Composition for forming film, method for producing cured film, cage silsesquioxane and cyclic siloxane

Abstract

To provide a composition for forming a film comprising a silicon-containing compound and having an enhanced effect of reducing pattern roughness, a method for producing a patterned cured film using the composition and a cage silsesquioxane and a cyclic siloxane used in the composition for forming a film.SOLUTION: There is provided a composition for forming a film, which comprises a silicon-containing polymer (A) containing a phenolic hydroxyl group, a photoacid generator (B), a silicon-containing cross-linking agent (C1) having a methylol group and / or an alkoxymethyl group and a base component (D) which controls diffusion of an acid generated by exposure or the photoacid generator (B), a silicon-containing cross-linking agent (C2) having a methylol group and / or an alkoxymethyl group and a phenolic hydroxyl group and the base component (D).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a film-forming composition, a method for manufacturing a patterned cured film, a cage-type silsesquioxane, and a cyclic siloxane.

Background Art

[0002] In the manufacture of electronic components, a process including etching is performed on a laminate in which a resist film is formed on a substrate such as a silicon wafer using a resist material. For example, a resist pattern is formed on the resist film by selectively exposing the resist film, and dry etching is performed using this as a mask to form a pattern on the substrate.

[0003] In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has been rapidly progressing due to the advancement of lithography technology. As a method for pattern miniaturization, generally, the short wavelength (high energy) of the exposure light source is being performed.

[0004] For resist materials, lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions are required. As a resist material that satisfies such requirements, a chemically amplified resist composition containing a base material component whose solubility in a developer changes by the action of an acid and an acid generator component that generates an acid upon exposure has been conventionally used. In a chemically amplified resist composition, generally, a resin having a plurality of structural units is used to improve lithography characteristics and the like. Further, a chemically amplified resist composition in which an acid diffusion controller that controls the diffusion of an acid generated from the acid generator component upon exposure is used in combination with the acid generator component has been proposed.

[0005] Furthermore, as a resist material, a material having etching resistance is required to function as a mask for substrate processing. In contrast, a silicon-containing compound is usually used as the base material component. For example, Patent Document 1 discloses a resist composition containing a silicon-containing resin, an acid generator component, and a photo-disintegrating base that controls the diffusion of acid in order to cope with pattern miniaturization and etching.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] With further progress in lithography technology, expansion of application fields, etc., pattern miniaturization is rapidly advancing. Along with this, when manufacturing semiconductor elements, etc., a technology capable of forming a pattern with fine dimensions in a good shape is required. For example, in lithography using EUV (extreme ultraviolet light), formation of fine patterns of a dozen or so nm is targeted. As the pattern dimensions become smaller in this way, it becomes more difficult to achieve both etching resistance and lithography characteristics. On the other hand, a film-forming composition containing a silicon-containing compound as a base material component, as disclosed in Patent Document 1, has the advantage of high dry etching resistance compared to a film-forming composition using a general organic material as a base material component. However, in the formation of the target fine patterns, further improvement is required in terms of the effect of reducing pattern roughness.

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a film-forming composition containing a silicon-containing compound and having an enhanced effect of reducing pattern roughness, a method for manufacturing a patterned cured film using the same, and a cage-type silsesquioxane used in the film-forming composition.

Means for Solving the Problems

[0009] In order to solve the above problems, as a result of intensive studies by the present inventors, it has been found that when a silicon-containing crosslinking agent having a methylol group and / or an alkoxymethyl group is used, the above problems can be solved, and the present invention has been completed. Specifically, the present invention provides the following.

[0010] [1] A film-forming composition comprising a silicon-containing polymer (A) having a phenolic hydroxyl group, a photoacid generator (B), a silicon-containing crosslinking agent (C1) having a methylol group and / or an alkoxymethyl group, and a base component (D) that controls the diffusion of the acid generated by exposure, or The photoacid generator (B), a silicon-containing crosslinking agent (C2) having a methylol group and / or an alkoxymethyl group and a phenolic hydroxyl group, and the base component (D). Film-forming composition.

[0011] [2] The film-forming composition according to [1], wherein the methylol group and / or the alkoxymethyl group of the silicon-containing crosslinking agent (C1) or the silicon-containing crosslinking agent (C2) is bonded to an aromatic group or a nitrogen atom.

[0012] [3] The silicon-containing crosslinking agent (C1) contains at least one selected from the group consisting of a cage-type silsesquioxane (C1-1) represented by the following formula (c1-1) and a cyclic siloxane (C1-2) represented by the following formula (c1-2), The silicon-containing crosslinking agent (C2) contains at least one selected from the group consisting of a cage-type silsesquioxane (C2-1) represented by the following formula (c2-1) and a cyclic siloxane (C2-2) represented by the following formula (c2-2), and the film-forming composition according to [1] or [2]. [Chemical formula] (In formula (c1-1), R 1 ~R 8is, independently of one another, an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, R 1 ~R 8 at least one of which is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group. L 1 ~L 8 is, independently of one another, a divalent linking group represented by any one of the following formulas (c1-L-1) to (c1-L-7).) [Chemical formula] (In formulas (c1-L-1) to (c1-L-7), Z X and Z Y are, independently of one another, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom. n1 to n7 are, independently of one another, an integer of 0 or more and 10 or less. * represents a bond to Si. ** represents a bond to any one of R 1 ~R 8 .) [Chemical formula] (In formula (c1-2), R 9 are, independently of one another, an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, R 9 at least one of which is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group. L 9 is, independently of one another, a divalent linking group represented by any one of the following formulas (c2-L-1) to (c2-L-6). nc2 is an integer of 3 or more and 7 or less. Z Z are, independently of one another, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom.) [Chemical formula] (In formulas (c2-L-1) to (c2-L-6), n8 to n13 are each independently an integer of 0 or more and 10 or less. * represents a bond to Si. ** represents a bond to R 9 .) [Chemical formula] (In formula (c2-1), R 1 ~R 8 are each independently an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R 1 ~R 8 is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, and at least one of the others is an aromatic group having a phenolic hydroxyl group. L 1 ~L 8 are each independently a divalent linking group represented by any of the above formulas (c1-L-1) to (c1-L-7).) [Chemical formula] (In formula (c2-2), R 9 are each independently an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R 9 is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, and at least one of the others is an aromatic group having a phenolic hydroxyl group. L 9 are each independently a divalent linking group represented by any of the above formulas (c2-L-1) to (c2-L-6). nc2 is an integer of 3 or more and 7 or less. ZZ is independently a hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom.

[0013] [4] The composition for film formation according to any one of [1] to [3], wherein the silicon-containing polymer (A) contains a silicon-containing polymer (A0) having a structural unit represented by the following formula (a0-1).

Chemical formula

[0014] [5] The composition for film formation according to [4], wherein the silicon-containing polymer (A0) has a structural unit represented by the following formula (a0-1-1).

Chemical formula

[0015] [6] The composition for film formation according to any one of [1] to [5], wherein the photoacid generator (B) contains an onium salt represented by the following formula (b0).

Chemical formula

[0016] [7] The film-forming composition according to any one of [1] to [6], wherein the base component (D) contains at least one selected from the group consisting of a compound represented by the following formula (d0-1) and a compound represented by the following formula (d0-2).

Chemical formula

[0017] [8] Forming a coating film comprising the film-forming composition according to any one of [1] to [7] on a support, Selectively exposing the coating film Developing the coating film after the exposure to form a patterned cured film, and A method for producing a patterned cured film.

[0018] [9] The method for producing a patterned cured film according to [8], wherein the coating film is exposed to EUV (extreme ultraviolet rays).

[0019]

[10] A cage-type silsesquioxane represented by the following formula (c0-1).

Chemical formula

Chemical formula

[0020]

[11] A cyclic siloxane represented by the following formula (c0-2).

Chemical formula

[0021] According to the present invention, there can be provided a film-forming composition containing a silicon-containing compound and having an enhanced effect of reducing pattern roughness, a method for producing a patterned cured film using the same, and a cage-type silsesquioxane and a cyclic siloxane used in the film-forming composition. [Modes for Carrying Out the Invention]

[0022] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments and can be implemented with appropriate modifications within the scope of the object of the present invention.

[0023] ≪Film-Forming Composition≫ The film-forming composition contains a silicon-containing polymer (A) having a phenolic hydroxyl group, a photoacid generator (B), a silicon-containing crosslinking agent (C1) having a methylol group and / or an alkoxymethyl group, and a base component (D) that controls the diffusion of the acid generated by exposure, or It contains the photoacid generator (B), a silicon-containing crosslinking agent (C2) having a methylol group and / or an alkoxymethyl group, and a phenolic hydroxyl group, and the base component (D). Hereinafter, a film-forming composition containing a silicon-containing polymer (A), a photoacid generator (B), a silicon-containing crosslinking agent (C1), and a base component (D) is referred to as a first film-forming composition. In addition, a film-forming composition containing a photoacid generator (B), a silicon-containing crosslinking agent (C2), and a base component (D) is referred to as a second film-forming composition.

[0024] <First Film-Forming Composition> As described above, the first film-forming composition contains a silicon-containing polymer (A), a photoacid generator (B), a silicon-containing crosslinking agent (C1), and a base component (D). Hereinafter, the essential components and other components of the first film-forming composition will be described.

[0025] [Silicon-Containing Polymer (A)] The first film-forming composition contains a silicon-containing polymer (A) having a phenolic hydroxyl group (hereinafter, also referred to as component (A)). Component (A) has a phenolic hydroxyl group and a silicon atom in the same polymer. By using the silicon-containing polymer (A), in particular, the etching resistance of the resist film formed by the negative resist composition is enhanced. Further, the aromatic group having a phenolic hydroxyl group in the silicon-containing polymer and the methylol group and / or alkoxymethyl group of the silicon-containing crosslinking agent (C1) are subjected to the action of an acid generated from the component (B) described below by exposure to form a crosslinked structure. As a result, component (A) has a higher molecular weight. Furthermore, since it has a phenolic hydroxyl group, component (A) is soluble in an alkaline developer, and the negative resist composition is imparted with alkali developability.

[0026] The content ratio of the silicon atom in component (A) is preferably 5% or more and 50% or less, more preferably 10% or more and 40% or less, still more preferably 15% or more and 30% or less, based on the total amount of all atoms constituting component (A).

[0027] (A) The content ratio of silicon atoms in the component can be calculated by the following formula. Content ratio of silicon atoms (%) = (Number of silicon atoms present in the silicon-containing polymer × Atomic weight of silicon atom) / (Total atomic weight calculated by adding the values obtained by multiplying the number of each atom constituting the silicon-containing polymer by its atomic weight) × 100 For example, in the case of polysiloxane composed of a repeating structure of a structural unit represented by -[Si(H)O3 / 2]-, the content ratio of silicon atoms is {(28×1)×100} / [{(28×1)+(16×1.5)+(1×1)}×100]≒52.8%.

[0028] The silicon-containing polymer (A) preferably contains a silicon-containing polymer (A0) having a structural unit represented by the following formula (a0-1).

Chemical formula

[0029] Ra 0 As the organic group in Ra, an aliphatic hydrocarbon group, an aromatic hydrocarbon group which may have a substituent, or a combination thereof is preferable.

[0030] Ra 0 The number of carbon atoms of the aliphatic hydrocarbon group in Ra is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5. Ra 0 As the aliphatic hydrocarbon group in Ra, a saturated aliphatic hydrocarbon group is preferable, and a linear aliphatic hydrocarbon group is more preferable. Ra 0 The number of carbon atoms of the aromatic hydrocarbon group in Ra is preferably 6 to 20, more preferably 6 to 15, still more preferably 6 to 12, particularly preferably 6 to 10. Ra 0 Examples of the aromatic ring of the aromatic group in Ra include a benzene ring and a naphthalene ring. Ra 0Examples of the substituent that the aromatic hydrocarbon group in [compound name] may have include a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the like.

[0031] The silicon-containing polymer (A0) preferably has a structural unit represented by the following formula (a0-1-1). [Chemical formula] (In formula (a0-1-1), R Ar1 is an aromatic hydrocarbon group. Ra 11 is a divalent linking group or a single bond. Ra 12 is a hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom. Ra 13 is a hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom. na2 is 1 or 2. na3 is an integer of 0 or more and 4 or less.)

[0032] R Ar1 The number of carbon atoms of the aromatic hydrocarbon group in [compound name] is preferably 6 or more and 20 or less, more preferably 6 or more and 15 or less, still more preferably 6 or more and 12 or less, and particularly preferably 6 or more and 10 or less. R Ar1 Examples of the aromatic hydrocarbon group in [compound name] include a group obtained by removing one or more hydrogen atoms from a benzene ring, a naphthalene ring, or the like. Among them, a group obtained by removing one or more hydrogen atoms from a benzene ring is preferable.

[0033] Ra 11 The divalent linking group in [compound name] is preferably an alkylene group, and more preferably a linear alkylene group. 11 The number of carbon atoms of the alkylene group in [compound name] is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less. Ra 11Examples of the alkylene group include a methylene group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and the like. Among them, a methylene group, an ethane-1,2-diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group are preferable, a methylene group and an ethane-1,2-diyl group are more preferable, and a methylene group is even more preferable.

[0034] Ra 12 The hydrocarbon group in is preferably an aliphatic hydrocarbon group, more preferably an alkyl group. Ra 12 Examples of the alkyl group in include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, and the like. Ra 12 is preferably a hydrogen atom.

[0035] Ra 13 The hydrocarbon group in is preferably an aliphatic hydrocarbon group, more preferably an alkyl group. Ra 13 Examples of the alkyl group in include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, and the like.

[0036] na2 is preferably 1. na3 is preferably 0 or 1, more preferably 0.

[0037] The constitutional unit (a0-1-1) contained in the silicon-containing polymer (A0) may be one kind or two or more kinds. When the silicon-containing polymer (A0) has the structural unit (a0-1-1), the proportion of the structural unit (a0-1-1) in the silicon-containing polymer (A0) is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, based on the total of all the structural units constituting the silicon-containing polymer (A0). When the proportion of the structural unit (a0-1-1) is 30 mol% or more, a resist pattern with good lithography characteristics is likely to be formed. Further, the proportion of the structural unit (a0-1-1) is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less.

[0038] (Other structural units) The silicon-containing polymer (A0) may have other structural units. Examples of the other structural units include a structural unit (a2) containing an alkyl group, a structural unit (a3) represented by the following formula (a3-1), a structural unit (a4) represented by the following formula (a4-1), and the like.

[0039] ·Structural unit (a2) The structural unit (a2) is a structural unit containing an alkyl group. Examples of the structural unit (a2) include a structural unit in which the main chain portion is a Si—O bond and the side chain portion bonded to the Si atom is an alkyl group. By having the structural unit (a2), the properties of the resist film formed using the negative resist composition can be easily controlled.

[0040] Preferred examples of the structural unit (a2) include a structural unit represented by the following formula (a2-1), a structural unit represented by the following formula (a2-2), and the like.

[0041] [Chemical formula] (In the formula, Ra 21 , Ra 22 , and Ra 23 are each independently an alkyl group having 1 to 10 carbon atoms.)

[0042] Ra 21, Ra 22 , and Ra 23 The alkyl group in Ra may be linear, branched, or cyclic, but is preferably linear or branched. Ra 21 Ra 22 , and Ra 23 The number of carbon atoms of the alkyl group in Ra is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less. Ra 21 Ra 22 , and Ra 23 Examples of the alkyl group in Ra include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, 2-ethylhexyl group, etc. Among them, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group are preferred, methyl group, ethyl group, propyl group, isopropyl group are more preferred, methyl group, ethyl group are even more preferred, and methyl group is particularly preferred.

[0043] The constitutional unit (a2) contained in the silicon-containing polymer (A0) may be one kind or two or more kinds. When the silicon-containing polymer (A0) has the constitutional unit (a2), the proportion of the constitutional unit (a2) in the silicon-containing polymer (A0) is preferably 10 mol% or more and 70 mol% or less, more preferably 20 mol% or more and 60 mol% or less, still more preferably 30 mol% or more and 50 mol% or less, based on the total of all constitutional units constituting the silicon-containing polymer (A0). The proportion of the constitutional unit represented by the formula (a2-1) is preferably 10 mol% or more and 70 mol% or less, more preferably 20 mol% or more and 60 mol% or less, still more preferably 30 mol% or more and 50 mol% or less, based on the total of all constitutional units constituting the silicon-containing polymer (A0). The proportion of the structural unit represented by the formula (a2-2) is preferably 10 mol% or more and 40 mol% or less, more preferably 10 mol% or more and 30 mol% or less, still more preferably 15 mol% or more and 25 mol% or less, based on the total of all the structural units constituting the silicon-containing polymer (A0). When the proportion of the structural unit (a2) is equal to or higher than the lower limit of the above preferable range, the etching resistance is likely to be further enhanced. When the proportion is equal to or lower than the upper limit of the above preferable range, a resist pattern with good lithography characteristics is likely to be formed.

[0044] · Structural unit (a3) The structural unit (a3) is a structural unit represented by the following formula (a3-1). The structural unit (a3) is a structural unit useful for enhancing lithography characteristics. When the structural unit (a3) is introduced, the dissolution rate can be easily controlled.

[0045] [Chemical formula] (In the formula, Ra 24 is a hydrocarbon group having 1 to 6 carbon atoms, and na3 is an integer of 0 to 5.)

[0046] Ra 24 The hydrocarbon group in Ra may be linear, branched, or cyclic, but is preferably linear or branched. Also, the hydrocarbon group in Ra 24 may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group. Ra 24 The number of carbon atoms of the hydrocarbon group in Ra is preferably 1 to 5, more preferably 1 to 3. Ra 24As the hydrocarbon group in [reference], an alkyl group is preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and the like. Among them, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferred, a methyl group and an ethyl group are more preferred, and a methyl group is even more preferred. na3 is preferably an integer of 0 or more and 3 or less, more preferably 0 or 1, and even more preferably 0.

[0047] The structural unit (a3) contained in the silicon-containing polymer (A0) may be one type or two or more types. When the silicon-containing polymer (A0) has the structural unit (a3), the proportion of the structural unit (a3) in the silicon-containing polymer (A0) is preferably 10 mol% or more and 70 mol% or less, more preferably 20 mol% or more and 60 mol% or less, and even more preferably 30 mol% or more and 50 mol% or less, based on the total of all the structural units constituting the silicon-containing polymer (A0).

[0048] · Structural unit (a4) The structural unit (a4) is a structural unit represented by the following formula (a4-1). The structural unit (a4) is a structural unit useful for enhancing lithography characteristics. When the structural unit (a4) is introduced, it is easy to control the dissolution rate.

[0049]

Chemical formula

[0050] The structural unit (a4) contained in the silicon-containing polymer (A0) may be one type or two or more types. When the silicon-containing polymer (A0) has the structural unit (a4), the proportion of the structural unit (a4) in the silicon-containing polymer (A0) is preferably 30 mol% or less, more preferably 5 mol% or more and 30 mol% or less, and even more preferably 10 mol% or more and 25 mol% or less, based on the total of all the structural units constituting the silicon-containing polymer (A0).

[0051] The silicon-containing polymer (A0) may have a structural unit containing at least one of an alkoxy group and a hydroxy group.

[0052] As the component (A), a silicon-containing polymer (A0) having a repeating structure of the structural unit represented by the above formula (a0-1-1) is preferable. Among them, a silicon-containing polymer composed of a repeating structure of the structural unit represented by the formula (a0-1-1); a silicon-containing polymer having a repeating structure of the structural unit represented by the formula (a0-1-1) and the structural unit represented by the formula (a2-1); a silicon-containing polymer having a repeating structure of the structural unit represented by the formula (a0-1-1) and the structural unit represented by the formula (a2-2); a silicon-containing polymer having a repeating structure of the structural unit represented by the formula (a0-1-1) and the structural unit represented by the formula (a3-1); a silicon-containing polymer having a repeating structure of the structural unit represented by the formula (a0-1-1), the structural unit represented by the formula (a2-1), and the structural unit represented by the formula (a3-1); a silicon-containing polymer having a repeating structure of the structural unit represented by the formula (a0-1-1), the structural unit represented by the formula (a2-2), and the structural unit represented by the formula (a3-1); a silicon-containing polymer having a repeating structure of the structural unit represented by the formula (a0-1-1), the structural unit represented by the formula (a3-1), and the structural unit represented by the general formula (a4-1) are preferable, and a silicon-containing polymer having a repeating structure of the structural unit represented by the formula (a0-1-1) and the structural unit represented by the formula (a2-1), and a silicon-containing polymer having a repeating structure of the structural unit represented by the formula (a0-1-1) and the structural unit represented by the formula (a3-1) are more preferable.

[0053] The mass average molecular weight (Mw) of the component (A) (based on polystyrene conversion by gel permeation chromatography (GPC)) is not particularly limited, and is, for example, 1000 or more, preferably 1000 or more and 10000 or less, more preferably 1500 or more and 7500 or less, and even more preferably 2000 or more and 5000 or less. (A) component having an Mw equal to or less than the upper limit of the above preferred range is likely to have improved solubility in an organic solvent. On the other hand, being equal to or greater than the lower limit of the above preferred range makes it easier for the patterning property of the resist film to be good and enhances the lithography characteristics of the formed resist pattern.

[0054] (A) component may be one kind or two or more kinds. (A) component content is preferably less than 5% by mass, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.10% by mass or more and 1% by mass or less with respect to the total mass of the first film-forming composition. When the content of (A) component is within the preferred range, it is easy to thin the film in pattern formation.

[0055] 〔Photoacid generator (B)〕 The film-forming composition contains a photoacid generator (B) (hereinafter also referred to as “(B) component”). (B) component acts as an acid component that causes crosslinking between the above-mentioned (A) component and the following (C1) component in the film-forming composition. (B) component is not particularly limited, and an acid generator proposed as an acid generator for a chemically amplified resist composition can be used. Such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisaryl sulfonyldiazomethanes, poly(bissulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, disulfone-based acid generators, and various other acid generators.

[0056] Preferred (B) component includes, for example, an onium salt represented by the following formula (b0) (hereinafter also referred to as “(B0) component”).

[0057]

Chemical formula

[0058] R b10 Examples of the organic group in include a hydrocarbon group which may have a substituent, a divalent linking group containing an oxygen atom, or a combination thereof. As this onium salt, a sulfonate represented by the following formula (b0-1b) is preferable.

[0059]

Chemical formula

[0060] ·Regarding the anion part Cyclic group which may have a substituent: R b101 The cyclic group in is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic group or an aliphatic hydrocarbon group, but is preferably an aromatic group. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0061] R b101 The number of carbon atoms of the aromatic group in is preferably 3 or more and 30 or less, more preferably 5 or more and 30 or less, still more preferably 5 or more and 20 or less, particularly preferably 6 or more and 15 or less, and most preferably 6 or more and 10 or less. However, this number of carbon atoms does not include the carbon atoms in the substituent. Rb101 Examples of the aromatic ring contained in the aromatic group in b101 include a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a biphenyl ring, or an aromatic heterocyclic ring in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, etc. R b101 Examples of the aromatic group in b101 include a group obtained by removing one hydrogen atom from the above aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), and a group in which one hydrogen atom of the above aromatic ring is substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). The number of carbon atoms of the above alkylene group (alkyl chain in the arylalkyl group) is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, and still more preferably 1.

[0062] R b101 Examples of the cyclic aliphatic hydrocarbon group in b101 include an aliphatic hydrocarbon group containing a ring in its structure. Examples of the aliphatic hydrocarbon group containing a ring in this structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc. The number of carbon atoms of the above alicyclic hydrocarbon group is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less. The above alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from monocycloalkane is preferable. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferable. Specifically, cyclopentane, cyclohexane and the like can be mentioned. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from polycycloalkane is preferable. As the polycycloalkane, a polycycloalkane having 7 to 30 carbon atoms is preferable. Among them, as the polycycloalkane, polycycloalkanes having a crosslinked ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane; polycycloalkanes having a condensed ring system polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferable.

[0063] Among them, R b101 As the cyclic aliphatic hydrocarbon group in, a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane is preferable, a group obtained by removing one hydrogen atom from polycycloalkane is more preferable, an adamantyl group and a norbornyl group are further preferable, and an adamantyl group is particularly preferable.

[0064] The number of carbon atoms of the linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, still more preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-] and the like can be mentioned. The number of carbon atoms of the branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group is preferably 2 or more and 10 or less, more preferably 3 or more and 6 or less, still more preferably 3 or 4, and most preferably 3. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and the like, and alkylalkylene groups and the like can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 or more and 5 or less carbon atoms is preferable.

[0065] Also, R b101 The cyclic hydrocarbon group in may contain a hetero atom such as a heterocyclic ring.

[0066] R b101 The cyclic hydrocarbon group in may be a condensed ring group containing a condensed ring in which an aliphatic hydrocarbon ring and an aromatic ring are condensed. Examples of the condensed ring include a ring in which one or more aromatic rings are condensed to a polycycloalkane having a bridged ring system polycyclic skeleton. Specific examples of the bridged ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. As the condensed ring type, a group containing a condensed ring in which 2 or 3 aromatic rings are condensed to a bicycloalkane is preferable, and a group containing a condensed ring in which 2 or 3 aromatic rings are condensed to bicyclo[2.2.2]octane is more preferable. Specific examples of the condensed ring group in R b101 include condensed ring groups represented by the following formulas (r-br-1) to (r-br-2). In the formula, * is Yb in the above formula (b0-1b)0 Represents a bonding hand that binds to

[0067]

Chemical formula

[0068] R b101 The cyclic group of may have a substituent. Examples of this substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, and the like. From the viewpoint of high sensitivity, as this substituent, a halogen atom is preferable, an iodine atom or a bromine atom is more preferable, and an iodine atom is even more preferable. When having an iodine atom as a substituent, the number of iodine atoms bonded to the cyclic group is preferably 1 or more and 3 or less, and more preferably 2 or 3.

[0069] A chain alkyl group that may have a substituent: R b101 The chain alkyl group in may be either linear or branched. The number of carbon atoms of the linear alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and even more preferably 1 or more and 10 or less. The number of carbon atoms of the branched-chain alkyl group is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and even more preferably 3 or more and 10 or less. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, etc. can be mentioned.

[0070] A chain alkenyl group that may have a substituent: R b101The chain alkenyl group in [context] may be either linear or branched. The number of carbon atoms in the chain alkenyl group is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, still more preferably 2 or more and 4 or less, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butenyl group, etc. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group, etc. Among these, the linear alkenyl group is preferred as the chain alkenyl group, the vinyl group and the propenyl group are more preferred, and the vinyl group is still more preferred.

[0071] R b101 The chain alkyl group or chain alkenyl group in [context] may have a substituent. Examples of this substituent include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, etc. From the viewpoint of high sensitivity, a halogen atom is preferred as this substituent, an iodine atom and a bromine atom are more preferred, and an iodine atom is still more preferred. When having an iodine atom as a substituent, the number of iodine atoms bonded to the chain alkyl group or chain alkenyl group is preferably 1 or more and 3 or less, and more preferably 2 or 3, respectively.

[0072] Among the above, R b101 is preferably a cyclic group having an iodine atom or a cyclic group having a bromine atom, more preferably a cyclic group having an iodine atom, still more preferably an aromatic hydrocarbon group having an iodine atom, and particularly preferably a phenyl group having an iodine atom, a naphthyl group having an iodine atom, or a group containing these. Preferred R b101 includes, for example, a group represented by the following formula (b0-r-1p), or a cyclic group to which a group represented by the following formula (b0-r-1p) is bonded.

[0073]

Chemical formula

[0074] R b02 The number of carbon atoms of the hydrocarbon group in is preferably 1 to 5. R b02 As the hydrocarbon group in, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable, a methyl group and an ethyl group are more preferable, and a methyl group is even more preferable. R b02 is preferably a hydrogen atom. That is, -OR b02 is preferably a phenolic hydroxyl group.

[0075] R b03 The number of carbon atoms of the hydrocarbon group in is preferably 1 to 5. R b03 As the hydrocarbon group in, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable, a methyl group and an ethyl group are more preferable. nb1 is preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3. nb2 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. nb3 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0076] Yb 0 As the divalent linking group in, a divalent linking group containing an oxygen atom is preferable. Yb 0 When is a divalent linking group containing an oxygen atom, the Yb 0It may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, etc. Examples of the divalent linking group containing an oxygen atom include non-hydrocarbon-based oxygen atom-containing linking groups such as an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), an amide bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), a carbonate bond (-O-C(=O)-O-); combinations of the non-hydrocarbon-based oxygen atom-containing linking group and an alkylene group, etc. A sulfonyl group (-SO2-) may be further linked to this combination. Among the divalent linking groups containing an oxygen atom, an ester bond (-C(=O)-O-) and an oxycarbonyl group (-O-C(=O)-) are more preferable. Yb 0 As [it], a divalent linking group is preferable, a divalent linking group containing an oxygen atom is more preferable, and an ester bond (-C(=O)-O-) and an oxycarbonyl group (-O-C(=O)-) are even more preferable.

[0077] Vb 0 The number of carbon atoms of the alkylene group and the fluorinated alkylene group in [it] is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, respectively. Vb 0 Examples of the fluorinated alkylene group in [it] include groups in which some or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms. Among them, Vb 0 is preferably an alkylene group having 1 to 4 carbon atoms, a fluorinated alkylene group having 1 to 4 carbon atoms, or a single bond, more preferably a group in which some of the hydrogen atoms of an alkylene group having 1 to 3 carbon atoms are substituted with fluorine atoms or a single bond, and -CH(CF3)- and -CH2- are even more preferable.

[0078] R 0 As [it], a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is preferable, and a fluorine atom is more preferable.

[0079] Specific examples of the anionic moiety of the sulfonate represented by formula (b0-1b) are shown below.

[0080]

Chemical formula

[0081] As the anionic moiety of the sulfonate represented by formula (b0-1b), at least one selected from the group consisting of the anions represented by the above formulas (b0-an-1) to (a0-an-11) is preferable, and at least one selected from the group consisting of the anions represented by the above formulas (a0-an-1) to (a0-an-6), (a0-an-9) to (a0-an-11) is more preferable.

[0082] ·Regarding the cationic moiety M m+ is an m-valent onium cation, preferably a sulfonium cation or an iodonium cation. m is an integer of 1 or more. M m+ Examples of the onium cation in M include organic cations represented by the following formulas (ca-1) to (ca-3).

[0083]

Chemical formula

[0084] R 201 ~R 207 Examples of the aryl group in include an aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferred. R 201 ~R 207 Examples of the alkyl group in include a linear or cyclic alkyl group, and an alkyl group having 1 to 30 carbon atoms is preferred. R 201 ~R 207 The number of carbon atoms of the alkenyl group in is preferably 2 to 10. R 201 ~R 207 , and R 210 Examples of the substituent that and R may have include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, a group represented by the following formulas (ca-r-1) to (ca-r-7), etc.

[0085]

Chemical formula

[0086] Cyclic group which may have a substituent: R’ 201 Examples of the cyclic group in include a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0087] R’201 The number of carbon atoms in the aromatic hydrocarbon group in 201 is preferably 3 or more and 30 or less, more preferably 5 or more and 30 or less, still more preferably 5 or more and 20 or less, particularly preferably 6 or more and 15 or less, and most preferably 6 or more and 10 or less. However, this number of carbon atoms does not include the carbon atoms in the substituent. R’ 201 Examples of the aromatic ring of the aromatic hydrocarbon group in 201 include a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a biphenyl ring, or an aromatic heterocyclic ring in which a part of the carbon atoms constituting these aromatic rings is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, etc. R’ 201 Examples of the aromatic hydrocarbon group in 201 include a group obtained by removing one hydrogen atom from the above aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and a group in which one hydrogen atom of the above aromatic ring is substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms of the above alkylene group (alkyl chain in the arylalkyl group) is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.

[0088] R’ 201 The cyclic aliphatic hydrocarbon group in 201 includes an aliphatic hydrocarbon group containing a ring in its structure. Examples of the aliphatic hydrocarbon group containing a ring in this structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The number of carbon atoms of the above alicyclic hydrocarbon group is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less. The above alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from monocycloalkane is preferable. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferable. Specifically, cyclopentane, cyclohexane and the like can be mentioned. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from polycycloalkane is preferable. As the polycycloalkane, a polycycloalkane having 7 to 30 carbon atoms is preferable. Among them, as the polycycloalkane, polycycloalkanes having a crosslinked ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane; polycycloalkanes having a condensed ring system polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferable.

[0089] Among them, R’ 201 As the cyclic aliphatic hydrocarbon group in, a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane is preferable, a group obtained by removing one hydrogen atom from polycycloalkane is more preferable, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

[0090] The number of carbon atoms of the linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, still more preferably 1 or more and 4, particularly preferably 1 or more and 3 or less. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-] and the like can be mentioned. As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferred. Specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and other alkylalkylene groups can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0091] Also, R’ 201 The cyclic hydrocarbon group in may contain a hetero atom such as a heterocyclic ring or the like.

[0092] R’ 201 Examples of the substituent in the cyclic group of include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group and the like. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group are more preferred. As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a tert-butoxy group are more preferred, and a methoxy group, an ethoxy group are even more preferred. As the halogen atom as the substituent, a fluorine atom is preferred. Examples of the alkyl halide group as a substituent include groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, etc., are substituted with the above halogen atoms. The carbonyl group as a substituent is a group that substitutes the methylene group (-CH2-) constituting the cyclic hydrocarbon group.

[0093] A chain alkyl group which may have a substituent: R’ 201 The chain alkyl group of may be either linear or branched. The number of carbon atoms of the linear alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, still more preferably 1 or more and 10 or less. The number of carbon atoms of the branched-chain alkyl group is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, still more preferably 3 or more and 10 or less. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, etc. can be mentioned.

[0094] A chain alkenyl group which may have a substituent: R’ 201 The chain alkenyl group of may be either linear or branched. The number of carbon atoms of the chain alkenyl group is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, still more preferably 2 or more and 4 or less, particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group, etc. Examples of the branched-chain alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group, etc. As the chain alkenyl group, a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is still more preferable.

[0095] R’ 201 Examples of the substituent in the chain-like alkyl group or alkenyl group of 201 include, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the above R’ 201 and cyclic groups in 201 etc. may be mentioned.

[0096] R’ 201 Examples of the cyclic group which may have a substituent, the chain-like alkyl group which may have a substituent, or the chain-like alkenyl group which may have a substituent of 201 also include an acid dissociable group.

[0097] R’ 201 As R’ 201 , a cyclic group which may have a substituent is preferable, and a cyclic hydrocarbon group which may have a substituent is more preferable. More specifically, for example, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane, etc. are preferable.

[0098] R 201 ~R 203 、R 206 、and R 207 When R N ~R N are bonded to each other to form a ring together with the sulfur atom in the formula, they may be bonded via a hetero atom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or a functional group such as a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(wherein R N is an alkyl group having 1 to 5 carbon atoms).). As the ring formed, it is preferable that one ring containing the sulfur atom in the formula in its ring skeleton is 3-membered or more and 10-membered or less including the sulfur atom, and more preferably 5-membered or more and 7-membered or less. Specific examples of the ring formed include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium ring, etc.

[0099] R 208 、and R 209Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. When it is an alkyl group, they may be bonded to each other to form a ring.

[0100] R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a -SO2-containing cyclic group which may have a substituent. R 210 Examples of the aryl group in R include aryl groups having 6 to 20 carbon atoms. Among them, a phenyl group and a naphthyl group are preferable. R 210 Examples of the alkyl group in R include linear or cyclic alkyl groups, preferably alkyl groups having 1 to 30 carbon atoms. R 210 The number of carbon atoms of the alkenyl group in R is preferably 2 or more and 10 or less. R 210 Examples of the -SO2-containing cyclic group which may have a substituent in R include "-SO2-containing polycyclic groups".

[0101] Examples of suitable cations represented by formula (ca-1) include cations represented by the following chemical formulas respectively.

[0102]

Chem.

[0103]

Chem.

[0104]

Chem.

[0105]

Chem.

[0106]

Chem.

[0107]

Chem.

[0108]

Chem.

[0109] Suitable cations represented by formula (ca-2) specifically include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0110] Suitable cations represented by formula (ca-3) specifically include cations represented by the following formulas (ca-3-1) to (ca-3-6), respectively.

[0111]

Chem.

[0112] M m+ The onium cation of is preferably at least one selected from the group consisting of cations represented by the above formulas (ca-1) to (ca-3), and among these, the cation represented by the above formula (ca-1) is more preferable, and the cation represented by the following formula (b0-ca) is even more preferable.

[0113] [Chemical formula] (In the formula, Rb 1 is a fluorinated alkyl group or a fluorine atom. q1 is an integer of 1 or more and 5 or less. Rb 2 , and Rb 3 each independently represent an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. Rb 2 , and Rb 3 may be bonded to each other to form a ring together with the sulfur atom in the formula. Rb 2 , or Rb 3 may form a condensed ring together with the sulfur atom and the benzene ring in the formula.)

[0114] Rb 1 As the fluorinated alkyl group in Rb, a linear or branched fluorinated alkyl group having 1 to 5 carbon atoms is preferable, a linear fluorinated alkyl group having 1 to 5 carbon atoms is more preferable, and a trifluoromethyl group is even more preferable. As q1, an integer of 1 or more and 4 or less is preferable, and 2 or 3 is more preferable. Rb 1 is preferably bonded to the ortho-position or meta-position of the benzene ring from the viewpoint of photodegradation efficiency. Rb 2 , and Rb 3 are the same as R 201 ~R 203 in formula (ca-1).

[0115] Particularly from the viewpoint of high sensitivity, as a preferable cation represented by formula (ca-1), a cation having an electron-withdrawing group such as a fluorine atom, a fluorinated alkyl group, or a sulfonyl group as a substituent is preferable. For example, a cation selected from the group consisting of the cations represented by the above formulas (ca-1-44), (ca-1-71) to (ca-1-77), (ca-1-80), and (ca-1-81) is more preferable.

[0116] Preferred specific examples of the onium salt ((B0) component) represented by formula (b0) are shown below.

[0117] [Chemical formula]

[0118] [Chemical formula]

[0119] [Chemical formula]

[0120] As the (B0) component, a compound selected from the group consisting of compounds represented by any of the above formulas (B0-1) to (B0-12) is preferable, and a compound represented by any of the above formulas (B0-11) and (B0-12) is more preferable.

[0121] (Cage-type silsesquioxane (B1)) The film-forming composition may contain, as the (B) component, a cage-type silsesquioxane (B1) (hereinafter also referred to as the "(B1) component"). The cage-type silsesquioxane (B1) has an ionic group that decomposes upon exposure to generate an acid. The cage-type silsesquioxane (B1) preferably has a complete cage structure.

[0122] The content ratio of silicon atoms in the (B1) component is preferably 5% or more and 45% or less, more preferably 10% or more and 35% or less, and still more preferably 10% or more and 25% or less with respect to the total amount of all atoms constituting the (B1) component. The method for calculating the content ratio of silicon atoms in the (B1) component is the same as the method for calculating the content ratio of silicon atoms in the (A) component.

[0123] The ionic group that decomposes upon exposure to light to generate an acid is not particularly limited, and examples include the ionic groups in onium salt-based acid generators such as iodonium salts and sulfonium salts, which have been proposed as acid generators for chemically amplified resist compositions.

[0124] As the ionic group that decomposes upon exposure to light to generate an acid, a group represented by the following formula (b9) is preferable. [Chemical formula] (In formula (b9), R b90 is a divalent organic group having 1 to 40 carbon atoms. M9 + is a sulfonium cation or an iodonium cation.)

[0125] R b90 Examples of the organic group in R include a hydrocarbon group which may have a substituent, a divalent linking group containing an oxygen atom, or a combination thereof.

[0126] As the group represented by formula (b9), a group represented by the following formula (b9-1) is preferable. -R b91 -Yb 9 -Vb 9 -SO3 - M9 + (b9-1) (In the formula, R b901 is a cyclic group which may have a substituent, a linear alkylene group which may have a substituent, a linear alkenylene group which may have a substituent, or a single bond. Yb 9 is a divalent linking group or a single bond. Vb 9 is an alkylene group, a fluorinated alkylene group, or a cyclic group which may have a substituent. M9 + is a sulfonium cation or an iodonium cation.)

[0127] ·Regarding the anion part R b91 is preferably a cyclic group which may have a substituent or a single bond, and more preferably a single bond.

[0128] R b91 The cyclic group in R is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but is preferably an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferably saturated.

[0129] R b91 The number of carbon atoms of the aromatic hydrocarbon group in R is preferably 3 or more and 30 or less, more preferably 5 or more and 30 or less, still more preferably 5 or more and 20 or less, particularly preferably 6 or more and 15 or less, and most preferably 6 or more and 10 or less. However, this number of carbon atoms does not include the number of carbon atoms in the substituent.

[0130] R b91 Examples of the aromatic ring of the aromatic hydrocarbon group in R include a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a biphenyl ring, or an aromatic heterocyclic ring in which a part of the carbon atoms constituting these aromatic rings is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, etc. R b91 Examples of the aromatic hydrocarbon group in R include a group obtained by removing two hydrogen atoms from the above aromatic ring (arylene group: for example, a phenylene group, a naphthylene group, etc.). Among them, a phenylene group is preferred.

[0131] R b91 Examples of the cyclic aliphatic hydrocarbon group in R include an aliphatic hydrocarbon group containing a ring in its structure. Examples of the aliphatic hydrocarbon group containing a ring in its structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc. The number of carbon atoms of the above alicyclic hydrocarbon group is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less. The above alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two or more hydrogen atoms from a monocycloalkane is preferred. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferred. Specifically, cyclopentane, cyclohexane and the like can be mentioned. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two or more hydrogen atoms from a polycycloalkane is preferred. As the polycycloalkane, a polycycloalkane having 7 to 30 carbon atoms is preferred. Among them, as the polycycloalkane, a polycycloalkane having a crosslinked ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane; a polycycloalkane having a condensed ring system polycyclic skeleton such as a cyclic group having a steroid skeleton is more preferred.

[0132] Among them, R b91 In the cyclic aliphatic hydrocarbon group, a group obtained by removing two or more hydrogen atoms from a monocycloalkane or a polycycloalkane is preferred, a group obtained by removing two hydrogen atoms from a polycycloalkane is more preferred, a group obtained by removing two hydrogen atoms from adamantane or norbornane is particularly preferred, and a group obtained by removing two hydrogen atoms from adamantane is most preferred.

[0133] The number of carbon atoms of the linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, still more preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred. Specifically, methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-] and the like can be mentioned. The number of carbon atoms in the branched-chain aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, is preferably 2 or more and 10 or less, more preferably 3 or more and 6 or less, still more preferably 3 or 4, and particularly preferably 3. As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferable. Specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and other alkylalkylene groups can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 or more and 5 or less carbon atoms is preferable.

[0134] Also, R b91 The cyclic hydrocarbon group in may contain a hetero atom such as a heterocyclic ring.

[0135] R b91 The cyclic hydrocarbon group as may be a condensed ring group containing a condensed ring in which an aliphatic hydrocarbon ring and an aromatic ring are condensed. Examples of the condensed ring include a ring in which one or more aromatic rings are condensed to a polycycloalkane having a bridged ring system polycyclic skeleton. Specific examples of the bridged ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. As the condensed ring group, a group containing a condensed ring in which 2 or 3 aromatic rings are condensed to a bicycloalkane is preferable, and a group containing a condensed ring in which 2 or 3 aromatic rings are condensed to bicyclo[2.2.2]octane is more preferable.

[0136] R b91The cyclic group may have a substituent. Examples of this substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, and the like. From the viewpoint of high sensitivity, as this substituent, a halogen atom is preferable, an iodine atom or a bromine atom is more preferable, and an iodine atom is even more preferable. When having an iodine atom as a substituent, the number of iodine atoms bonded to the cyclic group is preferably 1 or more and 3 or less, and more preferably 1 or 2.

[0137] R b91 The chain-like alkylene group in R may be either linear or branched. The number of carbon atoms of the linear alkylene group is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and even more preferably 1 or more and 10 or less. The number of carbon atoms of the branched alkylene group is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and even more preferably 3 or more and 10 or less.

[0138] R b91 The chain-like alkenylene group in R may be either linear or branched. The number of carbon atoms of the chain-like alkenylene group is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, even more preferably 2 or more and 4 or less, and particularly preferably 3.

[0139] R b91 The chain-like alkylene group or chain-like alkenylene group in R may have a substituent. Examples of this substituent include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, and the like. From the viewpoint of high sensitivity, as this substituent, a halogen atom is preferable, an iodine atom or a bromine atom is more preferable, and an iodine atom is even more preferable. When having an iodine atom as a substituent, the number of iodine atoms bonded to the chain-like alkylene group or chain-like alkenylene group is preferably 1 or more and 3 or less, and more preferably 1 or 2, respectively.

[0140] Preferred Rb91 Examples include a group represented by the following formula (b9-r-1p), or a cyclic group to which a group represented by the following formula (b9-r-1p) is bonded.

[0141] [Chemical formula] (In the formula, I is an iodine atom. R b92 is a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom. R b93 is a hydrocarbon group having 1 to 6 carbon atoms. nb91 is an integer of 1 to 4. nb92 is an integer of 0 to 3. nb93 is an integer of 0 to 3. 1 ≤ nb91 + nb92 + nb93 ≤ 4. * represents a bond that binds to Yb in the above formula (b9-1) 9 or a bond that binds to a cyclic group. ** represents a bond different from *. )

[0142] R b92 The number of carbon atoms of the hydrocarbon group in is preferably 1 to 5. R b92 As the hydrocarbon group in, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable, a methyl group and an ethyl group are more preferable, and a methyl group is even more preferable. R b92 is preferably a hydrogen atom. That is, -OR b92 is preferably a phenolic hydroxyl group.

[0143] R b93 The number of carbon atoms of the hydrocarbon group in is preferably 1 to 5. R b93 As the hydrocarbon group in, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable, a methyl group and an ethyl group are more preferable. nb91 is preferably 1 or 2, and more preferably 1. nb92 is preferably 0 or 1, and more preferably 0. nb93 is preferably 0 or 1, and more preferably 0.

[0144] Yb 9 As the divalent linking group in Yb, a divalent linking group containing an oxygen atom is preferred. Yb 9 When Yb is a divalent linking group containing an oxygen atom, the Yb 9 may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include, for example, carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, and the like. Examples of the divalent linking group containing an oxygen atom include non-hydrocarbon-based oxygen atom-containing linking groups such as an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), an amide bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), a carbonate bond (-O-C(=O)-O-), etc.; combinations of the non-hydrocarbon-based oxygen atom-containing linking group and an alkylene group, etc. A sulfonyl group (-SO2-) may be further linked to this combination. Among the divalent linking groups containing an oxygen atom, an ester bond (-C(=O)-O-) and an oxycarbonyl group (-O-C(=O)-) are more preferred. Yb 9 is preferably a divalent linking group containing an oxygen atom or a single bond, more preferably an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), or a single bond, and even more preferably a single bond.

[0145] Vb 9 The number of carbon atoms of the alkylene group and the fluorinated alkylene group in Vb is each preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less.

[0146] Vb 9 As the alkylene group in Vb, a linear or branched chain is preferred, and a linear chain is more preferred. Vb 9 As the alkylene group in Vb, a methylene group, an ethane-1,2-diyl group, and a propane-1,3-diyl group are preferred, and an ethane-1,2-diyl group is more preferred. Vb 9 As the fluorinated alkylene group in Vb, Vb 9Examples of the group in which some or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms include Vb. 9 As the fluorinated alkylene group in, -CH2CF2-, -CHFCF2-, -CH2CH2CF2- are preferable.

[0147] Vb 9 As the cyclic group in, an aromatic hydrocarbon group is preferable. Vb 9 The number of carbon atoms of the aromatic hydrocarbon group in is preferably 3 or more and 30 or less, more preferably 6 or more and 15 or less, and even more preferably 6 or more and 10 or less. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. Vb 9 Examples of the aromatic hydrocarbon group in include a phenylene group, a naphthylene group, and the like. Vb 9 Examples of the substituent that the aromatic hydrocarbon group in may have include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, and the like. From the viewpoint of high sensitivity, this substituent is preferably a halogen atom, and more preferably a fluorine atom.

[0148] The following shows preferred specific examples of the anion part of the group represented by the formula (b9-1). Among these, the anion part represented by (b-R1-2) or (b-R1-5) is preferred.

Chemical formula

[0149] ·Regarding the cation part M9 + Examples of the sulfonium cation or iodonium cation in include the organic cations represented by the above formulas (ca-1) to (ca-3), respectively.

[0150] (Component (B1) may have an aromatic group having a phenolic hydroxyl group in addition to the ionic group that decomposes upon exposure to generate an acid.

[0151] As the aromatic group having a phenolic hydroxyl group, examples of the aromatic group include hydrocarbon groups having at least one aromatic ring. The aromatic ring may be monocyclic or polycyclic. The number of carbon atoms of the aromatic ring is preferably 5 or more and 30 or less, more preferably 5 or more and 20 or less, still more preferably 6 or more and 15 or less, and particularly preferably 6 or more and 12 or less. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring herein include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like. Among them, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable. Examples of the aromatic group include a group obtained by removing one hydrogen atom from the above aromatic ring (aryl group: for example, phenyl group, naphthyl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.).

[0152] The number of phenolic hydroxyl groups in the aromatic group is preferably 1, 2, or 3 per aromatic group, more preferably 1 or 2, and particularly preferably 1.

[0153] In the aromatic group, the hydrogen atom bonded to the aromatic ring may be substituted with a substituent other than the phenolic hydroxyl group. Examples of this substituent include an alkyl group, a halogenated alkyl group, a halogen atom, and the like. Examples of the alkyl group as the substituent include alkyl groups having 1 to 5 carbon atoms, which may be linear or branched. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. The halogen atom as the substituent is preferably a fluorine atom.

[0154] Preferred specific examples of the aromatic group having a phenolic hydroxyl group are shown below. Among these, the group represented by (b-R2-1) or (b-R2-4) is preferable.

Chemical formula

[0155] As the cage-type silsesquioxane (B1), a cage-type silsesquioxane represented by the following formula (b11) is preferable.

Chemical formula

[0156] The organic group in R b11 ~R b18 is preferably an ionic group that decomposes upon exposure to generate an acid, an aromatic group having a phenolic hydroxyl group, or a hydrocarbon group having 1 to 10 carbon atoms.

[0157] At least one of the other R b11 ~R b18 is preferably an aromatic group having a phenolic hydroxyl group.

[0158] The number of ionic groups in R b11 ~R b18 that decompose upon exposure to generate an acid is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less, and even more preferably 1. The number of aromatic groups having a phenolic hydroxyl group in R b11 ~R b18 is preferably 1 or more and 7 or less, more preferably 6 or more and 7 or less, and even more preferably 7.

[0159] Regarding the ionic group that generates an acid upon exposure and the aromatic group having a phenolic hydroxyl group, it is as described above.

[0160] R b11 ~R b18 The hydrocarbon group having 1 to 10 carbon atoms in R~R may be linear, branched, or cyclic, and is preferably linear or branched. Further, the hydrocarbon group here may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferred. The number of carbon atoms of the hydrocarbon group here is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and even more preferably 1 or more and 3 or less. Among them, a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferred, a methyl group and an ethyl group are even more preferred, and a methyl group is particularly preferred.

[0161] L b11 ~L b18 The number of carbon atoms of the divalent linking group as L~L is preferably 1 or more and 30 or less, more preferably 1 or more and 20 or less, even more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less.

[0162] L b11 ~L b18 The divalent linking group as L~L preferably contains at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a silicon atom, more preferably contains at least two selected from the group consisting of an oxygen atom, a sulfur atom, and a silicon atom, and even more preferably contains an oxygen atom and a silicon atom.

[0163] L b11 ~L b18 As the divalent linking group as L~L, a divalent linking group represented by any of the following formulas (a1-L-1) to (a1-L-8) is preferred.

[0164]

Chemical formula

[0165] Z Xb Z Yb and Z Zb The hydrocarbon group having 1 to 6 carbon atoms as Z Xb Z Yb and Z Zb The hydrocarbon group as Z Z Xb Z Yb and Z Zb The number of carbon atoms of the hydrocarbon group as Z Xb Z Yb The hydrocarbon group as Z

[0166] In formulas (a1-L-1) to (a1-L-2), Z Xb and Z Yb are each preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably both are hydrocarbon groups having 1 to 6 carbon atoms, even more preferably both are hydrocarbon groups having 1 to 3 carbon atoms, and particularly preferably both are methyl groups. Z Zbis preferably a hydrocarbon group having 1 to 6 carbon atoms or a single bond, more preferably a hydrocarbon group having 1 to 3 carbon atoms or a single bond, even more preferably a methyl group or a single bond, and particularly preferably a single bond. In formula (a1-L-3), Z Xb and Z Yb are each preferably a hydrogen atom, and more preferably both are hydrogen atoms. In formula (a1-L-4), Z Xb and Z Yb are each preferably a hydrogen atom, and more preferably both are hydrogen atoms. In formulas (a1-L-5) to (a1-L-6), Z Xb and Z Yb are each preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably both are hydrocarbon groups having 1 to 6 carbon atoms, even more preferably both are hydrocarbon groups having 1 to 3 carbon atoms, and particularly preferably both are methyl groups. In formulas (a1-L-7) to (a1-L-8), Z Xb and Z Yb are each preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably both are hydrocarbon groups having 1 to 6 carbon atoms, even more preferably both are hydrocarbon groups having 1 to 3 carbon atoms, and particularly preferably both are methyl groups.

[0167] In formula (a1-L-1), n1b is preferably an integer of 0 or more and 7 or less, more preferably an integer of 2 or more and 5 or less, even more preferably 2 or 3. In formula (a1-L-2), n2b is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less, even more preferably 0 or 1. n2a is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less, even more preferably 0 or 1. In formula (a1-L-3), n3b is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less, and still more preferably 0 or 1. In the above formula (a1-L-4), n4b is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less, and still more preferably 1. In the above formula (a1-L-5), n5b is preferably an integer of 0 or more and 8 or less, more preferably an integer of 2 or more and 5 or less, and still more preferably 2 or 3. In the above formula (a1-L-6), n6b is preferably an integer of 0 or more and 6 or less, more preferably an integer of 0 or more and 3 or less, and still more preferably 0 or 1. In the above formula (a1-L-7), n7b is preferably an integer of 0 or more and 8 or less, more preferably an integer of 2 or more and 5 or less, and still more preferably 2 or 3. In the above formula (a1-L-8), n8b is preferably an integer of 0 or more and 6 or less, more preferably an integer of 0 or more and 3 or less, and still more preferably 0 or 1.

[0168] Y b As the divalent linking group in, a divalent linking group containing an oxygen atom is preferred. Y b When is a divalent linking group containing an oxygen atom, the Y may contain atoms other than the oxygen atom. Examples of the atoms other than the oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, a nitrogen atom, and the like. Examples of the divalent linking group containing an oxygen atom include non-hydrocarbon-based oxygen atom-containing linking groups such as an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), an amide bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), and a carbonate bond (-O-C(=O)-O-); combinations of the non-hydrocarbon-based oxygen atom-containing linking group and an alkylene group, and the like. A sulfonyl group (-SO2-) may be further linked to this combination. Among the divalent linking groups containing an oxygen atom, an ester bond (-C(=O)-O-) and an oxycarbonyl group (-O-C(=O)-) are more preferred. Y b is preferably a divalent linking group containing an oxygen atom or a single bond, more preferably an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), or a single bond.

[0169] The following shows preferred specific examples of L b11 ~L b18 ** represents a bond to Si. * represents a bond to any one of R b11 ~R b18 Among these, groups represented by (b-L-2) to (b-L-9) and (b-L-33) are preferred.

[0170]

Chemical formula

[0171]

Chemical formula

[0172] L b11 ~L b18 is preferably a divalent linking group selected from the group consisting of the groups represented by the above formulas (a1-L-1), (a1-L-2), and (a1-L-7).

[0173] The weight average molecular weight (Mw) of the cage-type silsesquioxane (B1) (based on polystyrene conversion by gel permeation chromatography (GPC)) is not particularly limited, preferably 1000 or more and 5000 or less, more preferably 1200 or more and 4000 or less, and even more preferably 1500 or more and 3500 or less. When the Mw of the cage-type silsesquioxane (B1) is below the preferred upper limit of this range, it has sufficient solubility in a solvent. When it is above the preferred lower limit of this range, the dry etching resistance is enhanced, and the resist pattern cross-sectional shape is good. The dispersity (Mw / Mn) of the cage-type silsesquioxane (B1) is not particularly limited, preferably 1.00 or more and 1.40 or less, more preferably 1.00 or more and 1.30 or less, and even more preferably 1.00 or more and 1.20 or less. Note that Mn represents the number average molecular weight.

[0174] The component (B1) can be produced using a known production method. For example, the cage-type silsesquioxane represented by (b11) can be produced by reacting the following raw material (X) and raw material (Y) and appropriately performing a deprotection reaction, as in Synthesis Examples (1) to (7) described later.

[0175] Raw material (X): An octasilsesquioxane having a cage structure in which a functional group capable of reacting with raw material (Y) is bonded to silicon (Si) at each vertex. Examples of the functional group capable of reacting with raw material (Y) include a dimethylsilyloxy group and a vinyl group.

[0176] Raw material (Y): A raw material having an "ionic group that decomposes upon exposure to generate an acid" or a part thereof. Examples of this raw material include benzyltrimethylammonium 1,1-difluoro-2-(methacryloyloxy)ethanesulfonate and 4-ethenyl-2,3,5,6-tetrafluorobenzenesulfonic acid.

[0177] The component (B) may be used alone or in combination of two or more. The content of the component (B) (particularly, the component (B0)) is preferably 10 parts by mass or more and 50 parts by mass or less, more preferably 20 parts by mass or more and 45 parts by mass or less, and even more preferably 25 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the component (A). When the content of the component (B) is at least the lower limit value of the above preferred range, lithography characteristics such as sensitivity, resolution performance, and reduction of LWR (line width roughness) are more likely to be improved in resist pattern formation. On the other hand, when it is at most the upper limit value of the preferred range, a uniform solution is more likely to be obtained when each component of the film-forming composition is dissolved in an organic solvent, and the storage stability of the composition is more likely to be enhanced.

[0178] [Silicon-containing crosslinking agent (C1)] The first film-forming composition contains, as a crosslinking agent (C), a silicon-containing crosslinking agent (C1) (hereinafter also referred to as the "(C1) component"). The silicon-containing crosslinking agent (C1) has a methylol group and / or an alkoxymethyl group.

[0179] The content ratio of silicon atoms in the (C1) component is preferably 5% or more and 45% or less, more preferably 8% or more and 35% or less, and still more preferably 10% or more and 25% or less with respect to the total amount of all atoms constituting the (C1) component. The method for calculating the content ratio of silicon atoms in the (C1) component is the same as the method for calculating the content ratio of silicon atoms in the (A) component.

[0180] The methylol group and / or alkoxymethyl group possessed by the (C1) component is preferably bonded to an aromatic group or a nitrogen atom. Thereby, the action as a crosslinking agent is likely to be exhibited.

[0181] The (C1) component may have a phenolic hydroxyl group in addition to the methylol group and / or alkoxymethyl group.

[0182] As the silicon-containing crosslinking agent (C1), siloxane is preferable, and cage-type silsesquioxane and cyclic siloxane are more preferable.

[0183] The silicon-containing crosslinking agent (C1) preferably contains at least one selected from the group consisting of a cage-type silsesquioxane (C1-1) represented by the following formula (c1-1) and a cyclic siloxane (C1-2) represented by the following formula (c1-2).

[0184] (Cage-type silsesquioxane (C1-1)) [Chemical formula] (In formula (c1-1), R 1 ~R 8is, independently of one another, an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, R 1 ~R 8 at least one of which is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group. L 1 ~L 8 is, independently of one another, a divalent linking group represented by any one of the following formulas (c1-L-1) to (c1-L-7).) [Chemical Formula] (In formulas (c1-L-1) to (c1-L-7), Z X and Z Y are, independently of one another, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom. n1 to n7 are, independently of one another, an integer of 0 or more and 10 or less. * represents a bond to Si. ** represents a bond to any one of R 1 ~R 8 .)

[0185] R 1 ~R 8 is preferably an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, or an aromatic group having a phenolic hydroxyl group, more preferably an aromatic group having a methylol group or an alkoxymethyl group, or an aromatic group having a phenolic hydroxyl group, and still more preferably an aromatic group having a methylol group or an alkoxymethyl group.

[0186] R 1 ~R 8 At least one of the others may be an aromatic group having a phenolic hydroxyl group.

[0187] R 1 ~R 8Among them, the number of aromatic groups having a methylol group or an alkoxymethyl group is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, particularly preferably 7 or more, and may be 8. Also, the number of aromatic groups having a methylol group or an alkoxymethyl group may be, for example, 7 or less, 5 or less, 3 or less, or 1 or less. R 1 ~R 8 Among them, the number of nitrogen atom-containing groups having a methylol group or an alkoxymethyl group is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, particularly preferably 7 or more, and may be 8. Also, the number of aromatic groups having a methylol group or an alkoxymethyl group may be, for example, 7 or less, 5 or less, 3 or less, or 1 or less. R 1 ~R 8 Among them, the total number of aromatic groups having a methylol group or an alkoxymethyl group and nitrogen-containing groups having a methylol group or an alkoxymethyl group is preferably 3 or more, more preferably 5 or more, still more preferably 7 or more, and may be 8. Also, the total number may be, for example, 7 or less, 5 or less, 3 or less, or 1. R 1 ~R 8 Among them, the number of aromatic groups having a phenolic hydroxyl group may be, for example, 1 or more, 3 or more, 5 or more, or 7 or more, and may also be 7 or less, 5 or less, 3 or less, or 1 or less.

[0188] R 1 ~R 8 The aromatic group having a methylol group or an alkoxymethyl group in is preferably an aromatic group in which a hydrogen atom bonded to the aromatic ring is substituted with a methylol group or an alkoxymethyl group. R 1 ~R 8Examples of the aromatic group herein include hydrocarbon groups having at least one aromatic ring. The aromatic ring may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 or more and 30 or less, more preferably 5 or more and 20 or less, still more preferably 6 or more and 15 or less, and particularly preferably 6 or more and 12 or less. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring herein include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc. Among them, benzene ring and naphthalene ring are preferred, and benzene ring is more preferred. Examples of the aromatic group include a group obtained by removing one hydrogen atom from the above aromatic ring (aryl group: for example, phenyl group, naphthyl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.).

[0189] R 1 ~R 8 The number of methylol groups and alkoxymethyl groups in the aromatic group in R

[0190] R 1 ~R 8 In R ~R

[0191] the hydrogen atom bonded to the above aromatic ring in the aromatic group may be substituted with a substituent other than a methylol group and an alkoxymethyl group. Examples of this substituent include an alkyl group, a halogenated alkyl group, a halogen atom, etc. Examples of the alkyl group as the substituent include alkyl groups having 1 to 5 carbon atoms. The alkyl group may be linear or branched. Examples of the halogenated alkyl group as the substituent include a group in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom as the substituent, a fluorine atom is preferred.

[0191] Hereinafter, preferred specific examples of the aromatic group having a methylol group or an alkoxymethyl group are shown. Among these, the group represented by (c1-R1-1) is preferred.

[0192]

Chem.

[0193] R 1 ~R 8 As the nitrogen atom-containing group having a methylol group or an alkoxymethyl group in R, a nitrogen atom-containing heterocyclic group in which the N-position is substituted with a methylol group or an alkoxymethyl group is preferable.

[0194] R 1 ~R 8 The number of carbon atoms of the nitrogen atom-containing heterocyclic group in R is preferably 3 or more and 20 or less, more preferably 4 or more and 15 or less, still more preferably 4 or more and 10 or less. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. Examples of the nitrogen atom-containing heterocyclic group here include groups composed of succinimide, cyclohexyldicarboximide, and the like.

[0195] Hereinafter, preferred specific examples of the nitrogen atom-containing group having a methylol group or an alkoxymethyl group are shown.

[0196]

Chem.

[0197] R 1 ~R 8 As the aromatic group having a phenolic hydroxyl group in R, a hydrocarbon group having at least one aromatic ring can be mentioned. The aromatic ring may be monocyclic or polycyclic. The number of carbon atoms of the aromatic ring is preferably 5 or more and 30 or less, more preferably 5 or more and 20 or less, still more preferably 6 or more and 15 or less, and particularly preferably 6 or more and 12 or less. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring herein include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc. Among them, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable. Examples of the aromatic group include a group obtained by removing one hydrogen atom from the above aromatic ring (aryl group: for example, phenyl group, naphthyl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.).

[0198] R 1 ~R 8 The number of phenolic hydroxyl groups in the aromatic group as R

[0199] ~R is preferably 1, 2, or 3, more preferably 1 or 2, and particularly preferably 1 per aromatic group. The hydrogen atom bonded to the aromatic ring of the aromatic group may be substituted with a substituent other than a phenolic hydroxyl group. Examples of this substituent include an alkyl group, a halogenated alkyl group, a halogen atom, etc.

[0200] Preferred specific examples of the aromatic group having a phenolic hydroxyl group are shown below. Among these, the group represented by (c1-R3-1) or (c1-R3-4) is preferable.

Chemical formula

[0201] R 1 ~R 8The hydrocarbon group having 1 to 10 carbon atoms may be linear, branched or cyclic, and is preferably linear or branched. Further, the hydrocarbon group here may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferred. The number of carbon atoms of the hydrocarbon group here is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and even more preferably 1 or more and 3 or less. Among them, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferred, a methyl group and an ethyl group are more preferred, and a methyl group is even more preferred.

[0202] Z X and Z Y The hydrocarbon group having 1 to 6 carbon atoms in may be linear, branched or cyclic, and is preferably linear or branched. Also, Z X and Z Y The hydrocarbon group in may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferred. Z X and Z Y The number of carbon atoms of the hydrocarbon group in is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less. Z X and Z Y As the hydrocarbon group in, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferred, a methyl group and an ethyl group are more preferred, and a methyl group is preferred.

[0203] In formula (c1-L-1), formula (c1-L-2), formula (c1-L-5), and formula (c1-L-6), Z X and Z Y are each preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably both are hydrocarbon groups having 1 to 6 carbon atoms, even more preferably both are hydrocarbon groups having 1 to 3 carbon atoms, and particularly preferably both are methyl groups. In formula (c1-L-3) and formula (c1-L-4), Z X and Z Yis preferably a hydrogen atom, and more preferably all are hydrogen atoms.

[0204] In formula (c1-L-1), n1 is preferably an integer of 0 or more and 7 or less, more preferably an integer of 2 or more and 5 or less, and still more preferably 2 or 3. In formula (c1-L-2), n2 is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less, and still more preferably 0 or 1. In formula (c1-L-3), n3 is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less. In formula (c1-L-4), n4 is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less. In formula (c1-L-5), n5 is preferably an integer of 0 or more and 8 or less. In formula (c1-L-6), n6 is preferably an integer of 0 or more and 6 or less. In formula (c1-L-7), n7 is preferably an integer of 0 or more and 8 or less.

[0205] The following shows preferred specific examples of L 1 ~L 8 * represents a bond to Si. ** represents a bond to any one of R 1 ~R 8 Among these, the group represented by (c1-L1-1) or (c1-L1-3) is preferred.

[0206]

Chemical formula

[0207]

Chemical formula

[0208] (Cyclic siloxane (C1-2))

Chemical formula

[0209] nc2 is preferably an integer of 3 or more and 5 or less, more preferably 4.

[0210] R 9 is preferably an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, or an aromatic group having a phenolic hydroxyl group, more preferably an aromatic group having a methylol group or an alkoxymethyl group, or an aromatic group having a phenolic hydroxyl group, and even more preferably an aromatic group having a methylol group or an alkoxymethyl group.

[0211] R 9 At least one of the others may be an aromatic group having a phenolic hydroxyl group.

[0212] R 9Among them, the number of aromatic groups having a hydroxymethyl group or an alkoxymethyl group is preferably 1 or more, more preferably 3 or more, still more preferably 4 or more. Further, the number of aromatic groups having a hydroxymethyl group or an alkoxymethyl group may be, for example, 7 or less, 5 or less, 3 or less, or 1 or less. R 9 Among them, the number of nitrogen atom-containing groups having a hydroxymethyl group or an alkoxymethyl group is preferably 1 or more, more preferably 3 or more, still more preferably 4 or more. Further, the number of aromatic groups having a hydroxymethyl group or an alkoxymethyl group may be, for example, 7 or less, 5 or less, 3 or less, or 1 or less. R 9 Among them, the total number of the aromatic groups having a hydroxymethyl group or an alkoxymethyl group and the nitrogen atom-containing groups having a hydroxymethyl group or an alkoxymethyl group is preferably 2 or more, more preferably 4 or more. Further, the total number may be, for example, 7 or less, 5 or less, 3 or less, or 1. R 9 Among them, the number of aromatic groups having a phenolic hydroxyl group may be, for example, 1 or more, 3 or more, 6 or less, 4 or less, 2 or less, or 1 or less.

[0213] R 9 The aromatic groups having a hydroxymethyl group or an alkoxymethyl group, the nitrogen atom-containing groups having a hydroxymethyl group or an alkoxymethyl group, the aromatic groups having a phenolic hydroxyl group, and the hydrocarbon groups having 1 to 10 carbon atoms in R 1 ~R 8 are the same as these groups in R

[0214] In formula (c2-L-1), n8 is preferably an integer of 0 or more and 7 or less, more preferably an integer of 2 or more and 5 or less, still more preferably 2 or 3. In formula (c2-L-2), n9 is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less, still more preferably 0 or 1. In formula (c2-L-3), n10 is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less. In formula (c2-L-4), n11 is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less. In formula (c2-L-5), n12 is preferably an integer of 0 or more and 5 or less, more preferably an integer of 2 or more and 5 or less. In formula (c2-L-6), n13 is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 3 or less.

[0215] Hereinafter, preferred specific examples of L 9 are shown. * represents a bond to Si. ** represents a bond to R 9 and. Among these, the group represented by (c2-L1-1) or (c2-L1-2) is preferred.

[0216]

Chemical formula

[0217] Z Z is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0218] (C1) component weight average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography (GPC)) is not particularly limited, preferably 300 or more and 5000 or less, more preferably 400 or more and 3000 or less, and even more preferably 500 or more and 2000 or less. When the Mw of the (C1) component is below the preferred upper limit of this range, there is sufficient solubility in the solvent, and when it is above the preferred lower limit of this range, the dry etching resistance is enhanced, and the resist pattern cross-sectional shape is good. (C1) component dispersity (Mw / Mn) is not particularly limited, preferably 1.00 or more and 1.40 or less, more preferably 1.00 or more and 1.30 or less, and even more preferably 1.00 or more and 1.20 or less. Note that Mn represents the number average molecular weight.

[0219] The content of the component (C1) is preferably less than 5% by mass, more preferably 2% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.01% by mass or more and 1% by mass or less, and most preferably 0.01% by mass or more and 0.5% by mass or less with respect to the total mass of the first film-forming composition. In the first film-forming composition, the content of the component (C1) is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less, still more preferably 5 parts by mass or more and 20 parts by mass or less, and particularly preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the component (A). When the content of the component (C1) is within the above preferable range, it is effective for thinning in pattern formation.

[0220] The component (C1) can be produced using a known production method. For example, the cage-type silsesquioxane represented by the formula (c1-1) can be produced by reacting the following raw material (X) and raw material (Y) and appropriately performing a deprotection reaction as in Synthesis Examples (1) to (4) described later.

[0221] Raw material (X): An octasilsesquioxane having a cage structure in which a functional group capable of reacting with the raw material (Y) is bonded to silicon (Si) at each vertex. Examples of the functional group capable of reacting with the raw material (Y) include a dimethylsilyloxy group and a vinyl group.

[0222] Raw material (Y): A raw material having an "ionic group that decomposes upon exposure to generate an acid" or a part thereof. Examples of this raw material include (4-vinylphenyl)methanol, (4-allylphenyl)methanol, and 1-ethenyl-4-(methoxymethyl)benzene.

[0223] [Base component (D)] The film-forming composition contains a base component (D) (hereinafter also referred to as “component (D)”) that controls the diffusion of the acid generated by exposure. Component (D) acts as a quencher (acid diffusion controller) that traps the acid generated by exposure in the film-forming composition. As a result, particularly as a “negative resist composition for an alkali development process”, fine patterns are likely to be formed in a good shape. Examples of component (D) include a photo-dissociable base (D0) (hereinafter referred to as “component (D0)”) that decomposes upon exposure and loses acid diffusion controllability, and a nitrogen-containing organic compound (D2) that does not correspond to component (D0) (hereinafter referred to as “component (D2)”). Among these, a photo-dissociable base (component (D0)) is preferred because it is easy to enhance the characteristics of high sensitivity, roughness reduction, and suppression of the occurrence of coating defects.

[0224] ·Regarding the photo-dissociable base (component (D0)) Component (D0) is not particularly limited as long as it is a base that decomposes upon exposure and loses acid diffusion controllability, and preferably contains at least one onium salt selected from the group consisting of a compound represented by the following formula (d0-1) (hereinafter also referred to as “component (d0-1)”) and a compound represented by the following formula (d0-2) (hereinafter also referred to as “component (d0-2)”). Components (d0-1) and (d0-2) do not act as quenchers because they decompose in the exposed portion of the resist film and lose acid diffusion controllability (basicity), and act as quenchers in the unexposed portion of the resist film.

[0225]

Chemical formula

[0226] ···Regarding the component (d0-1) In the above formula (d0-1), R d20 As the organic group having 1 to 40 carbon atoms in, a hydrocarbon group which may have a substituent, a divalent linking group containing an oxygen atom, or a combination thereof can be mentioned. As this onium salt, the carboxylate represented by the following formula (d0-1d) is preferable.

[0227]

Chemical formula

[0228] R d201 is a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and is the same group as the group exemplified in the description about R b101 in the above formula (b0-1b). Among them, as R d201 a cyclic group having a hydroxyl group, a cyclic group having an iodine atom, or a cyclic group having a bromine atom is preferable, an aromatic hydrocarbon group having a hydroxyl group is more preferable, and a phenyl group having a hydroxyl group and a naphthyl group having a hydroxyl group are further preferable.

[0229] In the above formula (d0-1d), as the divalent linking group in Yd 0 a divalent linking group containing an oxygen atom can be preferably mentioned. Yd 0 When is a divalent linking group containing an oxygen atom, the Yd 0 may contain an atom other than an oxygen atom. Examples of the atom other than an oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, a nitrogen atom, etc. Examples of the divalent linking group containing an oxygen atom include non-hydrocarbon-based oxygen atom-containing linking groups such as an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), an amide bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), a carbonate bond (-O-C(=O)-O-), etc.; combinations of the non-hydrocarbon-based oxygen atom-containing linking group and an alkylene group, combinations of the non-hydrocarbon-based oxygen atom-containing linking group and an arylene group, etc. A sulfonyl group (-SO2-) may be further linked to this combination. Examples of the above arylene group include a phenylene group, a naphthylene group, etc. The above arylene group may have a substituent such as a halogen atom. Among them, Yd 0 is preferably a single bond, a combination of the non-hydrocarbon-based oxygen atom-containing linking group and an alkylene group, or a combination of the non-hydrocarbon-based oxygen atom-containing linking group and an arylene group, and more preferably a single bond.

[0230] Preferred specific examples of the anion part of the carboxylate represented by the formula (d0-1d) are shown below.

[0231]

Chemical formula

[0232]

Chemical formula

[0233]

Chemical formula

[0234] M2 + is an onium cation, and among them, a sulfonium cation and an iodonium cation are preferably used. M2 +Suitable examples of the cations are the same as those represented by the above formulas (ca-1) to (ca-3), more preferably the cation represented by the above formula (ca-1), and even more preferably the cations represented by the formulas (ca-1-1) to (ca-1-84). Among these, the cation represented by the above formula (b0-ca) is particularly preferred. The component (d0-1) may be used alone or in combination of two or more types.

[0235] Regarding the (d0-2) component R d10 The organic group having 1 to 40 carbon atoms in the formula (I) includes a hydrocarbon group which may have a substituent, a divalent linking group containing an oxygen atom, or a combination thereof. R d10 The organic group in the formula (b0-1b) is, for example, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. b101 Examples of the groups include the same groups as those exemplified in the description of Among them, R d10 is preferably a chain alkyl group having an iodine atom, or an aliphatic cyclic group having an iodine atom. The number of carbon atoms in the chain alkyl group is preferably 1 or more and 10 or less, more preferably 3 or more and 10 or less. The aliphatic cyclic group is more preferably a group (which may have a substituent) in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like; or a group in which one or more hydrogen atoms have been removed from camphor, or the like. However, R d10 In the above, the carbon atom adjacent to the S atom is not bonded to a fluorine atom (is not substituted with fluorine). This makes the anion portion of the sulfonate salt represented by general formula (d0-2) an appropriately weak acid anion, thereby improving the quenching ability.

[0236] R d10The hydrocarbon group may have a substituent, and examples of the substituent include the same groups as those that the hydrocarbon group (aromatic hydrocarbon group, alicyclic group, linear alkyl group, linear alkenyl group) in R in the above formula (b0-1b) may have. b101 The same groups as those that the hydrocarbon group (aromatic hydrocarbon group, alicyclic group, linear alkyl group, linear alkenyl group) in b101 may have are exemplified.

[0237] Hereinafter, preferred specific examples of the anionic part of the sulfonate represented by the formula (d0-2) are shown.

[0238] [Chemical formula]

[0239] M1 + is preferably a sulfonium cation or an iodonium cation. M1 + As M1, cations similar to the cations respectively represented by the above formulas (ca-1) to (ca-3) are preferably exemplified. Among them, the cation represented by the above formula (ca-1) is more preferable, and the cations respectively represented by the formulas (ca-1-1) to (ca-1-84) are even more preferable. Among them, the cation represented by the above formula (b0-ca) is particularly preferable. The component (d0-2) may be used alone or in combination of two or more.

[0240] The component (D0) may use only one of the above components (d0-1) and (d0-2), or may use two or more in combination. When the first film-forming composition contains the component (D0), the content of the component (D0) is appropriately set according to the molar ratio with the component (B). For example, with respect to 100 parts by mass of the component (A), 5 parts by mass or more and 60 parts by mass or less are preferable, 10 parts by mass or more and 50 parts by mass or less are more preferable, and 20 parts by mass or more and 45 parts by mass or less are even more preferable.

[0241] The component (D0) preferably contains the above component (d0-1). Of the entire (D0) component, the content of the (d0-1) component is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and the (D0) component may consist only of the (d0-1) component.

[0242] ·Regarding the nitrogen-containing organic compound ((D2) component) As the (D) component, a nitrogen-containing organic compound component ((D2) component) that does not correspond to the above (D0) component may be contained. As the (D2) component, it acts as an acid diffusion controller and is not particularly limited as long as it does not correspond to the (D0) component, and it may be arbitrarily used from known compounds. Among them, aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred. An aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms. Examples of the aliphatic amine include amines (alkylamines or alkyl alcohol amines) or cyclic amines in which at least one hydrogen atom of ammonia NH3 is substituted with an alkyl group or a hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of the alkylamine and alkyl alcoholamine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 6 to 30 carbon atoms are more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

[0243] Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine). Specific examples of the aliphatic monocyclic amine include piperidine and piperazine. The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, and specific examples include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0244] Examples of other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., and triethanolamine triacetate is preferred.

[0245] Further, as the component (D2), an aromatic amine may be used. Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert-butylpyridine, 2,6-di-tert-butylpyridine, etc.

[0246] The component (D2) may be used alone or in combination of two or more. When the film-forming composition contains the component (D2), in the film-forming composition, the content of the component (D2) is usually used in the range of 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the component (A). By setting the above range, the resist pattern shape, standing time stability, etc. are improved.

[0247] 〔Other Components〕 The film-forming composition may further contain other components in addition to the above-described components (A), (B), (C1), and (D). As other components, known components conventionally blended in film-forming compositions based on silicon-containing compounds as base components can be used. Examples of such other components include, for example, other crosslinking agents (C3), organic carboxylic acids, etc., fluorine additive components, organic solvent components, etc.

[0248] (Other Crosslinking Agent (C3)) The film-forming composition may contain a crosslinking agent (C3) other than the component (C1) as the crosslinking agent (C). Examples of the component (C3) include melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, glycoluril-based crosslinking agents, phenol-based crosslinking agents, epoxy-based crosslinking agents, and the like. In the following, "lower" means having 1 to 5 carbon atoms.

[0249] Examples of the melamine-based crosslinking agent include compounds obtained by reacting melamine with formaldehyde to substitute a hydrogen atom of an amino group with a hydroxymethyl group, and compounds obtained by reacting melamine with formaldehyde and a lower alcohol to substitute a hydrogen atom of an amino group with a lower alkoxymethyl group. Specifically, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, and the like can be mentioned. Among them, hexamethoxymethylmelamine is preferable.

[0250] Examples of the urea-based crosslinking agent include compounds obtained by reacting urea with formaldehyde to substitute a hydrogen atom of an amino group with a hydroxymethyl group, and compounds obtained by reacting urea with formaldehyde and a lower alcohol to substitute a hydrogen atom of an amino group with a lower alkoxymethyl group. Specifically, bis(methoxymethyl)urea, bis(ethoxymethyl)urea, bis(propoxymethyl)urea, bis(butoxymethyl)urea, and the like can be mentioned. Among them, bis(methoxymethyl)urea is preferable.

[0251] Examples of the alkylene urea-based crosslinking agent include compounds represented by the following formula (CA-1).

[0252]

Chemical formula

[0253] Rc 1 and Rc 2 When Rc 1 and Rc 2 are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, and may be linear or branched. Rc Rc 3 and Rc 4 When Rc 3 and Rc 4 may be the same as or different from each other, and it is more preferable that they are the same. vc is preferably 0 or 1. As the alkylene urea-based crosslinking agent, in particular, a compound in which vc is 0 (ethylene urea-based crosslinking agent) and / or a compound in which vc is 1 (propylene urea-based crosslinking agent) is preferable.

[0254] The compound represented by the above formula (CA-1) can be obtained by subjecting alkylene urea and formalin to a condensation reaction and further reacting the product with a lower alcohol.

[0255] Specific examples of the alkylene urea - based cross - linking agent include, for example, ethylene urea - based cross - linking agents such as mono - and / or di - hydroxymethylated ethylene urea, mono - and / or dimethoxymethylated ethylene urea, mono - and / or diethoxymethylated ethylene urea, mono - and / or dipropoxymethylated ethylene urea, mono - and / or dibutoxymethylated ethylene urea; propylene urea - based cross - linking agents such as mono - and / or di - hydroxymethylated propylene urea, mono - and / or dimethoxymethylated propylene urea, mono - and / or diethoxymethylated propylene urea, mono - and / or dipropoxymethylated propylene urea, mono - and / or dibutoxymethylated propylene urea; 1,3 - bis(methoxymethyl) - 4,5 - dihydroxy - 2 - imidazolidinone, 1,3 - bis(methoxymethyl) - 4,5 - dimethoxy - 2 - imidazolidinone, and the like.

[0256] Examples of the glycoluril - based cross - linking agent include glycoluril derivatives in which the N - position is substituted by one or both of a hydroxyalkyl group and an alkoxyalkyl group having 1 to 4 carbon atoms. The glycoluril derivative can be obtained by subjecting glycoluril and formalin to a condensation reaction and then reacting the product with a lower alcohol. Specific examples of the glycoluril - based cross - linking agent include, for example, mono -, di -, tri - and / or tetra - hydroxymethylated glycoluril; mono -, di -, tri - and / or tetra - methoxymethylated glycoluril; mono -, di -, tri - and / or tetra - ethoxymethylated glycoluril; mono -, di -, tri - and / or tetra - propoxymethylated glycoluril; mono -, di -, tri - and / or tetra - butoxymethylated glycoluril, and the like.

[0257] The phenol - based cross - linking agent is not particularly limited as long as it is a compound having a plurality of phenol nuclear structures in the same molecule, and can be arbitrarily selected and used. Having a plurality of phenol nuclear structures improves the cross - linking reactivity. The number of phenol nuclear structures is preferably 2 or more and 5 or less, more preferably 2 or more and 4 or less, and still more preferably 2 or 3.

[0258] Specific examples suitable as glycoluril - based cross - linking agents or phenolic cross - linking agents are shown below.

[0259]

Chemical formula

[0260] As the epoxy - based cross - linking agent, there is no particular limitation as long as it is a cross - linking agent having an epoxy group, and it can be arbitrarily selected and used. Among them, a cross - linking agent having two or more epoxy groups is preferable. By having two or more epoxy groups, the cross - linking reactivity is improved. The number of epoxy groups is preferably two or more, more preferably two or more and four or less, and most preferably two. Specific examples suitable as the epoxy - based cross - linking agent are shown below.

[0261]

Chemical formula

[0262] Among them, as the (C3) component, a compound having an alkylol group such as a methylol group or an alkoxyalkyl group such as a methoxymethyl group is preferable, a cross - linking agent selected from the group consisting of glycoluril - based cross - linking agents and phenolic cross - linking agents is more preferable, and a glycoluril - based cross - linking agent is even more preferable.

[0263] (At least one compound (E) selected from the group consisting of organic carboxylic acids and oxo - acids of phosphorus and their derivatives) In the film - forming composition, for the purpose of preventing sensitivity deterioration and improving resist pattern shape, standing - time stability, etc., at least one compound (E) (hereinafter referred to as "(E) component") selected from the group consisting of organic carboxylic acids and oxo - acids of phosphorus and their derivatives can be contained as an arbitrary component. Examples of the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. Among them, salicylic acid is preferred. Examples of the oxo acid of phosphorus include phosphoric acid, phosphonic acid, phosphinic acid, etc. Among them, phosphonic acid is particularly preferred.

[0264] (Component (E)) may be used alone or in combination of two or more. When the first film-forming composition contains component (E), the content of component (E) is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 5 parts by mass or less, based on 100 parts by mass of component (A). By setting the content within the above range, the stability of the film-forming composition over time is improved.

[0265] (Fluorine additive component (F)) The film-forming composition may contain a fluorine additive component (hereinafter referred to as "(F) component") as a hydrophobic resin. The (F) component is used to impart water repellency to the resist film, and by using it as a resin different from component (A), the lithography characteristics can be improved. As the (F) component, for example, the fluorine-containing polymer compounds described in JP-A-2010-002870, JP-A-2010-032994, JP-A-2010-277043, JP-A-2011-13569, and JP-A-2011-128226 can be used. More specifically, examples of the (F) component include polymers having a structural unit (f1) represented by the following formula (f1-1). As this polymer, a polymer consisting only of the structural unit (f1) represented by the following formula (f1-1) (homopolymer); a copolymer of the structural unit (f1) and a structural unit (a101) containing an acid-decomposable group whose polarity increases by the action of an acid; or a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a101) is preferred, and a copolymer of the structural unit (f1) and the structural unit (a101) is more preferred. Here, as the structural unit (a101) copolymerized with the structural unit (f1), a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate and a structural unit derived from 1-methyl-1-adamantyl (meth)acrylate are preferable, and a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate is more preferable.

[0266] [Chemical formula] (In the formula, R is the same as above, Rf 102 and Rf 103 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf 102 and Rf 103 may be the same or different. nf 1 is an integer of 0 or more and 5 or less, and Rf 101 is an organic group containing a fluorine atom.)

[0267] In formula (f1-1), examples of R bonded to the carbon atom at the α-position include an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a hydrogen atom. As R, a hydrogen atom or a methyl group is preferable. In formula (f1-1), as the halogen atom of Rf 102 and Rf 103 , a fluorine atom is preferable. As the alkyl group having 1 to 5 carbon atoms of Rf 102 and Rf 103 , a methyl group or an ethyl group is preferable. As the halogenated alkyl group having 1 to 5 carbon atoms of Rf 102 and Rf 103 , specifically, a group in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms can be mentioned. As the halogen atom, a fluorine atom is preferable. Among them, Rf 102 and Rf 103Examples thereof include a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, with a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group being more preferred, and a hydrogen atom being even more preferred. In formula (f1-1), nf 1 is an integer of 0 or more and 5 or less, preferably an integer of 0 or more and 3 or less, and more preferably 1 or 2.

[0268] In formula (f1-1), Rf 101 is an organic group containing a fluorine atom, preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing a fluorine atom may be linear, branched, or cyclic, preferably having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Further, in the hydrocarbon group containing a fluorine atom, preferably 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more, and particularly preferably 60% or more because the hydrophobicity of the resist film during immersion exposure is increased. Among them, Rf 101 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a trifluoromethyl group, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, -CH2-CH2-CF2-CF2-CF2-CF3.

[0269] The weight average molecular weight (Mw) (in terms of polystyrene conversion by gel permeation chromatography) of the component (F) is preferably 1,000 or more and 50,000 or less, more preferably 5,000 or more and 40,000 or less, and most preferably 10,000 or more and 30,000 or less. When it is below the upper limit of this range, there is sufficient solubility in the resist solvent for use as a resist, and when it is above the lower limit of this range, the water repellency of the resist film is good. (F) component's dispersity (Mw / Mn) is preferably 1.0 or more and 5.0 or less, more preferably 1.0 or more and 3.0 or less, and most preferably 1.0 or more and 2.5 or less.

[0270] (F) component may be used alone or in combination of two or more. When the first film-forming composition contains the (F) component, the content of the (F) component is preferably 0.5 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of the (A) component.

[0271] (Organic solvent component (S)) The film-forming composition can be produced by dissolving a resist material in an organic solvent component (hereinafter referred to as the "(S) component"). In the film-forming composition, the (S) component may be used alone or as a mixed solvent of two or more. Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether, γ-butyrolactone, ethyl lactate (EL), and cyclohexanone are preferable.

[0272] The usage amount of the (S) component is not particularly limited and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. From the viewpoint of coatability to a substrate or the like, the solid content concentration of the film-forming composition is preferably in the range of 0.1 mass% or more and 10 mass% or less, more preferably 0.2 mass% or more and 5 mass% or less, and still more preferably 0.3 mass% or more and 2 mass% or less.

[0273] <Second film-forming composition> As described above, the second film-forming composition contains a photoacid generator (B), a silicon-containing crosslinking agent (C2), and a base component (D). The photoacid generator (B), the base component (D), and other components are the same as those in the first film-forming composition.

[0274] Hereinafter, regarding the second film-forming composition, the silicon-containing crosslinking agent (C2) will be described.

[0275] [Silicon-containing crosslinking agent (C2)] The second film-forming composition contains a silicon-containing crosslinking agent (C2) (hereinafter also referred to as the "(C2) component") as the crosslinking agent (C). The silicon-containing crosslinking agent (C2) has a methylol group and / or an alkoxymethyl group, and a phenolic hydroxyl group.

[0276] Since the (C2) component has a phenolic hydroxyl group in addition to the methylol group and / or the alkoxymethyl group, it can exhibit the same action as the silicon-containing polymer (A).

[0277] The (C2) component is the same as the (C1) component except that it has a phenolic hydroxyl group in addition to the methylol group and / or the alkoxymethyl group.

[0278] The silicon-containing crosslinking agent (C2) preferably contains at least one selected from the group consisting of a cage-type silsesquioxane (C2-1) represented by the following formula (c2-1) and a cyclic siloxane (C2-2) represented by the following formula (c2-2).

[0279] (Cage-type silsesquioxane (C2-1)) [Chemical formula] (In the formula (c2-1), R 1 ~R 8 are each independently an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R 1 ~R 8 is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, and at least one of the others is an aromatic group having a phenolic hydroxyl group. L 1 ~L 8is each independently a divalent linking group represented by any one of the above formulas (c1-L-1) to (c1-L-7).)

[0280] (Cyclic siloxane (C2-2)) [Chemical formula] (In formula (c2-2), R 9 is each independently an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R 9 is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, and at least one of the others is an aromatic group having a phenolic hydroxyl group. L 9 is each independently a divalent linking group represented by any one of the above formulas (c2-L-1) to (c2-L-6). nc2 is an integer of 3 or more and 7 or less. Z Z is each independently a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom.)

[0281] The content of the silicon-containing crosslinking agent (C2) is preferably less than 5% by mass, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.10% by mass or more and 1% by mass or less with respect to the total mass of the second film-forming composition. When the content of the silicon-containing crosslinking agent (C2) is within the above preferable range, it is effective for thinning in pattern formation.

[0282] In the second film-forming composition, the content of the component (B) is preferably 1 part by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, still more preferably 15 parts by mass or more and 45 parts by mass or less, and particularly preferably 20 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the component (C2). When the content of the (B) component is equal to or higher than the lower limit of the above-preferred range, lithography characteristics such as sensitivity, resolution performance, and LWR (line width roughness) reduction properties are more likely to be improved in resist pattern formation. On the other hand, when it is equal to or lower than the upper limit of the preferred range, a uniform solution is more likely to be obtained when each component of the film-forming composition is dissolved in an organic solvent, and the storage stability of the composition is more likely to be enhanced.

[0283] When the second film-forming composition contains the (D0) component, the content of the (D0) component is appropriately set according to the molar ratio with the (B) component. For example, with respect to 100 parts by mass of the (C2) component, 5 parts by mass or more and 70 parts by mass or less are preferred, 20 parts by mass or more and 60 parts by mass or less are more preferred, and 30 parts by mass or more and 50 parts by mass or less are even more preferred.

[0284] When the second film-forming composition contains the (D2) component, the content of the (D2) component is usually used in the range of 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the (C2) component. By setting the range as above, the resist pattern shape, stability over time of standing, etc. are improved.

[0285] When the second film-forming composition contains the (E) component, the content of the (E) component is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the (C2) component. By setting the range as above, the stability over time of the film-forming composition is improved.

[0286] When the second film-forming composition contains the (F) component, the content of the (F) component is preferably 0.5 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (C2) component.

[0287] <Use of the Film-Forming Composition> The film-forming composition is suitable for applications where a cured film is used. For example, during etching in the formation of a processing pattern in a semiconductor manufacturing process, it can be used as a composition for a so-called resist mask, or as a composition for a hard mask, or as a composition for forming a resist underlayer film formed between a support and a resist film.

[0288] The film-forming composition is particularly useful for an alkali development process that uses an alkali developer during the development process for resist pattern formation, and among them, it is suitable as a "negative resist composition for an alkali development process".

[0289] ≪Method for manufacturing a patterned cured film≫ The method for manufacturing a patterned cured film includes forming a coating film composed of the film-forming composition on a support (hereinafter, also referred to as a "coating film formation step"), selectively exposing the coating film in a position-selective manner (hereinafter, also referred to as an "exposure step"), and developing the coating film after the exposure to form a patterned cured film (hereinafter, also referred to as a "development step").

[0290] <Coating film formation step> First, the above-described film-forming composition is applied onto a support using a spinner or the like, and a baking (post-apply bake (PAB)) treatment is performed at a temperature condition of, for example, 80°C or higher and 150°C or lower for 40 seconds or longer and 120 seconds or shorter, preferably 60 seconds or longer and 90 seconds or shorter, to form a coating film (resist film).

[0291] <Exposure step> Next, selective exposure is performed on the resist film, for example, by exposure through a mask (mask pattern) on which a predetermined pattern is formed using an exposure apparatus such as an electron beam lithography apparatus or an EUV (extreme ultraviolet) exposure apparatus, or by direct irradiation with an electron beam without passing through a mask pattern. After the above exposure, a baking (post-exposure bake (PEB)) treatment is performed at a temperature condition of, for example, 80°C or higher and 150°C or lower for 40 seconds or longer and 120 seconds or shorter, preferably 60 seconds or longer and 90 seconds or shorter.

[0292] <Development Process> Next, the resist film after the above exposure is developed. In the case of the alkali development process, an alkali developer is used, and in the case of the solvent development process, a developer containing an organic solvent (organic-based developer) is used.

[0293] After the development process, preferably a rinsing process is performed. In the case of the alkali development process, water rinsing with pure water is preferred, and in the case of the solvent development process, it is preferable to use a rinsing solution containing an organic solvent. In the case of the solvent development process, after the above development process or rinsing process, a process of removing the developer or rinsing solution adhering to the pattern with a supercritical fluid may be performed. After the development process or after the rinsing process, drying is performed. Also, in some cases, a baking process (post-bake) may be performed after the above development process.

[0294] The support is not particularly limited, and a conventionally known support can be used. For example, a substrate for electronic components, a support on which a predetermined wiring pattern is formed, etc. can be mentioned. More specifically, a silicon wafer, a metal substrate such as copper, chromium, iron, aluminum, a glass substrate, etc. can be mentioned. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold, etc. can be used. Also, as the support, a support provided with an inorganic and / or organic film on the above-mentioned substrate may be used. Examples of the inorganic film include an inorganic anti-reflection film (inorganic BARC). Examples of the organic film include an organic anti-reflection film (organic BARC) and an organic film such as a lower-layer organic film in the multilayer resist method. Here, the multilayer resist method is a method in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are provided on a substrate, and patterning of the lower organic film is performed using a resist pattern formed on the upper resist film as a mask, and it is said that a pattern with a high aspect ratio can be formed. That is, according to the multilayer resist method, since the required thickness can be ensured by the lower organic film, the resist film can be made thinner, and formation of a fine pattern with a high aspect ratio becomes possible. Basically, the multilayer resist method can be divided into a method of forming a two-layer structure of an upper resist film and a lower organic film (two-layer resist method), and a method of forming a multilayer structure of three or more layers in which one or more intermediate layers (such as a metal thin film) are provided between the upper resist film and the lower organic film (three-layer resist method).

[0295] The wavelength used for exposure is not particularly limited, and it can be performed using radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. The resist pattern forming method of the present embodiment is particularly useful for a method of exposing the resist film with EUV (extreme ultraviolet) or EB (electron beam) in the step of exposing the above resist film.

[0296] The exposure method of the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be liquid immersion exposure (Liquid Immersion Lithography). Liquid immersion exposure is an exposure method in which the space between the resist film and the lens at the lowest position of the exposure apparatus is filled with a solvent (liquid immersion medium) having a refractive index larger than that of air in advance, and exposure (immersion exposure) is performed in that state. As the liquid immersion medium, a solvent having a refractive index larger than that of air and smaller than that of the resist film to be exposed is preferable. The refractive index of such a solvent is not particularly limited as long as it is within the above range. Examples of the solvent having a refractive index greater than that of air and smaller than that of the resist film include water, fluorine-based inert liquids, silicon-based solvents, hydrocarbon-based solvents, and the like. Specific examples of the fluorine-based inert liquid include liquids mainly composed of fluorine-based compounds such as C3HCl2F5, C4F9OCH3, C4F9OC2H5, and C5H3F7. Liquids having a boiling point of 70°C or higher and 180°C or lower are preferred, and liquids having a boiling point of 80°C or higher and 160°C or lower are more preferred. It is preferable that the fluorine-based inert liquid is a liquid having a boiling point within the above range because the removal of the medium used for liquid immersion can be performed by a simple method after the exposure is completed. As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms is particularly preferred. Specific examples of the perfluoroalkyl compound include perfluoroalkyl ether compounds and perfluoroalkylamine compounds. More specifically, examples of the perfluoroalkyl ether compound include perfluoro(2-butyl-tetrahydrofuran) (boiling point 102°C), and examples of the perfluoroalkylamine compound include perfluorotributylamine (boiling point 174°C). As the liquid immersion medium, water is preferably used from the viewpoints of cost, safety, environmental issues, versatility, and the like.

[0297] Examples of the alkaline developer used for development in the alkaline development process include an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 0.1% by mass or more and 10% by mass or less.

[0298] The organic solvent contained in the organic developer used for development in the solvent development process may be any organic solvent that can dissolve the component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, amide-based solvents, and ether-based solvents, and hydrocarbon-based solvents can be mentioned. A ketone solvent is an organic solvent containing C-C(=O)-C in its structure. An ester solvent is an organic solvent containing C-C(=O)-O-C in its structure. An alcohol solvent is an organic solvent containing an alcoholic hydroxyl group in its structure. The "alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. A nitrile solvent is an organic solvent containing a nitrile group in its structure. An amide solvent is an organic solvent containing an amide group in its structure. An ether solvent is an organic solvent containing C-O-C in its structure. Among organic solvents, there are also organic solvents containing a plurality of types of functional groups characterizing the above solvents in their structures. In that case, it corresponds to any solvent type containing the functional groups possessed by the organic solvent. For example, diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification. A hydrocarbon solvent consists of a hydrocarbon which may be halogenated and has no substituent other than a halogen atom. As the halogen atom, a fluorine atom is preferred. As the organic solvent contained in the organic developing solution, among the above, a polar solvent is preferred, and a ketone solvent, an ester solvent, a nitrile solvent, etc. are preferred.

[0299] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone), etc. Among these, as the ketone solvent, methyl amyl ketone (2-heptanone) is preferred.

[0300] Examples of the ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, etc. Among these, butyl acetate is preferred as the ester solvent.

[0301] Examples of the nitrile solvents include acetonitrile, propionitrile, valeronitrile, butyronitrile, and the like.

[0302] Known additives can be incorporated into the organic developer as needed. Examples of the additives include surfactants. The surfactants are not particularly limited, and for example, ionic and nonionic fluorine-based and / or silicon-based surfactants can be used.

[0303] The development process can be carried out by a known development method. For example, a method of immersing the support in the developer for a certain period of time (dip method), a method of raising the developer on the support surface by surface tension and allowing it to stand still for a certain period of time (paddle method), a method of spraying the developer on the support surface (spray method), a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed on a support rotating at a constant speed (dynamic dispense method), and the like can be mentioned.

[0304] As the organic solvent contained in the rinse liquid used for the rinse treatment after the development process in the solvent development process, for example, among the organic solvents mentioned as the organic solvents used in the above organic developer, an organic solvent that is difficult to dissolve the resist pattern can be appropriately selected and used. Usually, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used alone or in combination of two or more. Also, they may be used in mixture with organic solvents other than the above and water.

[0305] The rinse treatment (washing treatment) using the rinse liquid can be carried out by a known rinse method. Examples of the method of the rinse treatment include a method of continuously discharging the rinse liquid on a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinse liquid for a certain period of time (dip method), a method of spraying the rinse liquid on the support surface (spray method), and the like.

[0306] According to the resist pattern forming method of the present embodiment described above, since the composition for film formation described above is used, even a composition containing a silicon-containing compound as a base material component can achieve both etching resistance and lithography characteristics such as a pattern roughness reduction effect, and can form a fine pattern with a fine dimension. For example, even in lithography using EUV, it has excellent fine resolution and sufficient etching resistance, and can form a fine pattern of a dozen nanometers in a good shape. In the case of a line and space pattern (LS pattern), the roughness of the line sidewall is small, and an LS pattern with a more uniform width can be easily formed. In particular, the resist pattern forming method of the present embodiment is a useful method for forming a negative resist pattern by alkali-developing the resist film after the exposure in the above step (iii).

[0307] In the composition for film formation of the above-described embodiment and various materials used in the resist pattern forming method of the above-described embodiment (for example, resist solvent, developer, rinse liquid, composition for antireflection film formation, composition for topcoat formation, etc.), it is preferable that they do not contain impurities such as metals, metal salts containing halogens, acids, alkalis, components containing sulfur atoms or phosphorus atoms. Here, examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The content of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, still more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially not contained (below the detection limit of the measuring device).

[0308] ≪Cage-type silsesquioxane≫ The cage-type silsesquioxane is represented by the following formula (c0-1).

Chemical formula

Chemical formula

[0309] R 01 ~R 08 preferred embodiments are the same as R 01 ~R 08 in formula (c1-1).

[0310] Z X and Z YThe preferred embodiments for Z in formulas (c1-L-1) to (c1-L-3) and (c1-L-5) to (c1-L-7) X and Z Y are the same.

[0311] In formula (c0-L-1), n01 is preferably an integer of 2 or more, more preferably an integer of 2 or more and 10 or less, still more preferably an integer of 2 or more and 7 or less, particularly preferably an integer of 2 or more and 5 or less, and most preferably 2 or 3. However, when 01 ~R 08 are all aromatic groups having a methylol group, n01 is preferably an integer of 3 or more and 10 or less, more preferably an integer of 3 or more and 7 or less, still more preferably an integer of 3 or more and 5 or less, and particularly preferably 3. In formula (c0-L-2), n02 is preferably an integer of 0 or more and 10 or less, more preferably an integer of 0 or more and 5 or less, still more preferably an integer of 0 or more and 3 or less, and particularly preferably 0 or 1. However, when 01 ~R 08 are all aromatic groups having a methylol group, n02 is preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 5 or less, still more preferably an integer of 1 or more and 3 or less, and particularly preferably 1. In formula (c1-L-3), n3 is preferably an integer of 0 or more and 10 or less, more preferably an integer of 0 or more and 5 or less, still more preferably an integer of 0 or more and 3 or less. In formula (c0-L-5), n05 is preferably an integer of 2 or more, more preferably an integer of 2 or more and 10 or less, still more preferably an integer of 2 or more and 8 or less. In formula (c0-L-6), n06 is preferably an integer of 0 or more and 10 or less, more preferably an integer of 0 or more and 6 or less. In formula (c0-L-7), n07 is preferably an integer of 0 or more and 10 or less, more preferably an integer of 0 or more and 8 or less.

[0312] ≪Cyclic siloxane≫ The cyclic siloxane is represented by the following formula (c0-2). [Chemical formula] (In formula (c0-2), R 09 is each independently an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R 09 is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group. L 09 is each independently a divalent linking group represented by any one of the following formulas (c0-L-8) to (c0-L-10), (c0-L-12), and (c0-L-13). nc2 is an integer of 3 or more and 7 or less. Z Z is each independently a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom.) [Chemical formula] (In formulas (c0-L-8) to (c0-L-12), n08 is an integer of 0 or more. n09 is an integer of 0 or more. n010 is an integer of 0 or more. n012 is an integer of 0 or more. n013 is an integer of 0 or more. However, when all of R 09 are aromatic groups having a methylol group or an alkoxymethyl group, n08 is an integer of 2 or more, and n012 is an integer of 2 or more. * represents a bond to Si. ** represents a bond to R 09 .)

[0313] The preferred embodiments of nc2, R 09 , and Z Z are the same as those of nc2, R 9 , Z Z in formula (c1-2).

[0314] In formula (c0-L-8), n8 is preferably an integer of 2 or more, more preferably an integer of 2 or more and 10 or less, still more preferably an integer of 2 or more and 7 or less, particularly preferably an integer of 2 or more and 5 or less, and most preferably 2 or 3. However, R 09 When all are aromatic groups having a methylol group or an alkoxymethyl group, n8 is preferably an integer of 2 or more and 10 or less, more preferably an integer of 2 or more and 7 or less, still more preferably an integer of 2 or more and 5 or less, and particularly preferably 2 or 3. In formula (c0-L-9), n9 is preferably an integer of 0 or more and 10 or less, more preferably an integer of 0 or more and 5 or less, still more preferably an integer of 0 or more and 3 or less, and particularly preferably 0 or 1. In formula (c0-L-10), n10 is preferably an integer of 0 or more and 10 or less, more preferably an integer of 0 or more and 5 or less, still more preferably an integer of 0 or more and 3 or less. In formula (c0-L-12), n12 is preferably an integer of 2 or more, more preferably an integer of 2 or more and 10 or less, still more preferably an integer of 2 or more and 5 or less, particularly preferably an integer of 2 or more and 5 or less. However, R 09 When all are aromatic groups having a methylol group or an alkoxymethyl group, n12 is preferably an integer of 2 or more and 10 or less, more preferably an integer of 2 or more and 5 or less, still more preferably an integer of 2 or more and 5 or less. In formula (c0-L-13), n13 is preferably an integer of 0 or more and 10 or less, more preferably an integer of 0 or more and 5 or less, still more preferably an integer of 0 or more and 3 or less.

Examples

[0315] Based on the examples, the present invention will be described in more detail, but the present invention is not limited by these examples.

[0316] ≪Production of silicon-containing crosslinking agent≫ The cage-shaped silsesquioxanes (C-1) to (C-4) and the cyclic siloxanes (C-5) to (C-8) were produced by the following Synthesis Examples (1) to (8), respectively.

[0317] <Synthesis Example (1): Production of Cage-Shaped Silsesquioxane (C-1)> 1.5 g of octakis(dimethylsilyloxy)octasilsesquioxane, 1.8 g of (4-vinylphenyl)methanol, 1.5 mg of a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%), and 18 g of toluene were mixed, and the mixture was stirred at room temperature for 13 hours. The mixture was concentrated using a rotary evaporator. 20 g of tetrahydrofuran and 0.15 g of activated carbon were added to the concentrated solution, and the mixture was stirred at room temperature for 30 minutes. Then, the filtrate was recovered by filtration using celite. The filtrate was concentrated using a rotary evaporator. 2.3 g of tetrahydrofuran was added to the concentrated solution to dissolve it, and then 9.0 g of heptane was added to reprecipitate the product. The supernatant was removed to purify the product. This purification by reprecipitation was repeated a total of 5 times. Propylene glycol monomethyl ether (PGME) was added to the obtained product, and the mixture was concentrated to dryness using a rotary evaporator three times. Then, PGME was added so that the concentration became 15%, and the concentrate was dissolved to obtain 19 g of a 15% PGME solution of cage-shaped silsesquioxane (C-1).

[0318]

Chemical formula

[0319] The obtained cage-shaped silsesquioxane (C-1) is a mixture of cage-shaped silsesquioxanes in which a group represented by formula (C-1-1) and a group represented by formula (C-1-2) are bonded to R in the cage structure. The introduction ratio of these groups to R in the cage structure was (C-1-1):(C-1-2) = 58:42 (molar ratio). The introduction ratio of the groups was calculated from the results of NMR (the same applies hereinafter).

[0320] For the obtained cage-type silsesquioxane (C-1), the weight-average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 2,000, the molecular weight dispersity (Mw / Mn) was 1.01, and the silicon content was 21%.

[0321] 1 H-NMR, 13 C-NMR, and 29 It was confirmed to have the following structure by Si-NMR analysis. 1 [H-NMR (600 MHz, DMSO-d6)] a: 8H, 4.9 ppm, b: 16H, 4.3 ppm 13 [C-NMR (150 MHz, DMSO-d6)] c: 16C, 65 ppm 29 [Si-NMR (120 MHz, DMSO-d6)] d: 8Si, 14 ppm, e: 8Si, -109 ppm

[0322]

Chemical Structure

[0323] <Synthesis Example (2): Preparation of Cage-Type Silsesquioxane (C-2)> Cage-type silsesquioxane (C-2) was synthesized in the same manner as in Synthesis Example (1), except that 1.8 g of (4-vinylphenyl)methanol was changed to 2.0 g of (4-allylphenyl)methanol.

[0324]

Chemical Structure

[0325] ​​​The obtained cage-type silsesquioxane (C-2) is a mixture of a cage-type silsesquioxane in which a group represented by the formula (C-2-1) and a group represented by the formula (C-2-2) are bonded to R in the cage structure. The introduction ratio of these groups to R in the cage structure was (C-2-1):(C-2-2)=61:39 (molar ratio). The introduction ratio of the groups was calculated from the results of NMR.

[0326] Regarding the obtained cage-type silsesquioxane (C-2), the weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 2,100, the molecular weight dispersity (Mw / Mn) was 1.01, and the silicon content was 20%.

[0327] 1 H-NMR, 13 C-NMR, and 29 It was confirmed to have the following structure by analysis of Si-NMR. 1 [H-NMR (600 MHz, DMSO-d6)] a: 8H, 4.8 ppm, b: 16H, 4.3 ppm 13 [C-NMR (150 MHz, DMSO-d6)] c: 16C, 64 ppm 29 [Si-NMR (120 MHz, DMSO-d6)] d: 8Si, 15 ppm, e: 8Si, -110 ppm

[0328]

Chemical formula

[0329] [Synthesis Example (3): Production of Cage-Type Silsesquioxane (C-3)] A cage-type silsesquioxane (C-3) was synthesized in the same manner as in Synthesis Example (1), except that 1.8 g of (4-vinylphenyl)methanol was changed to 2.0 g of 1-ethenyl-4-(methoxymethyl)benzene.

[0330]

Chemical formula

[0331] The obtained cage-type silsesquioxane (C-3) is a mixture of cage-type silsesquioxanes in which a group represented by the formula (C-3-1) and a group represented by the formula (C-3-2) are bonded to R in the cage structure. The introduction ratio of these groups to R in the cage structure was (C-3-1):(C-3-2) = 56:44 (molar ratio). The introduction ratio of the groups was calculated from the results of NMR.

[0332] For the obtained cage-type silsesquioxane (C-3), the weight-average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 2,100, the molecular weight dispersity (Mw / Mn) was 1.02, and the silicon content was 20%.

[0333] 1 H-NMR, 13 C-NMR, and 29 It was confirmed to have the following structure by analysis of Si-NMR. 1 [H-NMR (600 MHz, DMSO-d6)] a: 24H, 3.4 ppm, b: 16H, 4.1 ppm 13 [C-NMR (150 MHz, DMSO-d6)] c: 16C, 75 ppm 29 [Si-NMR (120 MHz, DMSO-d6)] d: 8Si, 14 ppm, e: 8Si, -109 ppm

[0334] [Chemical formula]

[0335] [Synthesis Example (4): Production of Cage-Type Silsesquioxane (C-4)] ​​​1.5 g of octakis(dimethylsilyloxy)octasilsequioxane, 1.26 g of 4-vinylphenol, 15 mg of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content 2%), and 15 g of toluene were mixed, and the mixture was stirred at room temperature for 1.5 hours. To the mixture, 0.40 g of (4-vinylphenyl)methanol and 15 mg of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content 2%) were added and stirred at room temperature for 14 hours. 0.15 g of activated carbon was added to the mixture and stirred at room temperature for 30 minutes, and then the filtrate was recovered by filtration using celite. The filtrate was concentrated with a rotary evaporator. After adding 1.5 g of tetrahydrofuran to the concentrated solution to dissolve it, 4.5 g of heptane was added to reprecipitate the product, and the product was purified by removing the supernatant. This purification by reprecipitation was repeated 5 times in total. Propylene glycol monomethyl ether (PGME) was added to the obtained product and concentrated to dryness with a rotary evaporator 3 times in a row. Then, PGME was added to dissolve it so that the concentration became 15%, and 17 g of a 15% PGME solution of cage-type silsesquioxane (C-4) was obtained.

[0336]

Chemical formula

[0337] The obtained cage-type silsesquioxane (C-4) is a mixture of cage-type silsesquioxanes in which a group represented by formula (C-4-1), a group represented by formula (C-4-2), a group represented by formula (C-4-3), and a group represented by formula (C-4-4) are bonded to R in the cage structure. The introduction ratio of these groups to R in the cage structure was (C-4-1):(C-4-2):(C-4-3):(C-4-4) = 7:5:49:39 (molar ratio). The introduction ratio of the groups was calculated from the results of NMR.

[0338] For the obtained basket-type silsesquioxane (C-4), the weight-average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 1,900, the molecular weight dispersity (Mw / Mn) was 1.04, and the silicon content was 22%.

[0339] 1 1H-NMR, 13 13C-NMR, and 29 1Si-NMR analysis confirmed that it had the following structure. 1 [1H-NMR (600 MHz, DMSO-d6)] a: 7.0H, 8.9 ppm, b: 0.96H, 4.3 ppm 13 [13C-NMR (150 MHz, DMSO-d6)] c: 7.0C, 156 ppm, d: 1.9C, 65 ppm 29 [29Si-NMR (120 MHz, DMSO-d6)] e: 8Si, 14 ppm, f: 8Si, -109 ppm

[0340]

Chemical formula

[0341] <Synthesis Example (5): Production of cyclic siloxane (C-5)> 1.0 g of 2,4,6,8-tetramethylcyclotetrasiloxane, 2.5 g of (4-vinylphenyl)methanol, 10 mg of a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content 2%), and 10 g of toluene were mixed, and the mixture was stirred at 80 °C for 6 hours. The mixture was concentrated using a rotary evaporator. ​​​10 g of tetrahydrofuran and 0.10 g of activated carbon were added to the concentrated solution, and the mixture was stirred at room temperature for 30 minutes. Then, the filtrate was collected by filtration using celite. The filtrate was concentrated using a rotary evaporator. After adding 2.0 g of tetrahydrofuran to the concentrated solution and dissolving it, 12 g of heptane was added to reprecipitate the product, and the product was purified by removing the supernatant. This purification by reprecipitation was repeated 5 times in total. Propylene glycol monomethyl ether (PGME) was added to the obtained product, and the mixture was concentrated to dryness using a rotary evaporator 3 times. Then, PGME was added to dissolve it to a concentration of 15%, and 17 g of a 15% PGME solution of cyclic siloxane (C-5) was obtained.

[0342]

Chemical formula

[0343] The obtained cyclic siloxane (C-5) is a mixture of cyclic siloxanes in which a group represented by the formula (C-5-1) and a group represented by the formula (C-5-2) are bonded to R in the cyclic structure. The introduction ratio of these groups to R in the cyclic structure was (C-5-1):(C-5-2) = 68:32 (molar ratio). The introduction ratio of the groups was calculated from the results of NMR.

[0344] For the obtained cyclic siloxane (C-5), the weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 700, the molecular weight dispersity (Mw / Mn) was 1.01, and the silicon content was 14%.

[0345] 1 1H-NMR, 13 13C-NMR, and 29 Si-NMR analysis confirmed that it had the following structure. 1 [1H-NMR (600 MHz, DMSO-d6)] a: 8H, 5.0 ppm, b: 16H, 4.4 ppm 13 [13C-NMR (150 MHz, DMSO-d6)]​​ c: 16C, 64 ppm 29 Si-NMR (120 MHz, DMSO-d6)] d: 4Si, -24, -20 ppm

[0346]

Chem.

[0347] <Synthesis Example (6): Production of Cyclic Siloxane (C-6)> Cyclic siloxane (C-6) was synthesized in the same manner as in Synthesis Example (5), except that 2.5 g of (4-vinylphenyl)methanol was changed to 2.7 g of (4-allylphenyl)methanol.

Chem.

[0348] The obtained cyclic siloxane (C-6) is a mixture of cyclic siloxanes in which a group represented by formula (C-6-1) and a group represented by formula (C-6-2) are bonded to R in the cyclic structure. The introduction ratio of these groups to R in the cyclic structure was (C-6-1):(C-6-2) = 72:28 (molar ratio). The introduction ratio of the groups was calculated from the results of NMR.

[0349] For the obtained cyclic siloxane (C-6), the weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 800, the molecular weight dispersity (Mw / Mn) was 1.01, and the silicon content was 13%.

[0350] 1 H-NMR, 13 C-NMR, and 29 It was confirmed to have the following structure by analysis of Si-NMR. 1 H-NMR (600 MHz, DMSO-d6)] a: 8H, 4.9 ppm, b: 16H, 4.4 ppm 13 ​​​C-NMR (150 MHz, DMSO-d6) c: 16C, 63 ppm 29 Si-NMR (120 MHz, DMSO-d6) d: 4Si, -25, -21 ppm

[0351]

Chem.

[0352] <Synthesis Example (7): Production of Cyclic Siloxane (C-7)> (Cyclic siloxane (C-7) was synthesized in the same manner as in Synthesis Example (5), except that 2.5 g of (4-vinylphenyl)methanol was changed to 2.7 g of 1-ethenyl-4-(methoxymethyl)benzene.)

Chem.

[0353] The obtained cyclic siloxane (C-7) is a mixture of cyclic siloxanes in which groups represented by formula (C-7-1) and groups represented by formula (C-7-2) are bonded to R in the cyclic structure. The introduction ratio of these groups to R in the cyclic structure was (C-7-1):(C-7-2) = 65:35 (molar ratio). The introduction ratio of the groups was calculated from the NMR results.)

[0354] For the obtained cyclic siloxane (C-7), the weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 800, the molecular weight dispersity (Mw / Mn) was 1.02, and the silicon content was 13%.)

[0355] 1 H-NMR, 13 C-NMR, and 29 It was confirmed to have the following structure by analysis of Si-NMR.) 1 H-NMR (600 MHz, DMSO-d6) a: 12H, 3.4 ppm, b: 16H, 4.2 ppm ​​13 C-NMR (150 MHz, DMSO-d6)] c: 16C, 75 ppm 29 Si-NMR (120 MHz, DMSO-d6)] d: 4Si, -24, -20 ppm

[0356]

Chemical formula

[0357] <Synthesis Example (8): Production of Cyclic Siloxane (C-8)> 1.0 g of 2,4,6,8-tetramethylcyclotetrasiloxane, 1.8 g of 4-vinylphenol, 10 mg of a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content 2%), and 10 g of toluene were mixed and stirred at 80 °C for 2 hours. To the mixture, 0.56 g of (4-vinylphenyl)methanol and 10 mg of a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content 2%) were added and stirred at 80 °C for 6 hours. The mixture was concentrated using a rotary evaporator. To the concentrated solution, 10 g of tetrahydrofuran and 0.10 g of activated carbon were added and stirred at room temperature for 30 minutes, and then the filtrate was recovered by filtration using celite. The filtrate was concentrated using a rotary evaporator. After dissolving by adding 2.0 g of tetrahydrofuran to the concentrated solution, 12 g of heptane was added to reprecipitate the product, and the product was purified by removing the supernatant. This purification by reprecipitation was repeated 5 times in total. Propylene glycol monomethyl ether (PGME) was added to the obtained product, and the mixture was concentrated to dryness using a rotary evaporator 3 times. Then, PGME was added to dissolve to a concentration of 15%, and 18 g of a 15% PGME solution of cyclic siloxane (C-8) was obtained.

[0358]

Chemical formula

[0359] The obtained cyclic siloxane (C-8) is a mixture of cyclic siloxanes in which a group represented by the formula (C-8-1), a group represented by the formula (C-8-2), a group represented by the formula (C-8-3), and a group represented by the formula (C-8-4) are bonded to R in the cyclic structure. The introduction ratios of these groups to R in the cyclic structure were (C-8-1):(C-8-2):(C-8-3):(C-8-4) = 8:4:53:35 (molar ratio). The introduction ratios of the groups were calculated from the results of NMR.

[0360] Regarding the obtained cyclic siloxane (C-8), the weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 700, the molecular weight dispersity (Mw / Mn) was 1.04, and the silicon content was 15%.

[0361] 1 H-NMR, 13 C-NMR, and 29 It was confirmed to have the following structure by analysis of Si-NMR. 1 [H-NMR (600 MHz, DMSO-d6)] a: 3.5H, 8.9 ppm, b: 0.48H, 5.0 ppm 13 [C-NMR (150 MHz, DMSO-d6)] c: 3.5C, 155 ppm, d: 0.96C, 64 ppm 29 [Si-NMR (120 MHz, DMSO-d6)] e: 4Si, -24, -20 ppm

[0362]

Chemical formula

[0363] ≪Preparation of Composition for Film Formation≫ <Examples 1 to 24 and Comparative Examples 1 to 6> Each of the components shown in Tables 1 to 3 was mixed and dissolved to prepare a composition for film formation for each example. ​​​

[0364]

Table 1

[0365]

Table 2

[0366]

Table 3

[0367] In Tables 1 to 3, each abbreviation has the following meaning. The numerical value in [] is the blending amount (parts by mass).

[0368] A-1: Resin represented by the following formula (weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC: 4,400, molecular weight dispersity (Mw / Mn): 1.89, silicon content: 24.9%)

Chemical formula

[0369] A-2: Resin represented by the following formula (weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC: 4,400, molecular weight dispersity (Mw / Mn): 1.75, silicon content: 20.4%)

Chemical formula

[0370] B-1: Compound represented by the following formula

Chemical formula

[0371] B-2: Compound represented by the following formula

Chemical formula

[0372] C-1 to C-4: The above-mentioned cage-type silsesquioxane (C-1) to (C-4) C-5 to C-8: The above-mentioned cyclic siloxane (C-5) to (C-8)

[0373] C-9: The compound represented by the following formula (molecular weight dispersity (Mw / Mn): 1.01)

Chemical formula

[0374] C-10: The compound represented by the following formula

Chemical formula

[0375] C-11: The cage-type silsesquioxane represented by the following formula (molecular weight dispersity (Mw / Mn): 1.02)

Chemical formula

[0376] C-12: The cage-type silsesquioxane represented by the following formula (the introduction ratio of the upper group to the lower group for R in the cyclic structure is upper group: lower group = 56:44 (molar ratio); molecular weight dispersity (Mw / Mn): 1.01)

Chemical formula

[0377] C-13: The cyclic siloxane represented by the following formula (molecular weight dispersity (Mw / Mn): 1.01)

Chemical formula

[0378] C-14: The cyclic siloxane represented by the following formula (molecular weight dispersity (Mw / Mn): 1.01)

Chemical formula

[0379] D-1: A compound represented by the following formula

Chemical formula

[0380] D-2: A compound represented by the following formula

Chemical formula

[0381] E-1: Salicylic acid S-1: Propylene glycol monomethyl ether S-2: Propylene glycol monomethyl ether acetate

[0382] <Formation of resist pattern> On a 12-inch silicon wafer, the resist organic underlayer film composition "AL412" (manufactured by Brewer Science) was applied using a spin coater and baked on a hot plate at 205 °C for 60 seconds to form an organic underlayer film with a thickness of 20 nm. On the organic underlayer film, each film-forming composition of each example was applied using a spin coater, and a pre-bake (PAB) treatment was performed on a hot plate at 90 °C for 60 seconds to form a resist film with a thickness of 22 nm. The resist film was irradiated with EUV light (13.5 nm) through a photomask using an EUV exposure apparatus NXE3400 (manufactured by ASML, NA (numerical aperture) = 0.33, illumination condition: Annular σ-in = 0.60, σ-out = 0.82). Thereafter, a PEB treatment was performed at 90 °C for 60 seconds. Next, alkali development was performed at 23 °C for 10 seconds with a 2.38 mass% TMAH aqueous solution (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thereafter, a water rinse was performed for 30 seconds using pure water, and spin drying was performed. As described above, a line and space pattern (LS pattern) with a line width of 14 nm was formed.

[0383] [Evaluation of Optimum Exposure Dose (Eop)] The optimum exposure dose Eop (mJ / cm 2 ) at which an LS pattern with a line width of 14 nm is formed by forming a resist pattern was determined. The results are shown in Tables 4 to 6.

[0384] [Evaluation of LWR (Line-Wise Roughness)] For the LS pattern with a line width of 14 nm formed by forming a resist pattern, 3σ, which is a measure indicating LWR, was determined. The results are shown in Tables 4 to 6. "3σ" indicates three times the standard deviation (σ) (unit: nm) obtained from measuring the line positions 400 times in the longitudinal direction of the line using a scanning electron microscope (acceleration voltage: 800 V, product name: S-9380, manufactured by Hitachi High-Technologies Corporation). The smaller the value of 3σ, the smaller the roughness of the line sidewall, which means that an LS pattern with a more uniform width was obtained.

[0385] [Table 4]

[0386] [Table 5]

[0387] [Table 6]

[0388] From the results in Tables 4 to 6, it was confirmed that when using the film-forming compositions of Examples 1 to 24, the roughness of the line sidewall was reduced and a resist pattern with a better shape was formed compared to the cases of using the film-forming compositions of Comparative Examples 1 to 3 and Comparative Example 6. Note that when the film-forming compositions of Comparative Example 4 and Comparative Example 5 were used, they did not resolve.

Claims

1. A film-forming composition comprising a silicon-containing polymer (A) having a phenolic hydroxyl group, a photoacid generator (B), a silicon-containing crosslinking agent (C1) having a methylol group and / or an alkoxymethyl group, and a base component (D) that controls the diffusion of the acid generated by exposure, or the photoacid generator (B), a silicon-containing crosslinking agent (C2) having a methylol group and / or an alkoxymethyl group, and a phenolic hydroxyl group, and the base component (D). Film-forming composition.

2. The film-forming composition according to claim 1, wherein the methylol group and / or alkoxymethyl group of the silicon-containing crosslinking agent (C1) or the silicon-containing crosslinking agent (C2) is bonded to an aromatic group or a nitrogen atom.

3. The silicon-containing crosslinking agent (C1) includes at least one selected from the group consisting of a cage-type silsesquioxane (C1-1) represented by the following formula (c1-1) and a cyclic siloxane (C1-2) represented by the following formula (c1-2), The silicon-containing crosslinking agent (C2) includes at least one selected from the group consisting of a cage-type silsesquioxane (C2-1) represented by the following formula (c2-1) and a cyclic siloxane (C2-2) represented by the following formula (c2-2). The film-forming composition according to claim 1. 【Chemical 1】 (In formula (c1-1), R １ ~R ８ are each independently an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R １ ~R ８ is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group. L １ ~L ８ are each independently a divalent linking group represented by any one of the following formulas (c1-L-1) to (c1-L-7). ) [Chemical 2] (In Formula (c1-L-1) to Formula (c1-L-7), Z Ｘ and Z Ｙ are each independently a hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom.) n1 to n7 are each independently an integer of 0 or more and 10 or less. * represents a bond with Si. ** represents a bond with any one of R １ to R ８ (represents a bond with any one of them.) [Chemical 3] (In formula (c1-2), R ９ is, independently of one another, an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R ９ is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group. L ９ is, independently of one another, a divalent linking group represented by any one of the following formulas (c2-L-1) to (c2-L-6). nc2 is an integer of 3 or more and 7 or less. Z Ｚ is, independently of one another, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom.) 【Chemical Formula 4】 (In Formula (c2-L-1) to Formula (c2-L-6), n8 to n13 are each independently an integer of 0 or more and 10 or less. * represents a bond to Si. ** represents a bond to R ９ .) [Chemical Formula 5] (In formula (c2-1), R １ to R ８ each independently represents an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R １ to R ８ is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, and at least one of the others is an aromatic group having a phenolic hydroxyl group. L １ to L ８ each independently represents a divalent linking group represented by any of the above formulas (c1-L-1) to (c1-L-7).) [Chemical Formula 6] (In formula (c2-2), R ９ is, independently of one another, an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R ９ is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, and at least one of the others is an aromatic group having a phenolic hydroxyl group. L ９ is, independently of one another, a divalent linking group represented by any one of the above formulas (c2-L-1) to (c2-L-6). nc2 is an integer of 3 or more and 7 or less. Z Ｚ is, independently of one another, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom.)

4. The film-forming composition according to claim 1, wherein the silicon-containing polymer (A) includes a silicon-containing polymer (A0) having a structural unit represented by the following formula (a0-1). [Chemical Formula 7] (In formula (a0-1), Ra ０ is an organic group having 1 to 40 carbon atoms or a hydrogen atom.)

5. The film-forming composition according to claim 4, wherein the silicon-containing polymer (A0) has a structural unit represented by the following formula (a0-1-1). [Chemical Formula 8] (In formula (a0-1-1), R Ａｒ１ is an aromatic hydrocarbon group. Ra １１ is a divalent linking group or a single bond. Ra １２ is a hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom. Ra １３ is a hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom. na2 is 1 or 2. na3 is an integer of 0 or more and 4 or less.)

6. The film-forming composition according to claim 1, wherein the photoacid generator (B) includes an onium salt represented by the following formula (b0). 【Chemical Formula 9】 (In formula (b0), R ｂ１０ is an organic group having 1 to 40 carbon atoms. M ３ ＋ is an onium cation.)

7. The film-forming composition according to claim 1, wherein the base component (D) includes at least one selected from the group consisting of a compound represented by the following formula (d0-1) and a compound represented by the following formula (d0-2). 【Chemical 10】 (In formula (d0-1), R ｄ２０ is an organic group having 1 to 40 carbon atoms. M ２ ＋ is an onium cation. In formula (d0-2), R ｄ１０ is an organic group having 1 to 40 carbon atoms. M １ ＋ is an onium cation.)

8. Forming a coating film composed of the film-forming composition according to any one of claims 1 to 7 on a support, Selectively exposing the coating film by position, and Developing the exposed coating film to form a patterned cured film, including Method for producing a patterned cured film.

9. The method for producing a patterned cured film according to claim 8, wherein the coating film is exposed to EUV (extreme ultraviolet rays).

10. A cage-type silsesquioxane represented by the following formula (c0-1). 【Chemical Formula 11】 (In formula (c0-1), R ０１ to R ０８ each independently represents an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R ０１ to R ０８ is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group. L ０１ to L ０８ each independently represents a divalent linking group represented by any one of the following formulas (c0-L-1) to (c0-L-3) and (c0-L-5) to (c0-L-7).) 【Chemical Formula 12】 (In formulas (c0-L-1) to (c0-L-3) and (c0-L-5) to (c0-L-7), Z Ｘ and Z Ｙ are each independently a hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom. n01 is an integer of 0 or more. n02 is an integer of 0 or more. n03 is an integer of 0 or more. n05 is an integer of 0 or more. n06 is an integer of 0 or more. n07 is an integer of 0 or more. However, when R ０１ to R ０８ are all aromatic groups having a methylol group, n01 is an integer of 3 or more, and n02 is an integer of 1 or more. * represents a bond to Si. ** represents a bond to any one of R ０１ to R ０８ .)

11. A cyclic siloxane represented by the following formula (c0-2). 【Chemical 13】 (In formula (c0-2), R ０９ is, independently of each other, an aromatic group having a methylol group or an alkoxymethyl group, a nitrogen atom-containing group having a methylol group or an alkoxymethyl group, an aromatic group having a phenolic hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. However, at least one of R ０９ is an aromatic group having a methylol group or an alkoxymethyl group, or a nitrogen atom-containing group having a methylol group or an alkoxymethyl group. L ０９ is, independently of each other, a divalent linking group represented by any one of the following formulas (c0-L-8) to (c0-L-10), (c0-L-12), and (c0-L-13). nc2 is an integer of 3 or more and 7 or less. Z Ｚ is, independently of each other, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom.) 【Chemical Formula 14】 (In formulas (c0-L-8) to (c0-L-12), n08 is an integer of 0 or more. n09 is an integer of 0 or more. n010 is an integer of 0 or more. n012 is an integer of 0 or more. n013 is an integer of 0 or more. However, R ０９ When all are aromatic groups having a methylol group or an alkoxymethyl group, n08 is an integer of 2 or more, and n012 is an integer of 2 or more. * represents a bond to Si. ** represents a bond to R ０９ .)

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