen-containing gas plasma or reactive dry etching using a hydrogen-nitrogen-containing gas plasma, to etch the organic underlayer 2. This etching process yields a negative-type organic underlayer pattern 2a, but the topmost photoresist film is usually lost at the same time (Figure 1(IH)). Furthermore, by using the negative-type organic underlayer pattern 2a obtained here as an etching mask, the workpiece 1 can be precisely etched using dry etching, such as fluorine-based dry etching or chlorine-based dry etching, and the negative-type pattern 1a can be transferred to the workpiece 1 (Figure 1(II)).

[0219] Furthermore, in the above three-layer resist process, it is also possible to apply an organic hard mask formed by the CVD method instead of the organic underlayer film 2. In that case as well, the workpiece 1 can be processed using the same procedure as described above.

[0220] When using high-energy rays for exposure, such as ultraviolet light, far ultraviolet light, EUV, X-rays, soft X-rays, excimer laser light, gamma rays, or synchrotron radiation, the exposure amount is preferably 1 to 200 mJ / cm², either directly or using a mask to form the desired pattern. 2 To the extent, more preferably 10 to 100 mJ / cm² 2Irradiate to the extent of [a certain degree]. When using EB as the high-energy beam, the exposure dose is preferably 0.1 to 500 μC / cm². 2 To a degree, more preferably 0.5 to 400 μC / cm² 2 The drawing can be done either directly or using a mask to form the desired pattern, to achieve the desired result. [Examples]

[0221] The present invention will be specifically described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these descriptions. In the following examples, % represents mass%, and the weight-average molecular weight (Mw) is expressed in polystyrene equivalent by GPC using RI (differential refraction) as the detector and tetrahydrofuran as the eluent. Furthermore, in the following examples, the silicon-containing resist underlayer film formation composition prepared contained non-condensation reactive organic groups, and it was confirmed by measuring these organic groups using infrared spectroscopy that they remained unreacted even after the thermosetting reaction of the polysiloxane resin.

[0222] [Synthesis Example 1] A mixture of 0.5 g of 7% nitric acid and 76 g of deionized water was mixed with a mixture of monomers 102:32.0 g and 110:22.4 g, and hydrolysis condensation was carried out at room temperature for 24 hours. After the reaction was complete, 450 g of propylene glycol ethyl ether (PGEE) was added, and the water and by-product alcohols from the hydrolysis condensation were removed by distillation under reduced pressure to obtain 350 g of a PGEE solution of polymerizable group-containing polysiloxane compound 1 (compound concentration 10%). The polystyrene-equivalent molecular weight of this solution was measured to be Mw = 2,500.

[0223] Under the same conditions as in Synthesis Example 1, Synthesis Examples 2 through 18 were carried out using the monomers shown in Table 1, and the target products were obtained in each case.

[0224] [Table 1]

[0225] Monomer 100: PhSi(OCH3)3 Monomer 101: CH3Si(OCH3)3 Monomer 102:Si(OCH3)4 Monomer 103: Si(OC2H5)4

[0226] [ka]

[0227] [Examples, Comparative Examples] Polysiloxane compounds 1 to 18 obtained in the above synthesis examples 1 to 18, crosslinking catalyst, acid, solvent, and water were mixed in the proportions shown in Table 2, and filtered through a 0.1 μm fluororesin filter to prepare polysiloxane underlayer film forming composition solutions, which were designated Sol. 1 to 19, respectively.

[0228] The polysiloxane compounds 1 to 6 obtained in the above synthesis examples 1 to 6 are condensation reaction type thermosetting silicon-containing materials (Sx) in the present invention. On the other hand, polysiloxane compounds 7, 8, 17, and 18 do not have repeating units represented by general formula (Sx-4) or general formula (Sx-5), and polysiloxane compounds 17 and 18 in particular contain repeating units (T units) containing a phenyl group. Polysiloxane compounds 9 to 16 contain one or more of either repeating units represented by general formula (Sx-4) or repeating units represented by general formula (Sx-5) in the resin in an amount exceeding 70 mol%, and polysiloxane compounds 13 to 16 in particular contain repeating units (T units) having cyclic ether groups or diol groups, which are condensation reaction groups, instead of polymerizable double bonds. In other words, the above polysiloxane compounds 7 to 18 are not the above condensation reaction type thermosetting silicon-containing materials.

[0229] [Table 2]

[0230] TPSNO3: Triphenylsulfonium Nitrate QBANO3: Tetrabutylammonium nitrate PGEE: Propylene glycol monoethyl ether

[0231] Patterning Exam An organic underlayer film was formed on a silicon wafer using a coating-type organic underlayer film material to obtain a Si substrate. Next, silicon-containing resist underlayer film formation compositions Sol.1 to 19 were spin-coated onto the Si substrate and heated at 220°C for 60 seconds to produce silicon-containing resist underlayer films Film1 to 19 with a thickness of 25 nm.

[0232] EB lithography evaluation Next, Sol.1 to 19 were spin-coated onto a Si substrate with a 60nm thickness of Nissan Chemical Industries' DUV-42 anti-reflective coating. Then, the resist compositions shown in Table 3 were spin-coated onto Film1 to 19, and pre-baked at 110°C for 60 seconds using a hot plate to produce a 35nm thick resist film. This resist film was then exposed using an EB lithography system (ELS-F125, accelerating voltage 125kV) manufactured by Elionix Corporation. PEB was performed on a hot plate at 60°C for 60 seconds, and development was carried out with a 2.38 mass% TMAH aqueous solution for 30 seconds to obtain a line and space pattern with a space width of 20nm and a pitch of 40nm. Using a Hitachi High-Tech Corporation length-measuring SEM (CG-5000), the exposure amount when a line dimension of 40 nm was formed was measured and defined as the sensitivity. Additionally, using the same Hitachi High-Tech Corporation length-measuring SEM (CG-5000), dimensions were measured at 10 points along the longitudinal direction of the space width. From these results, three times the standard deviation (σ) (3σ) was calculated and defined as the LWR. Furthermore, the minimum line width (nm) of the separated LS pattern at the optimal exposure amount Eop was defined as the limiting resolution. The results are shown in Table 4.

[0233] [ka]

[0234] [Table 3] • Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) DAA (Diacetone Alcohol)

[0235] [Table 4]

[0236] EUV lithography evaluation Sol.1~19 were spin-coated onto a Si substrate and heated at 220°C for 60 seconds to create silicon-containing resist underlayer films (Film1~19) with a thickness of 25 nm. Resist materials dissolved in the proportions shown in Table 3 were spin-coated onto Film1~19, and pre-baked at 110°C for 60 seconds using a hot plate to produce a resist film with a thickness of 35 nm. An ASML EUV scanner NXE3300 (NA0.33, σ0.9 / 0.6, 90-degree dipole illumination) was used to expose a 22 nm LS1:1 pattern, followed by PEB on a hot plate at 60°C for 60 seconds, and development with a 2.38 mass% TMAH aqueous solution for 30 seconds to obtain a line and space pattern with a space width of 14 nm and a pitch of 28 nm. The aforementioned LS pattern was observed using a length-measuring SEM (CG-5000) manufactured by Hitachi High-Tech Corporation, and the optimal exposure dose Eop(mJ / cm²) was determined to obtain an LS pattern with a space width of 22 nm and a pitch of 44 nm. 2 The sensitivity was determined by calculating the following: The LS pattern obtained by irradiation with the optimal exposure (Eop) was measured at 10 points along the longitudinal direction of the space width using a length-measuring SEM (CG-5000) manufactured by Hitachi High-Tech Corporation. From these results, three times the standard deviation (σ) (3σ) was calculated and defined as the LWR. Furthermore, the minimum linewidth (nm) of the separated LS pattern at the optimal exposure (Eop) was defined as the limiting resolution. The results are shown in Table 5.

[0237] [Table 5]

[0238] The results shown in Tables 4 and 5 indicate that when a polysiloxane film with remaining crosslinkable organic groups, formed using a silicon-containing resist underlayer film formation composition containing the thermosetting silicon-containing material of the present invention, is used as a resist underlayer film, pattern collapse can be suppressed (Examples 1-14, 15-28). This shows that the above resist underlayer film can contribute to preventing pattern collapse. On the other hand, when a polysiloxane film formed using a silicon-containing resist underlayer film formation composition containing a thermosetting silicon-containing material that contains crosslinkable organic groups but whose repeating unit ratio is not within the scope of the present invention was used as a resist underlayer film, the minimum linewidth was inferior (Comparative Examples 1-6, 13-18). Furthermore, when a resist underlayer film formed using a resist underlayer film formation composition containing non-radical polymerizable organic groups and not containing radically crosslinkable organic groups was used, the LWR was similar to that of the examples, but the minimum linewidth was inferior (Comparative Examples 7-10, 19-22). In addition, when a polysiloxane film formed using a silicon-containing resist underlayer film formation composition containing a thermosetting silicon-containing material containing an aryl substituent, such as monomer 100, was used as a resist underlayer film, the lithography performance deteriorated and the minimum linewidth was inferior, possibly due to thermosetting degradation (Comparative Examples 11, 12, 23, 24). As described above, it has been found that the present invention, in EUV lithography as well as EB lithography, exhibits superior LWR and limiting resolution compared to conventional resist underlayer film formation compositions with excellent adhesion when forming negative-type patterns by alkaline solvent development.

[0239] This specification includes the following embodiments: [1]: A silicon-containing resist underlayer film formation composition comprising a condensation reaction type thermosetting silicon-containing material (Sx) which is a polysiloxane resin, wherein the material (Sx) has non-condensation reactive organic groups that react with radical chemical species generated by irradiation with high-energy rays, and contains in the resin in an amount greater than 0 and less than 70 mol% of either a repeating unit represented by the following general formula (Sx-4) or a repeating unit represented by the following general formula (Sx-5), and the organic groups remain unreacted even after the thermosetting reaction of the polysiloxane resin. [ka] (In the formula, R 4 (This is a non-aromatic substituent that may contain a hydrogen atom, a hydroxyl group, or a monovalent heteroatom having 1 to 30 carbon atoms.) [2]: The silicon-containing resist underlayer film forming composition of [1], characterized in that the polysiloxane resin of the material (Sx) contains one or more of the repeating units represented by the following general formula (Sx-1), the repeating units represented by the following general formula (Sx-2), and the substructures represented by the following general formula (Sx-3), with these repeating units present in the resin in an amount of 30 to 99 mol%, and one or more of the repeating units represented by the above general formula (Sx-4) or the repeating units represented by the above general formula (Sx-5) present in an amount of 1 to 70 mol%, and further comprises a crosslinking catalyst for siloxane polymerization (Xc), an alcohol-based organic solvent, and water. [ka] (In the formula, R 1 R is a non-condensation reactive organic group having one or more polymerizable double bonds, or a non-condensation reactive organic group that reacts with radical chemical species generated by irradiation with high-energy rays, 2 , R 3 R is independent 1 It is the same as, or a non-aromatic substituent that may contain a hydrogen atom, a hydroxyl group, or a monovalent heteroatom having 1 to 30 carbon atoms. 4 (As stated above.) [3]: The organic group R1 , R 2 and R 3 However, the following general formula R 5 or R 6 A silicon-containing resist underlayer film formation composition comprising the organic group represented by [2]. [ka] (In the formula, L 1 R is a divalent organic group with 1-15 carbon atoms that may contain an oxygen atom, Ar is an aromatic ring with 6-14 carbon atoms, and * represents the linkage with a silicon atom. 7 R is a hydrogen atom or a monovalent organic group with 1-5 carbon atoms. 1 , R 2 and R 3 They may be the same or different from each other. [4]: The organic group R 5 However, the following general formula R 8 The organic group is represented by the organic group R 6 However, the following general formula R 9 A silicon-containing resist underlayer film forming composition [3] characterized in that it is an organic group represented by . [ka] (In the formula, L 2 R is a divalent organic group having 1-10 carbon atoms that may contain an oxygen atom, 10 is a hydrogen atom or a monovalent organic group with 1-5 carbon atoms. * represents the linkage with a silicon atom. [5]: A silicon-containing resist underlayer film forming composition according to any one of [2] to [4], characterized in that the crosslinking catalyst for siloxane polymerization is a sulfonium salt, iodonium salt, phosphonium salt, ammonium salt, or a polysiloxane having these as part of its structure, or an alkali metal salt. [6]: The silicon-containing resist underlayer film forming composition is A step of forming a resist underlayer film using the silicon-containing resist underlayer film formation composition, A silicon-containing resist underlayer forming composition, one of any one of [1] to [5], characterized in that it is used in a pattern forming method comprising the step of forming a resist upper layer using a resist upper layer composition containing a compound having polymerizable functional groups on the resist underlayer. [7]: A step of forming a resist underlayer on a workpiece or a film formed on a workpiece using one of the silicon-containing resist underlayer forming compositions from [1] to [6], A step of forming a resist upper layer film using a resist upper layer film composition containing a compound having polymerizable functional groups on the resist lower layer film, Pattern formation including the step of forming a circuit pattern on the resist upper layer film. method The silicon-containing resist underlayer film forming composition is heated and cured to form the resist underlayer film, A pattern formation method characterized by forming the circuit pattern and causing crosslinking between the resist underlayer film and the resist upper layer film by irradiation with high-energy rays. [8] A step of forming an organic film on a workpiece using a coating-type organic film material, A step of forming a resist underlayer on the organic film using one of the silicon-containing resist underlayer forming compositions [1] to [6], A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern onto an organic film by etching, using the resist underlayer film on which the pattern has been transferred as a mask. A pattern forming method characterized by comprising the step of transferring the pattern to a workpiece by etching, using the organic film on which the pattern has been transferred as a mask. [9]: A step of forming an organic hard mask mainly composed of carbon on a workpiece by CVD, A step of forming a resist underlayer on the organic hard mask using one of the silicon-containing resist underlayer forming compositions [1] to [6], A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern onto the organic hard mask by dry etching, using the resist underlayer film on which the pattern has been transferred as a mask. A pattern forming method characterized by comprising the step of transferring the pattern to a workpiece by dry etching using the organic hard mask on which the pattern has been transferred as a mask.

[10] A step of forming an organic film on a workpiece using a coating-type organic film material, A step of forming an inorganic hard mask interlayer on the organic film by CVD or ALD, A step of forming a resist underlayer on the inorganic interlayer using one of the silicon-containing resist underlayer forming compositions [1] to [6], A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern to the inorganic interlayer by etching, using the resist underlayer film on which the circuit pattern is formed as a mask, A step of transferring the pattern onto an organic film by etching, using the inorganic interfilm on which the pattern has been transferred as a mask, A pattern forming method characterized by comprising the step of transferring the pattern to a workpiece by etching, using the organic film on which the pattern has been transferred as a mask.

[11] : A step of forming an organic hard mask mainly composed of carbon on a workpiece by CVD, A step of forming an inorganic hard mask interlayer on the organic film by CVD or ALD, A step of forming a resist underlayer on the inorganic interlayer using one of the silicon-containing resist underlayer forming compositions [1] to [6], A step of forming a resist upper layer on the resist lower layer using a resist upper layer composition consisting of a photoresist composition, The steps include forming a circuit pattern on the resist upper layer film, A step of transferring the pattern to the resist underlayer by etching, using the resist upper layer on which the circuit pattern is formed as a mask, A step of transferring the pattern to the inorganic interlayer by etching, using the resist underlayer film on which the circuit pattern is formed as a mask, A step of transferring the pattern by etching onto the organic hard mask mainly composed of carbon, using the inorganic interfilm on which the pattern has been transferred as a mask, A pattern forming method characterized by comprising the step of transferring the pattern to a workpiece by etching, using the organic hard mask on which the pattern has been transferred as a mask.

[12] : A pattern formation method according to any one of [7] to

[11] , characterized in that the pattern formation on the resist upper film is by photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[13] : A pattern forming method according to any one of the [7] to

[12] , characterized in that the workpiece is a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film.

[14] : A pattern forming method any one of [7] to

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

[0240] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention. [Explanation of Symbols]

[0241] 1...workpiece, 1a...negative pattern, 2...Organic underlayer film, 2a...Negative type organic underlayer film pattern, 3...Silicon-containing resist underlayer film, 3a...Negative silicon-containing resist underlayer film pattern, 4...Photoresist film, 4a...Negative resist pattern, 5...Mask P...Light source.

Claims

1. A step of forming a resist underlayer film on a workpiece or a film formed on a workpiece using a silicon-containing resist underlayer film forming composition, A step of forming a resist upper layer film using a resist upper layer film composition containing a compound having polymerizable functional groups on the resist lower layer film, A pattern forming method comprising the step of forming a circuit pattern on the resist upper layer film, wherein the resist lower layer film is formed by heat curing the silicon-containing resist lower layer film forming composition, This method involves irradiating the circuit pattern with high-energy rays and causing crosslinking between the resist underlayer and the resist upper layer. The above silicon-containing resist underlayer film forming composition comprises a condensation reaction type thermosetting silicon-containing material (Sx) which is a polysiloxane resin, wherein the material (Sx) has non-condensation reactive organic groups that react with radical chemical species generated by irradiation with high-energy rays, and contains one or more repeating units represented by the following general formula (Sx-4) or the following general formula (Sx-5), and the organic groups remain unreacted even after the thermosetting reaction of the polysiloxane resin. 【Chemistry 1】 (In the formula, R4 is a hydrogen atom, a hydroxyl group, or a linear alkyl group having 1 to 5 carbon atoms.) A pattern-forming method characterized in that the polysiloxane resin of the material (Sx) contains one or more of the repeating units represented by the following general formula (Sx-1), the repeating units represented by the following general formula (Sx-2), and the substructures represented by the following general formula (Sx-3), with the resin containing a total of 30 to 99 mol% of these repeating units and / or substructures, and containing one or more of the repeating units represented by the above general formula (Sx-4) or the repeating units represented by the above general formula (Sx-5) in an amount of 1 to 70 mol%, and further containing a crosslinking catalyst for siloxane polymerization (Xc), an alcohol-based organic solvent, and water. 【Chemistry 2】 (In the formula, R1, R2, and R3 are organic groups represented by the following general formula R8 or R9.) 【Transformation 3】 (In the formula, L2 is a divalent organic group having 1 to 10 carbon atoms that may contain an oxygen atom, and R10 is a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms. * represents the linkage with a silicon atom.)

2. The pattern forming method according to claim 1, characterized in that the crosslinking catalyst for siloxane polymerization is a sulfonium salt, iodonium salt, phosphonium salt, ammonium salt, or a polysiloxane having these as part of its structure, or an alkali metal salt.

3. The pattern formation method according to claim 1, characterized in that the pattern formation on the resist upper film is performed by photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

4. The pattern forming method according to claim 1, characterized in that the workpiece is a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film.

5. The pattern forming method according to claim 4, characterized in that the metal constituting the workpiece is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

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