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

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 used in the composition for forming a film.SOLUTION: There is provided a composition for forming a film, which comprises a silicon-containing polymer containing a phenolic hydroxyl group (A), a cage silsesquioxane having an ionic group which is decomposed by exposure to generate an acid (B1), a crosslinking agent (C) and a base component (D) which controls diffusion of the acid generated by exposure or a cage silsesquioxane (B2) having an ionic group and a phenolic hydroxyl group which is decomposed by exposure to generate an acid, a crosslinking agent (C) and a base component (D) which controls diffusion of an acid generated by exposure.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In the production 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 production 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 shortened.

[0004] Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions. 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 a fine dimension in a good shape is required. For example, in lithography using EUV (extreme ultraviolet light), formation of a fine pattern of a dozen or so nm is targeted. As the pattern dimension becomes smaller, 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 an advantage of high dry etching resistance compared to a film-forming composition using a general organic material as a base material component, but in forming a targeted fine pattern, 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, the present inventors have conducted intensive studies and as a result, have found that the use of a cage-type silsesquioxane having an ionic group that decomposes upon exposure to generate an acid can solve the above problems, and have completed the present invention. 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 cage-type silsesquioxane (B1) having an ionic group that decomposes upon exposure to generate an acid, a crosslinking agent (C), and a base component (D) that controls the diffusion of the acid generated upon exposure, or a cage-type silsesquioxane (B2) having an ionic group that decomposes upon exposure to generate an acid and a phenolic hydroxyl group, a crosslinking agent (C), and a base component (D) that controls the diffusion of the acid generated upon exposure. A film-forming composition.

[0011] [2] The cage-type silsesquioxane (B1) includes a cage-type silsesquioxane represented by the following formula (b1), The film-forming composition according to [1], wherein the cage-type silsesquioxane (B2) includes a cage-type silsesquioxane represented by the following formula (b2). [Chemical formula] (In formula (b1), R 1 ~R 8 are each independently an organic group having 1 to 40 carbon atoms or a hydrogen atom. However, at least one of R 1 ~R 8 is an ionic group that decomposes upon exposure to generate an acid. L 1 ~L 8 are each independently a divalent linking group having 1 to 40 carbon atoms containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.) [Chemical formula] (In formula (b2), R 1 ~R 8is independently an organic group having 1 to 40 carbon atoms or a hydrogen atom, provided that R 1 ~R 8 at least one of which is an ionic group that decomposes upon exposure to generate an acid, and at least one of the others is an aromatic group having a phenolic hydroxyl group. L 1 ~L 8 is independently a divalent linking group having 1 to 40 carbon atoms and containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. )

[0012] [3] The film-forming composition according to [1] or [2], wherein the ionic group is a group represented by the following formula (b0).

Chemical formula

[0013] [4] The film-forming composition according to any one of [1] to [3], wherein the dispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of the cage-type silsesquioxane (B1) or the cage-type silsesquioxane (B2) is 1.00 or more and 1.30 or less.

[0014] [5] The film-forming composition according to any one of [1] to [4], wherein the base component (D) contains a compound represented by the following formula (d0-2).

Chemical formula

[0015] [6] Forming a coating film composed of the film-forming composition according to any one of [1] to [5] on a support, and Selectively exposing the coating film; Developing the coating film after the exposure to form a patterned cured film, and A method for manufacturing a patterned cured film.

[0016] [7] The method for manufacturing a patterned cured film according to [6], wherein the coating film is exposed to EUV (extreme ultraviolet rays).

[0017] [8] A cage-type silsesquioxane having an ionic group that decomposes upon exposure to generate an acid.

[0018] [9] The cage-type silsesquioxane according to [8], represented by the following formula (b1). [Chemical formula] (In formula (b1), R 1 ~R 8 are each independently an organic group having 1 to 40 carbon atoms or a hydrogen atom. However, at least one of R 1 ~R 8 is an ionic group that decomposes upon exposure to generate an acid. L 1 ~L 8 are each independently a divalent linking group having 1 to 40 carbon atoms containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.) [Advantages of the Invention]

[0019] 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 manufacturing a patterned cured film using the same, and a cage-type silsesquioxane used in the film-forming composition. [Embodiments for Carrying Out the Invention]

[0020] 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.

[0021] ≪Composition for Film Formation≫ The composition for film formation contains a silicon-containing polymer (A) having a phenolic hydroxyl group, a cage-type silsesquioxane (B1) having an ionic group that decomposes upon exposure to generate an acid, a crosslinking agent (C), and a base component (D) that controls the diffusion of the acid generated upon exposure, or contains a cage-type silsesquioxane (B2) having an ionic group that decomposes upon exposure to generate an acid and a phenolic hydroxyl group, a crosslinking agent (C), and a base component (D) that controls the diffusion of the acid generated upon exposure. Hereinafter, the composition for film formation containing the silicon-containing polymer (A), the cage-type silsesquioxane (B1), the crosslinking agent (C), and the base component (D) is referred to as the first composition for film formation. Also, the composition for film formation containing the cage-type silsesquioxane (B2), the crosslinking agent (C), and the base component (D) is referred to as the second composition for film formation.

[0022] <First Composition for Film Formation> As described above, the first composition for film formation contains a silicon-containing polymer (A), a cage-type silsesquioxane (B1), a crosslinking agent (C), and a base component (D). Hereinafter, the essential components and other components of the first composition for film formation will be described.

[0023] 〔Silicon-Containing Polymer (A)〕 The first film-forming composition contains a silicon-containing polymer (A) having a phenolic hydroxyl group. The silicon-containing polymer (A) has a phenolic hydroxyl group and a silicon atom in the same polymer. By using the silicon-containing polymer, in particular, the etching resistance of the resist film formed by the negative resist composition is enhanced. Further, the phenolic hydroxyl group forms a crosslinked structure by receiving the action of an acid generated from the component (B1) described below by exposure. As a result, the component (A) has a higher molecular weight. Furthermore, since it has a phenolic hydroxyl group, the component (A) is soluble in an alkaline developer, and the negative resist composition is imparted with alkali developability.

[0024] The content ratio of the silicon atoms in the component (A) is preferably 5% or more and 50% or less, more preferably 10% or more and 40% or less, and still more preferably 15% or more and 30% or less with respect to the total amount of all atoms constituting the component (A).

[0025] The content ratio of the silicon atoms in the component (A) 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 a polysiloxane having 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%.

[0026] As the component (A), a polysiloxane having a structural unit (a1) containing a phenolic hydroxyl group is preferable.

[0027] (Structural unit (a1)) Examples of the structural unit (a1) 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 a "group containing a phenolic hydroxyl group".

[0028] Preferred structural unit (a1) includes a structural unit represented by the following formula (a1-1).

[0029] [Chemical formula] (In the formula, Ra 1 is a hydrocarbon group having a phenolic hydroxyl group, and * is a bond.)

[0030] Specific examples of the "hydrocarbon group having a phenolic hydroxyl group" in Ra 1 are shown below. In the formula, * represents a bond. [Chemical formula]

[0031] As the structural unit represented by the formula (a1-1), a structural unit represented by the following formula (a1-1-1) is preferred.

[0032] [Chemical formula] (In the formula, Ra 11 is an alkylene group having 1 to 5 carbon atoms or a single bond, and na1 is an integer of 1 to 3.)

[0033] As Ra 11 , an alkylene group having 1 to 5 carbon atoms is preferred. As Ra 11 , the alkylene group may be linear, branched, or cyclic, but is preferably linear or branched. As Ra 11 , the number of carbon atoms of the alkylene group is preferably 1 to 3. As 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, and a pentane-1,5-diyl group. 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] na1 is preferably 1 or 2, more preferably 1. The substitution position of the hydroxyl group on the benzene ring may be any of the o-position, m-position, and p-position, but industrially, the p-position is preferably used.

[0035] The structural unit (a1) contained in the polysiloxane may be one type or two or more types. The proportion of the structural unit (a1) in the polysiloxane is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more with respect to the total of all the structural units constituting the polysiloxane. When the proportion of the structural unit (a1) is 30 mol% or more, a resist pattern with good lithography characteristics is likely to be formed. Also, the proportion of the structural unit (a1) is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less.

[0036] (Other structural units) The polysiloxane having the structural unit (a1) may have other structural units in addition to the structural unit (a1). 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.

[0037] · Structural unit (a2) The structural unit (a2) is a structural unit containing an alkyl group. Examples of the structural unit (a2) include structural units 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.

[0038] 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.

[0039] [Chemical formula] (In the formula, Ra 21 , Ra 22 , and Ra 23 are each independently an alkyl group having 1 to 10 carbon atoms.)

[0040] Ra 21 , Ra 22 , and Ra 23 The alkyl group in may be linear, branched, or cyclic, but is preferably linear or branched. Ra 21 , Ra 22 , and Ra 23 The alkyl group in preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Ra 21 , Ra 22 , and Ra 23 Examples of the alkyl group in 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, and the like. 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.

[0041] The structural unit (a2) contained in the polysiloxane may be one type or two or more types. When the polysiloxane has a structural unit (a2) in addition to the structural unit (a1), the proportion of the structural unit (a2) in the polysiloxane 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 the structural units constituting the polysiloxane. The proportion of the structural 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 the structural units constituting the polysiloxane. 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 polysiloxane. When the proportion of the structural unit (a2) is at least the lower limit value of the above preferred range, the etching resistance is more easily enhanced, and when it is at most the upper limit value of the above preferred range, a resist pattern with good lithography characteristics is more easily formed.

[0042] · 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, it is easy to control the dissolution rate.

[0043] [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.)

[0044] Ra 24The hydrocarbon group in [description] may be linear, branched, or cyclic, but is preferably linear or branched. Also, Ra 24 The hydrocarbon group in [description] 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 or more and 5 or less, more preferably 1 or more and 3 or less. Ra 24 As the hydrocarbon group in Ra, an alkyl group is preferable. 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, and a neopentyl group. Among them, 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. na3 is preferably an integer of 0 or more and 3 or less, more preferably 0 or 1, and even more preferably 0.

[0045] The structural unit (a3) possessed by the polysiloxane may be one kind or two or more kinds. When the polysiloxane has the structural unit (a3) in addition to the structural unit (a1), the proportion of the structural unit (a3) in the polysiloxane 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 with respect to the total of all the structural units constituting the polysiloxane.

[0046] · 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.

[0047] [Chemical formula]

[0048] The structural unit (a4) possessed by the polysiloxane may be one kind or two or more kinds. When the polysiloxane has the structural unit (a4) in addition to the structural unit (a1), the proportion of the structural unit (a4) in the polysiloxane is preferably 30 mol% or less, more preferably 5 mol% or more and 30 mol% or less, still more preferably 10 mol% or more and 25 mol% or less, based on the total of all the structural units constituting the polysiloxane.

[0049] The polysiloxane may be a polysiloxane having a structural unit containing at least one of an alkoxy group and a hydroxy group in addition to the structural unit (a1).

[0050] As the component (A), a polysiloxane in which the polymer main chain is composed of a repeating structure of Si-O bonds and has a repeating structure of the structural unit represented by the above formula (a1-1) is preferable. Among them, a silsesquioxane resin composed of a repeating structure of the structural unit represented by the formula (a1-1); a silsesquioxane resin having a repeating structure of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a2-1); a silsesquioxane resin having a repeating structure of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a2-2); a silsesquioxane resin having a repeating structure of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a3-1); a silsesquioxane resin having a repeating structure of the structural unit represented by the formula (a1-1), the structural unit represented by the formula (a2-1), and the structural unit represented by the formula (a3-1); a silsesquioxane resin having a repeating structure of the structural unit represented by the formula (a1-1), the structural unit represented by the formula (a2-2), and the structural unit represented by the formula (a3-1); a silsesquioxane resin having a repeating structure of the structural unit represented by the formula (a1-1), the structural unit represented by the formula (a3-1), and the structural unit represented by the general formula (a4-1) are preferable, and a silsesquioxane resin having a repeating structure of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a2-1) is more preferable.

[0051] The mass average molecular weight (Mw) of component (A) (in terms of polystyrene equivalent 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, still more preferably 2000 or more and 5000 or less. When the Mw of component (A) is at or below the upper limit of the above preferred range, the solubility in an organic solvent is likely to be improved. On the other hand, when it is at or above the lower limit of the above preferred range, the patterning property of the resist film is likely to be good, and the lithography characteristics of the formed resist pattern are likely to be enhanced.

[0052] Component (A) may be one kind or two or more kinds. The content of component (A) 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, based on the total mass of the first film-forming composition. When the content of component (A) is within the preferred range, it is easy to form a thin film in pattern formation.

[0053] 〔Cage-type silsesquioxane (B1)〕 The first film-forming composition contains cage-type silsesquioxane (B1) as the acid generator (B). Cage-type silsesquioxane (B1) has an ionic group that decomposes upon exposure to generate an acid. Cage-type silsesquioxane (B1) preferably has a perfect cage structure.

[0054] The content ratio of silicon atoms in component (B1) is preferably 5% or more and 45% or less, more preferably 8% or more and 35% or less, still more preferably 10% or more and 25% or less, based on the total amount of all atoms constituting component (B1). The method for calculating the content ratio of silicon atoms in component (B1) is the same as the method for calculating the content ratio of silicon atoms in component (A).

[0055] 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.

[0056] As the ionic group that decomposes upon exposure to light to generate an acid, a group represented by the following formula (b0) is preferable. [Chemical formula] (In formula (b0), R b10 is a divalent organic group having 1 to 40 carbon atoms. M3 + is a sulfonium cation or an iodonium cation.)

[0057] 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.

[0058] As the group represented by formula (b0), a group represented by the following formula (b0-1) is preferable. -R b101 -Yb 0 -Vb 0 -SO3 - M3 + (b0-1) (In the formula, R b101 is a cyclic group which may have a substituent, a chain-like alkylene group which may have a substituent, a chain-like alkenylene group which may have a substituent, or a single bond. Yb 0 is a divalent linking group or a single bond. Vb 0 is an alkylene group, a fluorinated alkylene group, or a cyclic group which may have a substituent. M3 + is a sulfonium cation or an iodonium cation.)

[0059] ·Regarding the anion part R b101 is preferably a cyclic group which may have a substituent or a single bond, and more preferably a single bond.

[0060] R b101 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.

[0061] R b101 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.

[0062] R b101 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 hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, etc. R b101 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 preferable.

[0063] R b101 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 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 two or more hydrogen atoms from a polycycloalkane is preferable. As the polycycloalkane, a polycycloalkane having 7 to 30 carbon atoms is preferable. Among them, as the polycycloalkane, a polycycloalkane having a crosslinked ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane; a polycycloalkane having a condensed ring polycyclic skeleton such as a cyclic group having a steroid skeleton is more preferable.

[0064] Among them, R b101 As the cyclic aliphatic hydrocarbon group in, a group obtained by removing two or more hydrogen atoms from a monocycloalkane or a polycycloalkane is preferable, a group obtained by removing two hydrogen atoms from a polycycloalkane is more preferable, a group obtained by removing two hydrogen atoms from adamantane or norbornane is particularly preferable, and a group obtained by removing two hydrogen atoms from adamantane is most preferable.

[0065] 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 particularly preferably 3. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, 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 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 preferred.

[0066] Also, R b101 The cyclic hydrocarbon group in may contain a hetero atom such as a heterocyclic ring.

[0067] R b101 The cyclic hydrocarbon group as may be a condensed ring type group containing a condensed ring in which an aliphatic hydrocarbon ring and an aromatic ring are condensed. Examples of the above 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 above bridged ring system polycycloalkane include bicyclic alkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. As the above condensed ring type group, a group containing a condensed ring in which 2 or 3 aromatic rings are condensed to a bicycloalkane is preferred, and a group containing a condensed ring in which 2 or 3 aromatic rings are condensed to bicyclo[2.2.2]octane is more preferred.

[0068] R b101The 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.

[0069] R b101 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.

[0070] R b101 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.

[0071] R b101 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.

[0072] Preferred Rb101 Examples include 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 Preferred examples of the hydrocarbon group in include a methyl group, an ethyl group, a propyl group, and an isopropyl group, more preferably a methyl group and an ethyl group, and even more preferably a methyl group. 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 Preferred examples of the hydrocarbon group in include a methyl group, an ethyl group, a propyl group, and an isopropyl group, more preferably a methyl group and an ethyl group. nb1 is preferably 1 or 2, more preferably 1. nb2 is preferably 0 or 1, more preferably 0. nb3 is preferably 0 or 1, more preferably 0.

[0076] Yb0 As the divalent linking group in Yb 0 when it is a divalent linking group containing an oxygen atom, the Yb 0 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, 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 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.

[0077] Vb 0 The number of carbon atoms of the alkylene group and the fluorinated alkylene group in

[0078] Vb 0 is each preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less. 0 As the alkylene group in 0 Vb 0 the alkylene group is preferably linear or branched, more preferably linear. As the alkylene group in0 As the fluorinated alkylene group in [it], -CH2CF2-, -CHFCF2-, -CH2CH2CF2- are preferable.

[0079] Vb 0 As the cyclic group in [it], an aromatic hydrocarbon group is preferable. Vb 0 The number of carbon atoms of the aromatic hydrocarbon group in [it] is preferably 3 or more and 30 or less, more preferably 6 or more and 15 or less, and still 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 0 Examples of the aromatic hydrocarbon group in [it] include a phenylene group, a naphthylene group, and the like. Vb 0 Examples of the substituent that the aromatic hydrocarbon group in [it] 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.

[0080] The following shows preferable specific examples of the anion part of the group represented by the formula (b0-1). Among these, the anion part represented by (b-R1-2) or (b-R1-5) is preferable.

Chemical formula

[0081] ·Regarding the cation part M3 + Examples of the sulfonium cation or iodonium cation in [it] include organic cations respectively represented by the following formulas (ca-1) to (ca-3).

[0082]

Chemical formula

[0083] R 201 ~R 207 Examples of the aryl group in R R 201 ~R 207 include aryl groups having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferred. R 201 ~R 207 The number of carbon atoms of the alkenyl group in R R 201 ~R 207 、and R 210 Examples of the substituent which may be possessed 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), and the like.

[0084]

Chemical formula

[0085] R’ 201 As the cyclic group as R’, a cyclic hydrocarbon group is preferable. 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.

[0086] R’ 201 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. R’ 201 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 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’ 201 Examples of the aromatic hydrocarbon group in R’ 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.), 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 2, and still more preferably 1.

[0087] R’ 201 The cyclic aliphatic hydrocarbon group in R’ includes an aliphatic hydrocarbon group containing a ring in the 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, and the like. 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 a 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 a polycycloalkane is preferable. As the polycycloalkane, a polycycloalkane having 7 to 30 carbon atoms is preferable. 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 preferable.

[0088] Among them, R’ 201 The cyclic aliphatic hydrocarbon group in is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane, more preferably a group obtained by removing one hydrogen atom from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0089] 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 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, examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], and the like. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include 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. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0090] Also, the cyclic hydrocarbon group in R’ 201 may contain a hetero atom such as a heterocyclic ring or the like.

[0091] R’ 201 Examples of the substituent in the cyclic group of R’ 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, and 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, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred. As the halogen atom as a substituent, a fluorine atom is preferred. As the halogenated alkyl group as a substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and examples thereof include groups in which some or all of the hydrogen atoms of 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.

[0092] The chain alkyl group which may have a substituent: R’ 201 The chain alkyl group in is 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 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.

[0093] The chain alkenyl group which may have a substituent: R’ 201 The chain alkenyl group in is 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 alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group, etc. As the chain-like alkenyl group, a linear alkenyl group is preferred, a vinyl group or a propenyl group is more preferred, and a vinyl group is even more preferred.

[0094] R’ 201 Examples of the substituent in the chain-like alkyl group or alkenyl group of 201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic group in the above R’ 201 and the like.

[0095] 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 include, in addition to those described above, an acid dissociable group.

[0096] R’ 201 As R’ 201 , a cyclic group which may have a substituent is preferred, and a cyclic hydrocarbon group which may have a substituent is more preferred. 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 preferred.

[0097] R 201 ~R 203 、R 206 ~R 207 When R 201 to R 203 , R 206 to R 207 are bonded to each other to form a ring together with the sulfur atom in the formula, a hetero atom such as a sulfur atom, an oxygen atom, or a nitrogen atom, a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(the R Nis an alkyl group having 1 to 5 carbon atoms. It may be bonded via a functional group such as). As the ring formed, it is preferable that one ring containing the sulfur atom in the formula in its ring skeleton is a 3-membered ring or more and 10-membered ring or less including the sulfur atom, and more preferably a 5-membered ring or more and 7-membered ring or less. Specific examples of the formed ring include, for example, thiophene ring, thiazole ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxathiin ring, tetrahydrothiophenium ring, tetrahydrothiopyranium ring and the like.

[0098] R 208 ~R 209 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. When it is an alkyl group, they may be bonded to each other to form a ring.

[0099] 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 a linear or cyclic alkyl group, and an alkyl group having 1 to 30 carbon atoms is preferable. 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 a "-SO2-containing polycyclic group" is preferable.

[0100] Preferable cations represented by formula (ca-1) include cations represented by the following chemical formulas respectively.

[0101] [Chemistry]

[0102] [Chemistry]

[0103] [Chemistry] (In the formula, g1, g2, and g3 represent the number of repetitions, g1 is an integer of 1 or more and 5 or less, g2 is an integer of 0 or more and 20 or less, and g3 is an integer of 0 or more and 20 or less.)

[0104] [Chemistry]

[0105] [Chemistry]

[0106] [Chemistry] (In the formula, R” 201 is a hydrogen atom or a substituent, and examples of the substituent are the same as the groups listed as the substituents that R 201 ~R 207 , and R 210 ~R 212 may have.)

[0107] [Chemistry]

[0108] Specific examples of the preferred cation represented by formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0109] As the preferable cation represented by formula (ca-3), specifically, cations represented by the following formulas (ca-3-1) to (ca-3-6) can be mentioned.

[0110]

Chemical formula

[0111] M3 + As [M3], at least one selected from the group consisting of cations represented by the above formulas (ca-1) to (ca-3) is preferable. Among these, at least one selected from the group consisting of cations represented by the above formulas (ca-1) and (ca-2) is more preferable, the cation represented by the above formula (ca-1) is further preferable, and the cation represented by the following formula (b0-ca) is particularly preferable.

[0112]

Chemical formula

[0113] 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 further preferable. As q1, an integer of 1 or more and 4 or less is preferable, and 2 or 3 is more preferable. Rb1 Preferably, it is bonded to the ortho-position or meta-position of the benzene ring in terms of photodegradation efficiency. Rb 2 and Rb 3 is the R in formula (ca-1) 201 ~R 203 is the same as

[0114] Hereinafter, preferred specific examples of M3 which is the cationic part of the group represented by formula (b0-1) + are shown. Among these, the cationic part represented by (b-M-3) or (b-M-7) is preferred.

[0115]

Chemical formula

[0116] In addition to the ionic group that decomposes upon exposure to generate an acid, the component (B1) may have an aromatic group having a phenolic hydroxyl group.

[0117] Examples of the aromatic group having a phenolic hydroxyl 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, etc. Among them, a benzene ring and a naphthalene ring are preferred, and a 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.).

[0118] R 1 ~R 8As for the number of phenolic hydroxyl groups in the aromatic group, 1, 2, or 3 phenolic hydroxyl groups per aromatic group are preferable, 1 or 2 are more preferable, and 1 is particularly preferable.

[0119] 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, etc. Examples of the alkyl group as the substituent include an alkyl group having 1 to 5 carbon atoms, which 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 preferable.

[0120] Hereinafter, preferred specific examples of the aromatic group having a phenolic hydroxyl group are shown. Among these, the group represented by (b-R2-1) or (b-R2-4) is preferable.

Chemical formula

[0121] As the cage-type silsesquioxane (B1), the cage-type silsesquioxane represented by the following formula (b1) is preferable.

Chemical formula

[0122] R 1 ~R 8 The organic group in

[0123] R 1 ~R 8 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.

[0124] R 1 ~R 8 Among R 1 ~R 8 at least one of the others is preferably an aromatic group having a phenolic hydroxyl group.

[0125] Regarding the ionic group that generates an acid upon exposure and the aromatic group having a phenolic hydroxyl group, it is as described above.

[0126] R 1 ~R 8 The hydrocarbon group having 1 to 10 carbon atoms in

[0127] L 1 ~L 8 may be linear, branched, or cyclic, 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 to 6, more preferably 1 to 5, and still more preferably 1 to 3. 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 still more preferred, and a methyl group is particularly preferred.The number of carbon atoms of the divalent linking group as [the divalent linking group] is preferably 1 or more and 30 or less, more preferably 1 or more and 20 or less, still more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less.

[0128] L 1 ~L 8 The divalent linking group as [the divalent linking group] 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 still more preferably contains an oxygen atom and a silicon atom.

[0129] L 1 ~L 8 As the divalent linking group as [the divalent linking group], a divalent linking group represented by any of the following formulas (a1-L-1) to (a1-L-8) is preferable.

[0130]

Chemical formula

[0131] Z X , Z Y , and Z Z The hydrocarbon group having 1 to 6 carbon atoms as [the hydrocarbon group having 1 to 6 carbon atoms] may be linear, branched, or cyclic, and is preferably linear or branched. Further, the hydrocarbon group as [the hydrocarbon group] of Z X , Z Y , and Z Z may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferable. Z X 、Z Y 、and Z Z The number of carbon atoms of the hydrocarbon group as Z is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less. Z X and Z Y As the hydrocarbon group as Z, 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 preferable.

[0132] In formulas (a1-L-1) to (a1-L-2), Z X and Z Y are each preferably a hydrocarbon group having 1 or more and 6 or less carbon atoms, more preferably both are hydrocarbon groups having 1 or more and 6 or less carbon atoms, still more preferably both are hydrocarbon groups having 1 or more and 3 or less carbon atoms, and particularly preferably both are methyl groups. Z Z is preferably a hydrocarbon group having 1 or more and 6 or less carbon atoms, or a single bond, more preferably a hydrocarbon group having 1 or more and 3 or less carbon atoms, or a single bond, still more preferably a methyl group, or a single bond, and particularly preferably a single bond. In formula (a1-L-3), Z X and Z Y are each preferably a hydrogen atom, and more preferably both are hydrogen atoms. In formula (a1-L-4), Z X and Z Y are each preferably a hydrogen atom, and more preferably both are hydrogen atoms. In formulas (a1-L-5) to (a1-L-6), Z X and Z Y are each preferably a hydrocarbon group having 1 or more and 6 or less carbon atoms, more preferably both are hydrocarbon groups having 1 or more and 6 or less carbon atoms, still more preferably both are hydrocarbon groups having 1 or more and 3 or less carbon atoms, and particularly preferably both are methyl groups. In formulas (a1-L-7) to (a1-L-8), Z X and Z YIt is preferably a hydrocarbon group having 1 to 6 carbon atoms each, more preferably a hydrocarbon group having 1 to 6 carbon atoms each, still more preferably a hydrocarbon group having 1 to 3 carbon atoms each, and particularly preferably a methyl group.

[0133] In formula (a1-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 (a1-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. 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, and still more preferably 0 or 1. In formula (a1-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, and still more preferably 0 or 1. In the above formula (a1-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, and still more preferably 1. In the above formula (a1-L-5), n5 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), n6 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), n7 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), n8 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.

[0134] As the divalent linking group in Y, a divalent linking group containing an oxygen atom is preferred. When Y is a divalent linking group containing an oxygen atom, Y may contain atoms other than the oxygen atom. Examples of 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)-), 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 preferable. Yb 0 Preferably, it is a divalent linking group containing an oxygen atom or a single bond, and more preferably an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), or a single bond.

[0135] Hereinafter, preferred specific examples of L 1 ~L 8 are shown. ** represents a bond to Si. * represents a bond to any one of R 1 ~R 8 Among these, the groups represented by (b-L-2) to (b-L-9) and (b-L-33) are preferable.

[0136]

Chemical formula

[0137]

Chemical formula

[0138] L 1 ~L 8It 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).

[0139] The weight average molecular weight (Mw) (in terms of polystyrene as measured by gel permeation chromatography (GPC)) of the cage-type silsesquioxane (B1) 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 preferable upper limit of this range, it has sufficient solubility in solvents. When it is above the preferable lower limit of this range, the dry etching resistance is enhanced, and the cross-sectional shape of the resist pattern 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.

[0140] The content of the component (B1) is preferably less than 5% by mass, more preferably 2% by mass or less, even 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 film-forming composition. When the content of the component (B1) is within the above preferable range, it is effective for thinning in pattern formation.

[0141] The component (B1) can be produced using a known production method. For example, the cage-type silsesquioxane represented by (b1) 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.

[0142] Raw material (X): A cage-type octasilsesquioxane 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, a vinyl group, and the like.

[0143] 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, 4-ethenyl-2,3,5,6-tetrafluorobenzenesulfonic acid, and the like.

[0144] 〔Crosslinking agent (C)〕 The film-forming composition contains a crosslinking agent (C). Examples of the component (C) 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.

[0145] 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, 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, and the like. Specifically, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, and the like can be mentioned. Among them, hexamethoxymethylmelamine is preferable.

[0146] Examples of the urea-based crosslinking agent include compounds in which the hydrogen atom of an amino group is substituted with a hydroxymethyl group by reacting urea with formaldehyde, compounds in which the hydrogen atom of an amino group is substituted with a lower alkoxymethyl group by reacting urea, formaldehyde, and a lower alcohol, and the like. Specifically, examples thereof include bis(methoxymethyl)urea, bis(ethoxymethyl)urea, bis(propoxymethyl)urea, bis(butoxymethyl)urea, and the like. Among them, bis(methoxymethyl)urea is preferred.

[0147] Examples of the alkyleneurea-based crosslinking agent include compounds represented by the following formula (CA-1).

[0148]

Chemical formula

[0149] Rc 1 and Rc 2 When they are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, which may be linear or branched. Rc 1 and Rc 2 may be the same or different from each other, and it is more preferable that they are the same. Rc 3 and Rc 4 When they are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, which may be linear or branched. Rc 3 and Rc 4 may be the same 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 crosslinking agent, in particular, a compound in which vc is 0 (ethylene urea crosslinking agent) and / or a compound in which vc is 1 (propylene urea crosslinking agent) is preferable.

[0150] 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.

[0151] Specific examples of the alkylene urea crosslinking agent include, for example, ethylene urea crosslinking agents such as mono- and / or dihydroxymethylated 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 crosslinking agents such as mono- and / or dihydroxymethylated 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-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0152] Examples of the glycoluril crosslinking agent include glycoluril derivatives in which the N-position is substituted with 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 further reacting the product with a lower alcohol. Specific examples of glycoluril-based crosslinking agents include, for example, mono-, di-, tri- and / or tetrahydroxymethylated glycoluril; mono-, di-, tri- and / or tetramethoxymethylated glycoluril; mono-, di-, tri- and / or tetraethoxymethylated glycoluril; mono-, di-, tri- and / or tetrapropoxymethylated glycoluril; mono-, di-, tri- and / or tetrabutoxymethylated glycoluril, and the like.

[0153] The phenolic crosslinking agent is not particularly limited as long as it is a compound having a plurality of phenolic nuclear structures in the same molecule, and can be arbitrarily selected and used. By having a plurality of phenolic nuclear structures, the crosslinking reactivity is improved. The number of phenolic 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.

[0154] Specific examples suitable as the glycoluril-based crosslinking agent or the phenolic crosslinking agent are shown below.

[0155]

Chemical formula

[0156] The epoxy-based crosslinking agent is not particularly limited as long as it is a crosslinking agent having an epoxy group, and can be arbitrarily selected and used. Among them, a crosslinking agent having two or more epoxy groups is preferable. By having two or more epoxy groups, the crosslinking reactivity is improved. The number of epoxy groups is preferably 2 or more, more preferably 2 or more and 4 or less, and most preferably 2. Specific examples suitable as the epoxy-based crosslinking agent are shown below.

[0157]

Chemical formula

[0158] Among them, as the component (C), a compound having an alkylol group such as a methylol group or an alkoxyalkyl group such as a methoxymethyl group is preferable, a crosslinking agent selected from the group consisting of glycoluril-based crosslinking agents and phenol-based crosslinking agents is more preferable, and a glycoluril-based crosslinking agent is even more preferable.

[0159] (Silicon-containing crosslinking agent (C1)) The film-forming composition may contain, as the component (C), a silicon-containing crosslinking agent (C1) having a methylol group and / or an alkoxymethyl group.

[0160] The content ratio of the silicon atom in the component (C1) is preferably 5% or more and 45% or less, more preferably 8% or more and 35% or less, and even more preferably 10% or more and 25% or less with respect to the total amount of all atoms constituting the component (C1). The method for calculating the content ratio of the silicon atom in the component (C1) is the same as the method for calculating the content ratio of the silicon atom in the component (A).

[0161] The methylol group and / or alkoxymethyl group possessed by the component (C1) is preferably bonded to an aromatic group or a nitrogen atom. Thereby, the action as a crosslinking agent is likely to be exhibited.

[0162] The component (C1) may have a phenolic hydroxyl group in addition to the methylol group and / or alkoxymethyl group.

[0163] As the silicon-containing crosslinking agent (C1), siloxane is preferable, and cage-type silsesquioxane and cyclic siloxane are more preferable.

[0164] 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).

[0165] (Cage-type silsesquioxane (C1-1)) [Chemistry] (In formula (c1-1), R 1c ~R 8c 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 1c ~R 8c 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 1c ~L 8c are each independently a divalent linking group represented by any one of the following formulas (c1-L-1) to (c1-L-7).) [Chemistry] (In formulas (c1-L-1) to (c1-L-7), Z Xc and Z Yc are each independently a hydrocarbon group having 1 to 6 carbon atoms, or a hydrogen atom. n1c to n7c are each independently an integer of 0 or more and 10 or less. * represents a bond to Si. ** represents a bond to any one of R 1c ~R 8c .)

[0166] R 1c ~R 8c 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.

[0167] R 1c ~R 8c Among them, at least one of the others may be an aromatic group having a phenolic hydroxyl group.

[0168] R 1c ~R 8c Among 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 5 or more, particularly preferably 7 or more, and may be 8. Also, 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 1c ~R 8c 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 5 or more, particularly preferably 7 or more, and may be 8. Also, 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 1c ~R 8c Among them, the total number of aromatic groups having a hydroxymethyl group or an alkoxymethyl group and nitrogen-containing groups having a hydroxymethyl 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 1c ~R 8c 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.

[0169] R 1c ~R 8c The aromatic group having a hydroxymethyl 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 hydroxymethyl group or an alkoxymethyl group. R 1c ~R 8cExamples of the aromatic group in [description] 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 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, a phenyl group, a 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.).

[0170] R 1c ~R 8c The number of methylol groups and alkoxymethyl groups in the aromatic group in [description] is preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1 per aromatic group.

[0171] R 1c ~R 8c In [description], 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. The halogen atom as the substituent is preferably a fluorine atom.

[0172] Preferred specific examples of the aromatic group having a methylol group or an alkoxymethyl group are shown below. Among these, the group represented by (c1-R1-1) is preferable.

[0173]

Chem.

[0174] R 1c ~R 8c As the nitrogen atom-containing group having a methylol group or an alkoxymethyl group in R~R, a nitrogen atom-containing heterocyclic group in which the N-position is substituted with a methylol group or an alkoxymethyl group is preferable.

[0175] R 1c ~R 8c The number of carbon atoms of the nitrogen atom-containing heterocyclic group in R~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.

[0176] Preferred specific examples of the nitrogen atom-containing group having a methylol group or an alkoxymethyl group are shown below.

[0177]

Chem.

[0178] R 1c ~R 8c As the aromatic group having a phenolic hydroxyl group in R~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.).

[0179] R 1c ~R 8c The number of phenolic hydroxyl groups in the aromatic group as R~R is preferably 1, 2, or 3 per aromatic group, more preferably 1 or 2, and particularly preferably 1.

[0180] In the aromatic group, the hydrogen atom bonded to the aromatic ring 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. Examples of the alkyl group as the substituent include an alkyl group having 1 to 5 carbon atoms, which 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. The halogen atom as the substituent is preferably a fluorine atom.

[0181] 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

[0182] R 1c ~R 8cThe 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 still 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 still more preferred.

[0183] Z Xc and Z Yc The hydrocarbon group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and is preferably linear or branched. Also, Z Xc and Z Yc The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferred. Z Xc and Z Yc The number of carbon atoms of the hydrocarbon group is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less. Z Xc and Z Yc As the hydrocarbon group, 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.

[0184] In formula (c1-L-1), formula (c1-L-2), formula (c1-L-5), and formula (c1-L-6), Z Xc and Z Yc are each preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably both are hydrocarbon groups having 1 to 6 carbon atoms, still 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 Xc and Z YcPreferably, each is a hydrogen atom, and more preferably, all are hydrogen atoms.

[0185] In formula (c1-L-1), n1c 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), n2c 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), n3c 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), n4c 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), n5c is preferably an integer of 0 or more and 8 or less. In formula (c1-L-6), n6c is preferably an integer of 0 or more and 6 or less. In formula (c1-L-7), n7c is preferably an integer of 0 or more and 8 or less.

[0186] Hereinafter, preferred specific examples of L 1c ~L 8c are shown. * represents a bond to Si. ** represents a bond to any one of R 1c ~R 8c . Among these, the group represented by (c1-L1-1) or (c1-L1-3) is preferred.

[0187]

Chemical formula

[0188]

Chemical formula

[0189] (Cyclic siloxane (C1-2))

Chemical formula

[0190] nc2 is preferably an integer of 3 or more and 5 or less, more preferably 4.

[0191] 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.

[0192] R 9 At least one of the others may be an aromatic group having a phenolic hydroxyl group.

[0193] R 9Among 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 4 or more. Further, 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 9 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 4 or more. Further, 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 9 Among them, the total number of aromatic groups having a methylol group or an alkoxymethyl group and nitrogen atom-containing groups having a methylol 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.

[0194] R 9 The aromatic group having a methylol group or an alkoxymethyl group, the nitrogen atom-containing group having a methylol group or an alkoxymethyl group, the aromatic group having a phenolic hydroxyl group, and the hydrocarbon group having 1 to 10 carbon atoms in are the same as these groups in R 1 ~R 8 and are the same as these groups in.

[0195] 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.

[0196] The preferred specific examples of L are shown below. * represents a bond to Si. ** represents a bond to R. 9 Among these, the group represented by (c2-L1-1) or (c2-L1-2) is preferred. 9 Among these, the group represented by (c2-L1-1) or (c2-L1-2) is preferred.

[0197] [Chemical formula]

[0198] Z Zc 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.

[0199] The weight average molecular weight (Mw) of the component (C1) (based on polystyrene conversion 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 component (C1) is below the preferred upper limit of this range, there is sufficient solubility in the 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 component (C1) 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.

[0200] 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.

[0201] 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.

[0202] 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.

[0203] The component (C) may be used alone or in combination of two or more. In the first film-forming composition, the content of the component (C) 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 (C) is equal to or higher than the lower limit value of the above preferable range, crosslinking formation sufficiently proceeds, dissolution contrast is easily obtained, and resolution performance and lithography characteristics are more easily improved. Also, a good resist pattern with less swelling is easily obtained. When the content is equal to or lower than the upper limit value of the above preferable range, the storage stability of the film-forming composition is good, and deterioration of sensitivity with time is easily suppressed.

[0204] [Base component (D)] The film-forming composition contains a base 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 control properties, 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 preferable because it is easy to enhance the characteristics of high sensitivity, reduction of roughness, and suppression of the occurrence of coating defects.

[0205] ·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 control properties, 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) to (d0-2) do not act as a quencher because they decompose in the exposed portion of the resist film and lose acid diffusion control properties (basicity), and act as a quencher in the unexposed portion of the resist film.

[0206] [Chemical formula] (In formula (d0-1), R d10 is an organic group having 1 to 40 carbon atoms. M1 + is an onium cation. In formula (d0-2), R d20 is an organic group having 1 to 40 carbon atoms. M2 + is an onium cation.)

[0207] ··Regarding component (d0-1) R d10Examples of the organic group having 1 to 40 carbon atoms include a hydrocarbon group which may have a substituent, a divalent linking group containing an oxygen atom, or a combination thereof. R d10 Examples of the organic group in include a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent, and the monovalent group obtained by changing the divalent group exemplified in the description of R in the above formula (b0-1). b101 is mentioned. Among them, R d10 is preferably a linear alkyl group having an iodine atom or an aliphatic cyclic group having an iodine atom. The number of carbon atoms of the linear alkyl group is preferably 1 or more and 10 or less, more preferably 3 or more and 10 or less. Examples of the aliphatic cyclic group include a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have a substituent); and a group obtained by removing one or more hydrogen atoms from camphor or the like is more preferable. However, it is assumed that a fluorine atom is not bonded to the carbon atom adjacent to the S atom in R d10 (not fluorine-substituted). Thereby, the anion part of the sulfonate represented by the general formula (d0-1) becomes an appropriate weak acid anion, and the quenching ability is improved.

[0208] R d10 's hydrocarbon group may have a substituent, and examples of the substituent include the same groups as those which may be possessed by the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, linear alkyl group, linear alkenyl group) in R in the above formula (b0-1). b101 are mentioned.

[0209] Specific preferable examples of the anion part of the sulfonate represented by the formula (d0-1) are shown below.

[0210]

Chemical formula

[0211] M1 + is preferably a sulfonium cation or an iodonium cation. M1 + As M1, cations similar to the cations respectively represented by the above-described 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. (Component (d0-1) may be used alone or in combination of two or more.

[0212] ··Regarding component (d0-2) In the above formula (d0-2), R d20 As the organic group having 1 to 40 carbon atoms in R, 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, a carboxylate represented by the following formula (d0-2d) is preferable.

[0213]

Chemical formula

[0214] R d201 is 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, and is a group obtained by changing the divalent group exemplified in the description of R b101 in the above formula (b0-1) to monovalent. Among them, R d201Examples thereof include a cyclic group having a hydroxyl group, a cyclic group having an iodine atom, or a cyclic group having a bromine atom, preferably an aromatic hydrocarbon group having a hydroxyl group, more preferably a phenyl group having a hydroxyl group or a naphthyl group having a hydroxyl group.

[0215] In the above formula (d0-2d), Yd 0 As the divalent linking group in, a divalent linking group containing an oxygen atom is preferably mentioned. Yd 0 When Yd is a divalent linking group containing an oxygen atom, the Yd 0 may contain atoms other than an oxygen atom. Examples of the atoms other than an 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)-), a carbonate bond (-O-C(=O)-O-); 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, and the like. A sulfonyl group (-SO2-) may be further linked to this combination. Examples of the arylene group include a phenylene group, a naphthylene group and the like. The 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.

[0216] Preferred specific examples of the anionic part of the carboxylate represented by the formula (d0-2d) are shown below.

[0217]

Chemical formula

[0218] [Chemical formula]

[0219] [Chemical formula]

[0220] M2 + is an onium cation, and among these, it is preferably a sulfonium cation or an iodonium cation. M2 + As [M2], cations similar to the cations respectively represented by the above formulas (ca-1) to (ca-3) are preferably exemplified. 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.

[0221] The component (D0) may use only any one of the above components (d0-1) to (d0-2), or may use a combination of two or more. 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 (B1). 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.

[0222] The component (D0) preferably contains the above component (d0-2). Among the entire component (D0), the content of the component (d0-2) is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and the component (D0) may consist only of the component (d0-2).

[0223] ·Regarding the nitrogen-containing organic compound ((D2) component) As the (D) component, it may contain a nitrogen-containing organic compound component ((D2) component) that does not correspond to the above (D0) component. 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 can 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 aliphatic amines include 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 (alkylamine or alkyl alcohol amine) or cyclic amines. Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, 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, tri-n-dodecylamine; alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine. Among these, trialkylamines having 6 to 30 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.

[0224] 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, piperazine, etc. 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, 1,4-diazabicyclo[2.2.2]octane, etc.

[0225] 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.

[0226] Also, an aromatic amine may be used as the component (D2). Examples of the aromatic amine include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert-butylpyridine, 2,6-di-tert-butylpyridine, etc.

[0227] The component (D2) may be used alone or in combination of two or more. When the film-forming composition contains the component (D2), the content of the component (D2) in the film-forming composition 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 range as described above, the resist pattern shape, the stability over time of standing, etc. are improved.

[0228] [Other Components] In addition to the components (A), (B1), (C), and (D) described above, the film-forming composition may further contain other components. As the other components, known components that have been conventionally incorporated into film-forming compositions based on silicon-containing compounds as base components can be used. Examples of such other components include other acid generators (B3), organic carboxylic acids, etc., fluorine additive components, organic solvent components, and the like.

[0229] (Other Acid Generator (B3)) The film-forming composition may contain an acid generator (B3) other than the component (B1) as the acid generator (B). The component (B3) is not particularly limited, and acid generators that have been proposed as acid generators for chemically amplified resist compositions can be used. Examples of 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.

[0230] As a preferred component (B3), for example, in the group represented by the above formula (b0), a compound in which R b10 is changed to a monovalent group bonded only to a sulfur atom, or in the group represented by the above formula (b0-1), a compound in which Rb 101 is changed to a monovalent group bonded only to Yb 0 and the like can be mentioned.

[0231] (At least one compound (E) selected from the group consisting of an organic carboxylic acid, an oxo acid of phosphorus, and a derivative thereof) In the film-forming composition, for the purpose of preventing sensitivity deterioration and improving resist pattern shape, stability over time of standing, etc., as an optional component, at least one compound (E) selected from the group consisting of an organic carboxylic acid, an oxo acid of phosphorus, and a derivative thereof (hereinafter referred to as "(E) component") can be contained. Specific 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 preferable. Examples of the oxo acid of phosphorus include phosphoric acid, phosphonic acid, phosphinic acid, etc. Among them, phosphonic acid is particularly preferable.

[0232] (E) component may be used alone or in combination of two or more. When the first film-forming composition contains the (E) component, the content of the (E) component 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 with respect to 100 parts by mass of the (A) component. By setting it within the above range, the stability over time of the film-forming composition is improved.

[0233] ≪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 the (A) component, lithography characteristics can be improved. As the (F) component, for example, 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. (F) More specifically as the component, a polymer having a structural unit (f1) represented by the following formula (f1-1) can be mentioned. As this polymer, a polymer (homopolymer) consisting only of the structural unit (f1) represented by the following formula (f1-1); 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; preferably a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a101), and more preferably a copolymer of the structural unit (f1) and the structural unit (a101). 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.

[0234]

Chemical formula

[0235] In the 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 the formula (f1-1), as the halogen atoms of Rf 102 and Rf 103 , a fluorine atom is preferable. Rf 102 and Rf 103As the alkyl group having 1 to 5 carbon atoms, a methyl group or an ethyl group is preferable. Rf 102 and Rf 103 As the halogenated alkyl group having 1 to 5 carbon atoms, specifically, a group in which part or all of the hydrogen atoms of the 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 103 are preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom. 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.

[0236] In formula (f1-1), Rf 101 is an organic group containing a fluorine atom, and 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 having 1 to 15 carbon atoms, and particularly preferably having 1 to 10 carbon atoms. Further, in the hydrocarbon group containing a fluorine atom, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more are fluorinated, and particularly preferably 60% or more are fluorinated 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.

[0237] (F) component has a weight average molecular weight (Mw) (in terms of polystyrene conversion standard by gel permeation chromatography) of 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 value of this range, there is sufficient solubility in the resist solvent for use as a resist, and when it is above the lower limit value of this range, the water repellency of the resist film is good. (F) component has a dispersity (Mw / Mn) of 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.

[0238] (F) component may be used alone or in combination of two or more. When the first film-forming composition contains (F) component, the content of (F) component is preferably 0.5 part 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, based on 100 parts by mass of (A) component.

[0239] (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 "(S) component"). In the film-forming composition, (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 preferred.

[0240] The amount of (S) component used 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 on 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.

[0241] <Second film-forming composition> As described above, the second film-forming composition contains a cage-type silsesquioxane (B2), a crosslinking agent (C), and a base component (D). The crosslinking agent (C), the base component (D), and other components are the same as those in the first film-forming composition.

[0242] Hereinafter, the cage-type silsesquioxane (B2) in the second film-forming composition will be described.

[0243] 〔Cage-type silsesquioxane (B2)〕 The second film-forming composition contains a cage-type silsesquioxane (B2) as an acid generator (B). The cage-type silsesquioxane (B2) has an ionic group that decomposes upon exposure to generate an acid and a phenolic hydroxyl group. The cage-type silsesquioxane (B1) preferably has a perfect cage structure.

[0244] Since the cage-type silsesquioxane (B2) has a phenolic hydroxyl group in addition to the ionic group that decomposes upon exposure to generate an acid, it can exhibit the same action as the silicon-containing polymer (A).

[0245] The cage-type silsesquioxane (B2) is the same as the cage-type silsesquioxane (B1) except that it has a phenolic hydroxyl group in addition to the ionic group that decomposes upon exposure to generate an acid.

[0246] As the cage-type silsesquioxane (B2), a cage-type silsesquioxane represented by the following formula (b2) is preferable.

Chemical formula

[0247] The content of the cage-type silsesquioxane (B2) 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 cage-type silsesquioxane (B2) is within the above preferable range, it is effective for thinning in pattern formation.)

[0248] In the second film-forming composition, the content of the component (C) 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 (B2).) When the content of the component (C) is at least the lower limit value of the above preferable range, crosslink formation proceeds sufficiently and dissolution contrast is easily obtained, and resolution performance and lithography characteristics are more easily improved. Also, a good resist pattern with less swelling is easily obtained. When the content is at most the upper limit value of the above preferable range, the storage stability of the film-forming composition is good, and deterioration of sensitivity with time is easily suppressed.)

[0249] When the second film-forming composition contains the component (D0), the content of the component (D0) is appropriately set according to the molar ratio with the component (B2). For example, with respect to 100 parts by mass of the component (B2), 5 parts by mass or more and 60 parts by mass or less is preferable, 10 parts by mass or more and 50 parts by mass or less is more preferable, and 20 parts by mass or more and 45 parts by mass or less is still more preferable.)

[0250] When the second film-forming composition contains the component (D2), the content of the component (D2) is usually 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 (B2). By setting the content within the above range, the resist pattern shape, the stability over time of the standing, etc. are improved.

[0251] When the second film-forming composition contains the component (E), the content of the component (E) is preferably 0.1 part 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 component (B2). By setting the content within the above range, the stability over time of the film-forming composition is improved.

[0252] When the second film-forming composition contains the component (F), the content of the component (F) is preferably 0.5 part 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 component (B2).

[0253] <Use of the film-forming composition> The film-forming composition is suitable for applications where a cured film is used. For example, in the etching for forming 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.

[0254] The film-forming composition is particularly useful for an alkali development process that uses an alkali developer for the development process during resist pattern formation, and among them, it is suitable as a "negative resist composition for an alkali development process".

[0255] ≪Method for producing a patterned cured film≫ The method for producing a patterned cured film includes forming a coating film composed of the film-forming composition on a support (hereinafter, also referred to as "coating film forming step"), selectively exposing the above coating film in a position-selective manner (hereinafter, also referred to as "exposure step"), and developing the coating film after the exposure to form a patterned cured film (hereinafter, also referred to as "development step").

[0256] <Coating Film Formation Process> First, the above-described composition for film formation is applied onto a support using a spinner or the like, and 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).

[0257] <Exposure Process> Next, selective exposure is performed on the resist film using an exposure apparatus such as an electron beam lithography apparatus or an EUV (extreme ultraviolet) exposure apparatus through a mask (mask pattern) on which a predetermined pattern is formed, or by direct irradiation of an electron beam without passing through a mask pattern, such as drawing. After the above exposure, 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.

[0258] <Development Process> Next, the resist film after the above exposure is developed. In the case of an alkali development process, an alkali developer is used, and in the case of a solvent development process, a developer containing an organic solvent (organic-based developer) is used.

[0259] After the development process, preferably a rinsing process is performed. In the case of an alkali development process, water rinsing using pure water is preferred, and in the case of a solvent development process, it is preferable to use a rinsing solution containing an organic solvent. In the case of a 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. Drying is performed after the development process or rinsing process. Also, in some cases, baking treatment (post-bake) may be performed after the above development process.

[0260] The support is not particularly limited, and conventionally known supports can be used. For example, substrates for electronic components, supports with a predetermined wiring pattern formed thereon, etc. can be mentioned. More specifically, silicon wafers, metal substrates such as copper, chromium, iron, aluminum, etc., glass substrates, etc. can be mentioned. As the material for 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 substrate as described above may be used. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). Examples of the organic film include an organic antireflection film (organic BARC) and organic films such as the lower 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 the 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 with one or more intermediate layers (such as a metal thin film) provided between the upper resist film and the lower organic film (three-layer resist method).

[0261] 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 this 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 resist film.

[0262] 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 lithography. Liquid immersion lithography 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 greater than that of air in advance, and exposure (immersion exposure) is performed in this state. As the liquid immersion medium, a solvent having a refractive index greater 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, and hydrocarbon-based solvents. 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 preferable, and liquids having a boiling point of 80°C or higher and 160°C or lower are more preferable. 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. As the fluorine-based inert liquid, in particular, perfluoroalkyl compounds in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms are preferable. 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). From the viewpoints of cost, safety, environmental issues, versatility, etc., water is preferably used as the liquid immersion medium.

[0263] As the alkaline developer used for development in the alkaline development process, for example, an aqueous solution of tetramethylammonium hydroxide (TMAH) of 0.1 mass% or more and 10 mass% or less can be mentioned.

[0264] As the organic solvent contained in the organic developer used for development in the solvent development process, any organic solvent that can dissolve the component (A) (component (A) before exposure) may be used, and it can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents, and hydrocarbon 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 that may be halogenated and is a hydrocarbon solvent having no substituent other than a halogen atom. As the halogen atom, a fluorine atom is preferred. As the organic solvent contained in the organic developer, among the above, polar solvents are preferred, and ketone solvents, ester solvents, nitrile solvents, etc. are preferred.

[0265] Examples of the 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), and the like. Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0266] 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.

[0267] Examples of the nitrile solvents include acetonitrile, propionitrile, valeronitrile, butyronitrile, and the like.

[0268] Known additives can be incorporated into the organic developer as needed. Examples of the additives include surfactants. The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.

[0269] 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 surface of the support 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 surface of the support (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.

[0270] Examples of the organic solvent contained in the rinse liquid used for the rinse treatment after the development process in the solvent development process include, among the organic solvents mentioned as the organic solvents used for the above organic developer, an organic solvent that is difficult to dissolve the resist pattern, which 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. They may also be used in mixture with organic solvents other than those described above and water.

[0271] The rinse treatment (cleaning 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 surface of the support (spray method), and the like.

[0272] 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 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).

[0273] 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 solution, composition for forming an antireflection film, composition for forming a top coat, 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 the 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 the 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).

[0274] ≪Cage-type silsesquioxane≫ The cage-type silsesquioxane has an ionic group that decomposes upon exposure to generate an acid.

[0275] The preferred embodiment of the cage-type silsesquioxane is the same as the cage-type silsesquioxane (B1) contained in the first film-forming composition.

Examples

[0276] Based on the examples, the present invention will be described in more detail, but the present invention is not limited by these examples.

[0277] ≪Production of cage-type silsesquioxane≫ By the following Synthesis Examples (1) to (7), cage-type silsesquioxanes (B-1) to (B-7) were produced, respectively.

[0278] <Synthesis Example (1): Production of cage-type silsesquioxane (B-1)> 8.0 g of octakis(dimethylsilyloxy)octasilsesquioxane, 12.1 g of 1-(1-ethoxyethoxy)-4-vinylbenzene, 3.0 g of benzyltrimethylammonium 1,1-difluoro-2-(methacryloyloxy)ethanesulfonate, platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content 2%) 0.08 g, and 20 g of tetrahydrofuran were mixed, and the mixture was stirred at 30 °C for 2 hours and 30 minutes. 0.53 g of activated carbon was added to the mixture, and the mixture was stirred at room temperature for 30 minutes, and then the filtrate was collected by filtration using celite. The filtrate was concentrated using a rotary evaporator. 80 g of tetrahydrofuran was added to the concentrated solution, and the mixture was cooled in an ice bath and stirred, and 100 g of 2M hydrochloric acid was added dropwise over 5 minutes, and then the mixture was stirred at room temperature for 2 hours. The solution was extracted 4 times with 40 g of methyl isobutyl ketone and then washed 3 times with 50 g of saturated brine. 32 g of a 6% aqueous solution of bis(3,5-difluorophenyl)phenylsulfonium hydrochloride, 2 g of isopropyl alcohol, and 18 g of pure water were added to the obtained organic layer, and the mixture was stirred for 5 minutes and then allowed to stand to remove the aqueous layer, and this was repeated 5 times. The obtained solution was concentrated to dryness using a rotary evaporator, and then 50 g of propylene glycol monomethyl ether was added, and the process of concentrating to dryness using a rotary evaporator was repeated three times. Thereafter, propylene glycol monomethyl ether was added so that the concentration became 10%, and the concentrate was dissolved to obtain a 10% propylene glycol monomethyl ether solution of cage-type silsesquioxane (B-1) having an ionic group that decomposes upon exposure to generate an acid and a phenolic hydroxyl group.

[0279] [Chemical formula]

[0280] The obtained cage-type silsesquioxane (B-1) is a mixture of cage-type silsesquioxane in which a group represented by the formula (B-1-1) (a group containing an ionic group that decomposes upon exposure to generate an acid), a group represented by the formula (B-1-2) (a group containing an aromatic group having a phenolic hydroxyl group), and a group represented by the formula (B-1-3) (a group containing an aromatic group having a phenolic hydroxyl group) are bonded to R in the cage structure. The introduction ratio of these groups to R in the cage structure was (B-1-1):(B-1-2):(B-1-3) = 12.5:55.7:31.8 (molar ratio). The introduction ratio of the groups was calculated from the results of NMR (the same applies hereinafter).

[0281] Regarding the obtained cage-type silsesquioxane (B-1), the weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 2,200, and the molecular weight dispersity (Mw / Mn) was 1.05. Also, the content ratio of silicon atoms was 18.5%.

[0282] 1 H-NMR, 13 C-NMR, 19 F-NMR, and 29 It was confirmed to have the following structure by analysis of Si-NMR. 1 [H-NMR (600 MHz, DMSO)] H a ​: 44.29H, -0.18 - 0.09 ppm, H b : 3H, 3.02 - 3.45 ppm, H c : 3H, 2.06 ppm, H d : 2H, 4.57 ppm, H e : 28H, 0.78 - 1.22, 2.45 ppm, H f : 29.55H, 6.50 - 6.87 ppm, H g : 7.00H, 8.90, 8.95 ppm, H h : 4.68H, 7.67 - 7.92 ppm 13 C - NMR(150 MHz, DMSO)] C a : 16.37C, -0.85, -0.90, 0 ppm, C b : 1.97C, 20.1 - 24.4 ppm, C c : 1.13C, 19.9 ppm, C d : 0.93C, 170 ppm, C e : 0.96C, 69.2 ppm, C f : 0.88C, 120 ppm, C g : 13.66C, 16.7, 28.4 ppm, C h : 3.67C, 134 ppm, C i : 7.08C, 117 ppm, C j : 4.61C, 120 ppm, C k : 3.50C, 158 ppm, C l : 3.45C, 132 ppm, C m : 6.96C, 117 ppm, C n : 6.89C, 118 ppm, C o : 2.39C, 155 ppm, C p : 2.12C, 139 ppm, C q : 4.23C, 166 ppm, C r : 4.11C, 127 ppm, C s : 2.03C, 123 ppm, C t : 1.09C, 124 ppm, C u : 2.22C, 125 ppm, C v : 1.98C, 163 ppm, C w : 0.97C, 137 ppm 19 ​​F-NMR (564 MHz, DMSO) F a : 2.17 F, -115 ppm, F b : 4.00 F, -104 ppm 29 Si-NMR (120 MHz, DMSO) S a : 1.08 Si, 12.5 ppm, S b : 0.67 Si, 10.8 ppm, S c : 1.70 Si, -110 ppm

[0283]

Chem.

Chem.

[0284] <Synthesis Example (2): Production of Cage-Type Silsesquioxane (B-2)> Cage-type silsesquioxane (B-2) was synthesized in the same manner as in Synthesis Example (1), except that 12.1 g of 1-(1-ethoxyethoxy)-4-vinylbenzene was changed to 8.4 g of 4-allylphenol.

[0285] The obtained cage-type silsesquioxane (B-2) is a mixture of a cage-type silsesquioxane in which a group represented by the formula (B-2-1) (a group containing an ionic group that decomposes upon exposure to generate an acid), a group represented by the formula (B-2-2) (a group containing an aromatic group having a phenolic hydroxyl group), and a group represented by the formula (B-2-3) (a group containing an aromatic group having a phenolic hydroxyl group) are bonded to R in the cage structure. The introduction ratio of these groups to R in the cage structure was (B-2-1):(B-2-2):(B-2-3) = 12.5:54.7:32.8 (molar ratio).

[0286] For the obtained cage-type silsesquioxane (B-2), the weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 2,300, and the molecular weight dispersity (Mw / Mn) was 1.07. Also, the content ratio of silicon atoms was 17.8%.​

[0287] 1 H-NMR, 13 C-NMR, 19 F-NMR, and 29 It was confirmed to have the following structure by the analysis of Si-NMR.

[0288]

Chemical formula

[0289] <Synthesis Example (3): Production of Cage-Type Silsesquioxane (B-3)> Cage-type silsesquioxane (B-3) was synthesized in the same manner as in Synthesis Example (1), except that 12.1 g of 1-(1-ethoxyethoxy)-4-vinylbenzene was changed to 8.7 g of 3,4-dihydroxystyrene.

[0290] The obtained cage-type silsesquioxane (B-3) is a mixture of cage-type silsesquioxanes in which groups represented by formula (B-3-1) (groups containing an ionic group that decomposes upon exposure to generate an acid), groups represented by formula (B-3-2) (groups containing an aromatic group having a phenolic hydroxyl group), and groups represented by formula (B-3-3) (groups containing an aromatic group having a phenolic hydroxyl group) are bonded to R in the cage structure. The introduction ratio of these groups to R in the cage structure was (B-3-1):(B-3-2):(B-3-3) = 14.5:57.7:27.8 (molar ratio).

[0291] Regarding the obtained cage-type silsesquioxane (B-3), the weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 2,300, and the molecular weight dispersity (Mw / Mn) was 1.08. Also, the content ratio of silicon atoms was 17.3%.

[0292] 1 H-NMR, 13 C-NMR, 19 F-NMR, and 29 It was confirmed to have the following structure by the analysis of Si-NMR.

[0293]

Chem.

[0294] <Synthesis Example (4): Production of Cage-Type Silsesquioxane (B-4)> Cage-type silsesquioxane (B-4) was synthesized in the same manner as in Synthesis Example (1), except that 32 g of a 6% aqueous solution of bis(3,5-difluorophenyl)phenylsulfonium hydrochloride was changed to 32 g of a 6% aqueous solution of diphenyliodonium hydrochloride.

[0295] The obtained cage-type silsesquioxane (B-4) is a mixture of a cage-type silsesquioxane in which a group represented by the formula (B-4-1) (a group containing an ionic group that decomposes upon exposure to generate an acid), a group represented by the formula (B-4-2) (a group containing an aromatic group having a phenolic hydroxyl group), and a group represented by the formula (B-4-3) (a group containing an aromatic group having a phenolic hydroxyl group) are bonded to R in the cage structure. The introduction ratio of these groups to R in the cage structure was (B-4-1):(B-4-2):(B-4-3) = 11.5:53.7:34.8 (molar ratio).

[0296] For the obtained cage-type silsesquioxane (B-4), the weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 2,400, and the molecular weight dispersity (Mw / Mn) was 1.06. Also, the content ratio of silicon atoms was 19.0%.

[0297] 1 1H-NMR, 13 13C-NMR, 19 19F-NMR, and 29 1H-NMR, 13C-NMR, 19F-NMR, and 29Si-NMR analyses confirmed that it had the following structure.

[0298]

Chem.

[0299] <Synthesis Example (5): Production of Cage-Type Silsesquioxane (B-5)> Cage-type silsesquioxane (B-5) was synthesized in the same manner as in Synthesis Example (1), except that 3.0 g of benzyltrimethylammonium 1,1-difluoro-2-(methacryloyloxy)ethanesulfonate was changed to 2.0 g of 4-ethenyl-2,3,5,6-tetrafluorobenzenesulfonic acid.

[0300] The obtained cage-type silsesquioxane (B-5) is a mixture of cage-type silsesquioxanes in which a group represented by the formula (B-5-1) (a group containing an ionic group that decomposes upon exposure to generate an acid), a group represented by the formula (B-5-2) (a group containing an ionic group that decomposes upon exposure to generate an acid), a group represented by the formula (B-5-3) (a group containing an aromatic group having a phenolic hydroxyl group), and a group represented by the formula (B-5-4) (a group containing an aromatic group having a phenolic hydroxyl group) are bonded to R in the cage structure. The introduction ratios of these groups to R in the cage structure were (B-5-1):(B-5-2):(B-5-3):(B-5-4) = 7.5:5.0:51.1:36.4 (molar ratio).

[0301] For the obtained cage-type silsesquioxane (B-5), the weight-average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 2,500, and the molecular weight dispersity (Mw / Mn) was 1.0. Also, the silicon atom content ratio was 18.0%.

[0302] 1 H-NMR, 13 C-NMR, 19 F-NMR, and 29 It was confirmed to have the following structure by analysis of Si-NMR.

[0303]

Chemical formula

[0304] <Synthesis Example (6): Production of Cage-Type Silsesquioxane (B-6)> 32.0 g of 4-hydroxybenzenethiol, 20.0 g of toluene, and 3.7 g of trimethylsilyl chloride were added and made uniform, and then 3.2 g of pyridine was added dropwise over 15 minutes while stirring. Thereafter, the mixture was stirred for 90 minutes, 5.0 g of heptakis(vinyldimethylsiloxy)mono(dimethylsiloxy)octasilsequioxane and 0.4 g of azobisisobutyronitrile were added, and the mixture was stirred at 70 °C for 2 hours. After cooling to room temperature, toluene and hot water were added to the solution, and the mixture was stirred and then allowed to stand to remove the aqueous layer, and further washed three times with 60 g of hot water. The obtained organic layer was concentrated using a rotary evaporator. After dissolving 20 g of tetrahydrofuran in the concentrated solution, 3.0 g of benzyltrimethylammonium 1,1-difluoro-2-(methacryloyloxy)ethanesulfonate and 0.08 g of a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content 2%) were added, and the mixture was stirred at 30 °C for 2 hours and 30 minutes. Thereafter, the same operations as those after the addition of activated carbon in Synthesis Example (1) were carried out to obtain a 10% propylene glycol monomethyl ether solution of a cage-type silsesquioxane (B-6) having an ionic group that decomposes upon exposure to generate an acid and a phenolic hydroxyl group.

[0305]

Chemical formula

[0306] The obtained cage-type silsesquioxane (B-6) is a mixture of a cage-type silsesquioxane in which a group represented by the formula (B-6-1) (a group containing an ionic group that decomposes upon exposure to generate an acid) and a group represented by the formula (B-6-2) (a group containing an aromatic group having a phenolic hydroxyl group) are bonded to R in the cage structure. The introduction ratio of these groups to R in the cage structure was (B-6-1):(B-6-2)=12.5:87.5 (molar ratio).

[0307] For the obtained cage-type silsesquioxane (B-6), the weight-average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 2,200, and the molecular weight dispersity (Mw / Mn) was 1.0. Also, the content ratio of silicon atoms was 17.0%.

[0308] 1 H-NMR, 13 C-NMR, 19 F-NMR, and 29 It was confirmed to have the above structure by analysis of Si-NMR.

[0309] <Synthesis Example (7): Production of Cage-Type Silsesquioxane (B-7)> Cage-type silsesquioxane (B-7) was synthesized in the same manner as in Synthesis Example (1), except that 12.1 g of 1-(1-ethoxyethoxy)-4-vinylbenzene was changed to 10.9 g and 3.0 g of benzyltrimethylammonium 1,1-difluoro-2-(methacryloyloxy)ethanesulfonate was changed to 6.0 g.

[0310] The obtained cage-type silsesquioxane (B-7) is a mixture of a cage-type silsesquioxane in which a group represented by the formula (B-7-1) (a group containing an ionic group that decomposes upon exposure to generate an acid), a group represented by the formula (B-7-2) (a group containing an aromatic group having a phenolic hydroxyl group), and a group represented by the formula (B-7-3) (a group containing an aromatic group having a phenolic hydroxyl group) are bonded to R in the cage structure. The introduction ratio of these groups to R in the cage structure was (B-7-1):(B-7-2):(B-7-3) = 26.3:48.2:25.5 (molar ratio).

[0311] For the obtained cage-type silsesquioxane (B-7), the weight-average molecular weight (Mw) in terms of standard polystyrene measured by GPC was 3,200, and the molecular weight dispersity (Mw / Mn) was 1.16. Also, the content ratio of silicon atoms was 15.4%.

[0312] 1 H-NMR, 13 C-NMR,19 F-NMR and 29 confirmed to have the following structure by Si-NMR analysis.

[0313]

Chemical formula

[0314] ≪Preparation of Film-Forming Composition≫ <Examples 1 to 15 and Comparative Examples 1 to 6> The respective components shown in Tables 1 and 2 were mixed and dissolved to prepare the film-forming compositions for each example.

[0315]

Table 1

[0316]

Table 2

[0317] In Tables 1 and 2, each abbreviation has the following meaning respectively. The numerical values in [] are the blending amounts (parts by mass).

[0318] 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 atom content ratio: 24.9%)

Chemical formula

[0319] 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 atom content ratio: 20.4%)

Chemical formula

[0320] B-1 to B-7: Cage-type silsesquioxane (B-1) to cage-type silsesquioxane (B-7) as described above

[0321] B-8: Compound represented by the following formula

Chemical formula

[0322] B-9: Compound represented by the following formula

Chemical formula

[0323] B-10: Cage-type silsesquioxane represented by the following formula (weight-average molecular weight (Mw): 1,829, molecular weight dispersity (Mw / Mn): 1.33, silicon atom content ratio: 12.4%)

Chemical formula

[0324] B-11: Cage-type silsesquioxane represented by the following formula

Chemical formula

[0325] C-1: Compound represented by the following formula

Chemical formula

[0326] D-1: Compound represented by the following formula

Chemical formula

[0327] E-1: Salicylic acid S-1: Propylene glycol monomethyl ether S-2: Propylene glycol monomethyl ether acetate

[0328] <Formation of Resist Pattern> On a 12-inch silicon wafer, a 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, the composition for film formation 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 conditions: 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, water rinsing was performed for 30 seconds using pure water, followed by spin drying. From the above, a line and space pattern (LS pattern) with a line width of 14 nm was formed.

[0329] [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 the formation of the resist pattern was determined. The results are shown in Tables 3 and 4.

[0330] [Evaluation of LWR (Line-Wise Roughness)] For the LS pattern with a line width of 14 nm formed by the formation of the resist pattern, 3σ, which is a measure indicating LWR, was determined. The results are shown in Tables 3 and 4. "3σ" represents three times the standard deviation (σ) (unit: nm) obtained from measuring the line positions at 400 locations in the longitudinal direction of the line using a scanning electron microscope (acceleration voltage 800 V, product name: S-9380, manufactured by Hitachi High-Tech Corporation). The smaller the value of 3σ, the smaller the roughness of the line sidewalls, meaning that a more uniform-width LS pattern was obtained.

[0331]

Table 3

[0332]

Table 4

[0333] From the results of Table 3 and Table 4, it was confirmed that when using the film-forming compositions of Examples 1 to 15, the roughness of the line sidewalls 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 4 and Comparative Example 6. Note that when using the film-forming composition of Comparative Example 5, it did not resolve.

Claims

1. A film-forming composition comprising a silicon-containing polymer (A) having a phenolic hydroxyl group, a cage-type silsesquioxane (B1) having an ionic group that decomposes upon exposure to generate an acid, a crosslinking agent (C), and a base component (D) that controls the diffusion of the acid generated upon exposure, or a cage-type silsesquioxane (B2) having an ionic group that decomposes upon exposure to generate an acid and a phenolic hydroxyl group, a crosslinking agent (C), and a base component (D) that controls the diffusion of the acid generated upon exposure. Film-forming composition.

2. The cage-type silsesquioxane (B1) includes a cage-type silsesquioxane represented by the following formula (b1), The cage-type silsesquioxane (B2) includes a cage-type silsesquioxane represented by the following formula (b2). The film-forming composition according to Claim 1. 【Chemical 1】 (In formula (b1), R １ to R ８ are each independently an organic group having 1 to 40 carbon atoms or a hydrogen atom. However, at least one of R １ to R ８ is an ionic group that decomposes upon exposure to generate an acid. L １ to L ８ are each independently a divalent linking group having 1 to 40 carbon atoms and containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.) 【Chemical 2】 (In formula (b2), R １ to R ８ are each independently an organic group having 1 to 40 carbon atoms or a hydrogen atom. However, at least one of R １ to R ８ is an ionic group that decomposes upon exposure to generate an acid, and at least one of the others is an aromatic group having a phenolic hydroxyl group. L １ to L ８ are each independently a divalent linking group having 1 to 40 carbon atoms and containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.)

3. The film-forming composition according to Claim 1, wherein the ionic group is a group represented by the following formula (b0). 【Chemical Formula 3】 (In formula (b0), R ｂ１０ is a divalent organic group having 1 to 40 carbon atoms. M ３ ＋ is a sulfonium cation or an iodonium cation.)

4. The film-forming composition according to Claim 1, wherein the dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the cage-type silsesquioxane (B1) or the cage-type silsesquioxane (B2) is 1.00 or more and 1.30 or less.

5. The film-forming composition according to Claim 1, wherein the base component (D) includes a compound represented by the following formula (d0-2). [Chemical Formula 4] (In formula (d0-2), R ｄ２０ is an organic group having 1 to 40 carbon atoms. M ２ ＋ is a sulfonium cation or an iodonium cation.)

6. Forming a coating film comprising the film-forming composition according to any one of Claims 1 to 5 on a support, Selectively exposing the coating film, Developing the exposed coating film to form a patterned cured film. A method for producing a patterned cured film. Method for producing a patterned cured film.

7. The method for producing a patterned cured film according to Claim 6, wherein the coating film is exposed to EUV (extreme ultraviolet rays).

8. A cage-type silsesquioxane having an ionic group that decomposes upon exposure to generate an acid.

9. The cage-type silsesquioxane according to Claim 8, represented by the following formula (b1). 【Chemical Formula 5】 (In formula (b1), R １ to R ８ are each independently an organic group having 1 to 40 carbon atoms or a hydrogen atom. However, at least one of R １ to R ８ is an ionic group that decomposes upon exposure to generate an acid. L １ to L ８ are each independently a divalent linking group having 1 to 40 carbon atoms and containing at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.)

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