Photosensitive composition and method for producing patterned silicon-containing resin film

Abstract

To provide a photosensitive composition capable of forming a patterned silicon-containing resin film with suppressed roughness, and a method for producing a patterned silicon-containing resin film.SOLUTION: In the photosensitive composition containing a silicone resin (A) and a photoacid generator (B), the silicone resin (A) contains a phenolic hydroxyl group and a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group by the action of an acid and the photoacid generator (B) is a fluorine-containing sulphonium cation (B1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition and a method for producing a patterned silicon-containing resin film. [Background technology]

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

[0003] In recent years, advances in lithography technology have led to rapid advances in the miniaturization of patterns in the manufacturing of semiconductor devices and liquid crystal display devices. A common method for miniaturizing patterns is to shorten the wavelength (increase the energy) of the exposure light source.

[0004] Resist materials are required to have lithography properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with minute dimensions. To satisfy these requirements, a chemically amplified resist composition has been used, which contains a base component whose solubility in a developer changes due to the action of acid, and an acid generator component that generates acid upon exposure. Chemically amplified resist compositions generally use resins having multiple structural units in order to improve lithography properties, etc. Furthermore, chemically amplified resist compositions have been proposed that use, in addition to an acid generator component, an acid diffusion controller that controls the diffusion of acid generated from the acid generator component upon exposure.

[0005] Furthermore, resist materials are required to have etching resistance in order to function as a mask for substrate processing, and therefore silicon-containing compounds are sometimes used as base components from the viewpoint of etching resistance. For example, Patent Document 1 discloses a resist composition containing a silicon-containing resin, an acid generator component, and a photodegradable base that controls acid diffusion in order to accommodate pattern miniaturization and etching processing. In the Examples of Patent Document 1, a pattern on the order of several μm is formed by irradiation with a KrF excimer laser, and a 50 nm pattern is formed by electron beam drawing. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-59575 Summary of the Invention [Problem to be solved by the invention]

[0007] With the further advancement of lithography technology and the expansion of its application fields, patterns are rapidly becoming finer. Accordingly, when manufacturing semiconductor devices and other devices, technology is required that can form fine patterns with good shapes. For example, in lithography using EUV (extreme ultraviolet), the goal is to form fine patterns of a dozen nanometers. As pattern dimensions become smaller, an extremely high level of control is required for the roughness of the pattern surface.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive composition capable of forming a patterned silicon-containing resin film with reduced roughness, and a method for producing a patterned silicon-containing resin film. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above problems and have found that the above problems can be solved by providing a photosensitive composition containing a silicon-containing resin (A) and a photoacid generator (B), in which the silicon-containing resin (A) contains a phenolic hydroxyl group and a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid, and the photoacid generator (B) uses a sulfonium salt (B1) containing a sulfonium cation having a fluorine atom. Specifically, the present invention provides the following.

[0010] The first aspect comprises a silicon-containing resin (A) and a photoacid generator (B), The silicon-containing resin (A) is a silicon-containing resin (A1) having a phenolic hydroxyl group and not having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid, and a silicon-containing resin (A2) having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid and not having a phenolic hydroxyl group; a silicon-containing resin (A3) having a phenolic hydroxyl group and a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid, The photosensitive composition contains a photoacid generator (B) that contains a sulfonium salt (B1) that contains a sulfonium cation having a fluorine atom.

[0011] The second aspect is Coating a support with the photosensitive composition according to the first aspect to form a coating film; position-selectively exposing the coating film; and developing the exposed coating film. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photosensitive composition capable of forming a patterned silicon-containing resin film with reduced roughness, and a method for producing a patterned silicon-containing resin film. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described in detail, but 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.

[0014] ≪Photosensitive composition≫ The photosensitive composition contains a silicon-containing resin (A) and a photoacid generator (B). The silicon-containing resin (A) is a silicon-containing resin (A1) having a phenolic hydroxyl group and not having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid, and a silicon-containing resin (A2) having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid and not having a phenolic hydroxyl group; It contains a silicon-containing resin (A3) having a phenolic hydroxyl group and a group that can crosslink with an aromatic group having a phenolic hydroxyl group under the action of an acid. The photoacid generator (B) includes a photoacid generator (B1) having a sulfonium cation containing a fluorine atom.

[0015] By using a photosensitive composition containing the above silicon-containing resin (A) in combination with a photoacid generator (B), it is possible to form a patterned silicon-containing resin film with reduced roughness. In particular, even when a finely patterned silicon-containing resin film is formed by exposure to extreme ultraviolet light, the roughness can be effectively suppressed. Furthermore, when the photosensitive composition is used, there is little film thickness reduction due to development and rinsing when a silicon-containing resin film is patterned by photolithography.

[0016] <Silicon-containing resin (A)> The photosensitive composition contains a silicon-containing resin (A). The silicon-containing resin (A) is a silicon-containing resin (A1) having a phenolic hydroxyl group and not having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid, and a silicon-containing resin (A2) having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid and not having a phenolic hydroxyl group; It contains a silicon-containing resin (A3) having a phenolic hydroxyl group and a group that can crosslink with an aromatic group having a phenolic hydroxyl group under the action of an acid.

[0017] The silicon-containing resin (A) is crosslinked by the action of the acid generated by the photoacid generator (B) upon exposure. As a result, the silicon-containing resin (A) becomes insoluble in an alkaline developer upon exposure. Furthermore, since the silicon-containing resin (A) has a phenolic hydroxyl group, the silicon-containing resin (A) is soluble in an alkaline developer. Therefore, when the photosensitive composition is exposed regioselectively, the unexposed areas are soluble in the alkaline developer. Therefore, the photosensitive composition has photolithographic properties that allow it to be patterned by regioselective exposure and development with an alkaline developer.

[0018] Examples of groups contained in the silicon-containing resin (A) that can crosslink with an aromatic group having a phenolic hydroxyl group under the action of an acid include hydroxymethyl groups bonded to an aromatic group or a nitrogen atom, and alkoxymethyl groups bonded to an aromatic group or a nitrogen atom. The number of carbon atoms in the alkoxy group contained in the alkoxymethyl group is preferably from 1 to 4. Specific preferred examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, an n-propyloxymethyl group, and an n-butyloxymethyl group.

[0019] Suitable examples of the silicon-containing resin (A) include polysilane and polysiloxane. As the silicon-containing resin (A), polysiloxane is preferred, and polysiloxane containing a silsesquioxane unit is more preferred. The silicon-containing resin (A) will be explained below using polysiloxane as an example. The polysiloxane is not particularly limited as long as it is a resin having a main chain composed of siloxane bonds (Si-O-Si). The polysiloxane may be a linear polysiloxane, a branched polysiloxane, or a silsesquioxane. The silsesquioxane may be any of a cage silsesquioxane, an incomplete cage silsesquioxane, a ladder silsesquioxane, and a random silsesquioxane. The polysiloxane may have a combination of a linear polysiloxane skeleton and / or a branched polysiloxane skeleton with a silsesquioxane skeleton.

[0020] As described above, the silicon-containing resin (A1) crosslinks through the reaction of the phenolic hydroxyl groups with groups capable of crosslinking with aromatic groups having phenolic hydroxyl groups, under the action of an acid. Therefore, the silicon-containing resin (A1) contains at least one resin having a structural unit having a group that can crosslink with an aromatic group having a phenolic hydroxyl group upon the action of an acid.

[0021] [Constituent unit (ai)] Examples of structural units having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group by the action of an acid include those represented by the following formula (a1): R a1 -SiO 3 / 2 (a1) (In formula (a1), R a1 is an organic group having a methylol group or an alkoxymethyl group, The methylol group or alkoxymethyl group is bonded to an aromatic hydrocarbon group or a nitrogen atom. A structural unit (ai) represented by the following formula is preferred.

[0022] R in formula (a1) a1 is an organic group having a methylol group or an alkoxymethyl group. The methylol group or the alkoxymethyl group is bonded to an aromatic hydrocarbon group or a nitrogen atom. Therefore, R a1is an aromatic hydrocarbon group-containing group having a methylol group or an alkoxymethyl group bonded to the aromatic hydrocarbon group, or a nitrogen-containing group having a methylol group or an alkoxymethyl group bonded to the nitrogen atom. R a1 The alkoxymethyl group contained in is as described above.

[0023] More specifically, the structural unit (ai) is preferably a structural unit (ai-1) represented by the following formula (a2), a structural unit (ai-2) represented by the following formula (a3), or a structural unit (ai-3) represented by the following formula (a4).

[0024] (R a3 ) n1 (OH) n2 Ar a1 -R a2 -SiO 3 / 2 (a2) (In formula (a2), R a2 is a divalent linking group that does not contain a single bond or an aromatic group, Ar a1 represents an (n1+n2+1)-valent aromatic hydrocarbon group which may have a substituent, R a3 is an organic group selected from a methylol group, an alkoxymethyl group, a hydrocarbon group having from 1 to 6 carbon atoms, and an alkoxy group having from 1 to 6 carbon atoms, R a3 The organic group is Ar a1 and bonded to an aromatic hydrocarbon group as n1 is an integer between 1 and 6, (OH) n2 Ar a1 n2 hydroxyl groups bonded to an aromatic hydrocarbon group as n2 is an integer between 0 and 4, R between 1 and 6 a3 At least one of the organic groups is a methylol group or an alkoxymethyl group.

[0025] In formula (a2), Ra2 is a divalent linking group that does not contain a single bond or an aromatic group. The structure of the divalent linking group may be linear, branched, cyclic, or a combination of these structures. The divalent linking group may or may not have an unsaturated bond, and preferably does not have an unsaturated bond. The divalent linking group is preferably an alkylene group, a group selected from -O-, -S-, -CO-O-, -CO-NH-, -CO-, -O-CO-O-, and -SO2-, or a combination of two or more selected from these groups.

[0026] The alkylene group as a divalent linking group or the alkylene group constituting the divalent linking group preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 6 or less, even more preferably 1 or more and 4 or less, and particularly preferably 1 or 2. Specific examples of alkylene groups as divalent linking groups or alkylene groups constituting divalent linking groups include methylene, ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, and decane-1,10-diyl groups.

[0027] R a2 Suitable examples of the divalent linking group as include the above alkylene groups, -O-CH2-, -O-CH2CH2-, -O-CH2CH2CH2-, -S-CH2-, -S-CH2CH2-, -S-CH2CH2CH2-, -CH2-O-CH2-, -CH2CH2-O-CH2CH2-, -CH2-S-CH2-, -CH2-S-CH2CH2-, and -CH2CH2-S-CH2CH2-.

[0028] Ar a1 is an (n1+n2+1)-valent aromatic hydrocarbon group which may have a substituent. a1Examples of the aromatic hydrocarbon group as the aromatic hydrocarbon group include groups in which (n1+n2+1) hydrogen atoms have been removed from aromatic hydrocarbon groups such as benzene, naphthalene, anthracene, phenanthrene, and biphenyl.

[0029] R a3 is an organic group selected from a methylol group, an alkoxymethyl group, a hydrocarbon group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. a3 At least one of the organic groups is a methylol group or an alkoxymethyl group. R a3 The alkoxymethyl group as the alkoxymethyl group is as described above. Examples of hydrocarbon groups having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and alkenyl groups having 1 to 6 carbon atoms.

[0030] Specific preferred examples of the structural unit (ai-1) represented by formula (a2) include the following structural units. [ka]

[0031] [ka]

[0032] R a6 -R a5 -Ar a2 -R a4 -SiO 3 / 2 (a3) (In formula (a3), R a4 is a divalent linking group that does not contain a single bond or an aromatic group, Ar a2 represents a divalent aromatic hydrocarbon group which may have a substituent, R a5 is a single bond or a divalent linking group, Ra6 is an aromatic hydrocarbon group having a methylol group or an alkoxymethyl group, or a nitrogen-containing group having a methylol group or an alkoxymethyl group, The methylol group and the alkoxymethyl group are bonded to an aromatic hydrocarbon group or a nitrogen atom, respectively.

[0033] In formula (a3), R a4 is a divalent linking group that does not contain a single bond or an aromatic group. a4 The divalent linking group as R in formula (a2) a2 The same applies to the divalent linking group as defined above.

[0034] Ar a2 is a divalent aromatic hydrocarbon group which may have a substituent. Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, and a biphenyldiyl group. Examples of the substituent which the divalent aromatic hydrocarbon group may have include an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a halogen atom, a halogenated alkyl group having from 1 to 6 carbon atoms, a halogenated alkoxy group having from 1 to 6 carbon atoms, a cyano group, and a nitro group.

[0035] R a5 is a single bond or a divalent linking group. a6 is an aromatic hydrocarbon group having a methylol group or an alkoxymethyl group, R a5 is a divalent linking group. a6 is an aromatic hydrocarbon group having a methylol group or an alkoxymethyl group, and R a5 is a single bond, Ar a2 and R a6 This is because the group in which and are bonded via a single bond can be interpreted as one aromatic hydrocarbon group. R a5 The divalent linking group as R in formula (a2) a2 The same applies to the divalent linking group as defined above.

[0036] R a6 is an aromatic hydrocarbon group having a methylol group or an alkoxymethyl group, or a nitrogen-containing group having a methylol group or an alkoxymethyl group. The methylol group and the alkoxymethyl group are bonded to the aromatic hydrocarbon group or the nitrogen atom, respectively.

[0037] R a6 Examples of the aromatic hydrocarbon group constituting the aromatic hydrocarbon group having a methylol group or an alkoxymethyl group as the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. In the nitrogen-containing group, a methylol group or an alkoxymethyl group is preferably bonded to the nitrogen atom in, for example, an amino group, a (H2N-) carbamoyl group (H2N-CO-), and an imide group.

[0038] R a6 The alkoxymethyl group contained in the aromatic hydrocarbon group having an alkoxymethyl group or the nitrogen-containing group having an alkoxymethyl group is as described above.

[0039] Specific preferred examples of the structural unit (ai-2) represented by formula (a3) ​​include the following structural units. [ka]

[0040] R a8 -R a7 -SiO 3 / 2 (a4) (In formula (a4), R a7 is a divalent linking group that does not contain an aromatic group, R a8 is a nitrogen-containing group having a methylol group or an alkoxymethyl group-containing group, The methylol group and the alkoxymethyl group are each bonded to a nitrogen atom.

[0041] In formula (a4), R a7is a divalent linking group that does not contain an aromatic group. a7 The divalent linking group as R in formula (a2) a2 The same applies to the divalent linking group as defined above. R a8 is a nitrogen-containing group having a methylol group or an alkoxymethyl group-containing group. a8 The nitrogen-containing group having a methylol group or an alkoxymethyl group-containing group as R a6 The same applies to a nitrogen-containing group having a methylol group or an alkoxymethyl group as the above. R a8 The alkoxymethyl group contained in the nitrogen-containing group having an alkoxymethyl group is as described above.

[0042] Specific preferred examples of the structural unit (ai-3) represented by formula (a4) include the following structural units. [ka]

[0043] The structural unit (ai-2) represented by formula (a3) ​​is a structural unit that does not correspond to the structural unit (ai-1) represented by formula (a2). The structural unit (ai-3) represented by formula (a4) is a structural unit that does not correspond to the structural unit (ai-1) represented by formula (a2) or the structural unit (ai-2) represented by formula (a3).

[0044] [Constituent unit (aii)] The silicon-containing resin (A) may contain a structural unit (aii) that has a phenolic hydroxyl group but does not have a group that can crosslink with an aromatic group that has a phenolic hydroxyl group by the action of an acid.

[0045] As the structural unit (aii), a unit represented by the following formula (a5) is preferred. R a10 -R a9 -SiO 3 / 2 (a5) (In formula (a5), R a9is a divalent linking group that does not contain a single bond or an aromatic group, R a10 is an aromatic hydrocarbon group having a phenolic hydroxyl group.

[0046] In formula (a5), R a9 is a divalent linking group that does not contain an aromatic group. a9 The divalent linking group as R in formula (a2) a2 The same applies to the divalent linking group as defined above. R a10 is an aromatic hydrocarbon group having a phenolic hydroxyl group. The number of hydroxyl groups bonded to the aromatic hydrocarbon group is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2. R a10 Examples of the aromatic hydrocarbon group constituting the aromatic hydrocarbon group having a phenolic hydroxyl group as the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. R a10 The aromatic hydrocarbon group having a phenolic hydroxyl group as the substituent may have a substituent, such as an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a halogen atom, a halogenated alkyl group having from 1 to 6 carbon atoms, a halogenated alkoxy group having from 1 to 6 carbon atoms, a cyano group, and a nitro group.

[0047] Specific preferred examples of the structural unit (aii) represented by formula (a5) include the structural units shown below. [ka]

[0048] [Other structural units] The polysiloxane may have another structural unit (aiii) in addition to the structural unit (ai) and the structural unit (aii). Other examples of the structural unit (aiii) include a structural unit (aiii-1) containing an alkyl group, a structural unit (aiii-2) represented by formula (a7-1) or formula (a7-2), and a structural unit (aiii-3) represented by formula (a8).

[0049] (Structural unit (aiii-1)) The structural unit (aiii-1) is a structural unit that contains an alkyl group. An example of the structural unit (aiii-1) is a structural unit in which the main chain portion is an Si—O bond and the side chain portion bonded to the Si atom is an alkyl group. By including the structural unit (aiii-1), the properties of the silicon-containing resin film formed using the photosensitive composition can be easily controlled.

[0050] As the structural unit (aiii-1), the structural unit (a2-1) represented by the following formula (a6-1) and the structural unit (a6-2) represented by the following formula (a2-2) are preferred. R a21 -SiO 3 / 2 ···(a6-1) Si(R a22 )(R a23 )O 2 / 2 ···(a6-2) (In formula (a6-1) and formula (a6-2), R a21 ~R a23 are each independently a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 10 carbon atoms which may have a substituent, or a trihydrocarbylsilyl group in which three hydrocarbon groups having from 1 to 10 carbon atoms are bonded to a silicon atom.

[0051] In formula (a6-1) and formula (a6-2), R a21 ~R a23 The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures. R a21 ~R a23The aliphatic hydrocarbon group may have a substituent, such as a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, a mercapto group, or an amino group. R a21 ~R a23 is preferably a hydrogen atom, an alkyl group, or an alkenyl group. R a21 ~R a23 The number of carbon atoms in the alkyl group is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less. R a21 ~R a23 Examples of the alkyl group as include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a 2-ethylhexyl group. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group are preferred, a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferred, a methyl group and an ethyl group are even more preferred, and a methyl group is particularly preferred. R a21 ~R a23 The alkenyl group as the alkyl group preferably has 2 or more and 5 or less carbon atoms, and more preferably 2 or 3 carbon atoms. R a21 ~R a23 As the alkenyl group for , a vinyl group and an allyl group are preferred.

[0052] R a21 ~R a23 The trihydrocarbylsilyl group as defined above is a trihydrocarbylsilyl group in which three hydrocarbon groups having 1 to 10 carbon atoms are bonded to a silicon atom. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures. The aliphatic hydrocarbon group may have one or more unsaturated bonds. Specific examples of the aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, sec-butyl, and tert-butyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aromatic hydrocarbon groups such as phenyl and naphthyl; and aralkyl groups such as benzyl and phenethyl. Specific examples of the trihydrocarbylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a phenyldimethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, a benzyldimethylsilyl group, a dibenzylmethylsilyl group, and a tribenzylsilyl group.

[0053] The structural unit (aiii-1) contained in the polysiloxane may be of one type or of two or more types. When the polysiloxane contains the structural unit (aiii-1) in addition to the structural unit (ai) and the structural unit (aii), the proportion of the structural unit (aiii-1) in the polysiloxane, relative to the total (100 mol%) of all structural units constituting the polysiloxane, is preferably 10 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 55 mol% or less, and even more preferably 30 mol% or more and 50 mol% or less.

[0054] (Structural unit (aiii-2)) The structural unit (aiii-2) is a structural unit represented by the following formula (a7-1) or the following formula (a7-2). The structural unit (aiii-2) is useful for improving lithography properties. The introduction of the structural unit (aiii-2) makes it easy to control the dissolution rate. [ka] (In formula (a7-1) and formula (a7-2), Ph is a phenyl group when na is 0, and na R a24 is a phenyl group substituted with Ra24 is a hydrocarbon group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or a phenolic hydroxyl group protected by an acid-dissociable group, and R a25 is a single bond or a divalent linking group, and na is an integer of 0 or more and 5 or less.

[0055] R a24 The hydrocarbon group as R may be either linear or branched. a24 The hydrocarbon group as may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, with a saturated hydrocarbon group being preferred. R a24 The number of carbon atoms in the hydrocarbon group as R is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less. a24 The hydrocarbon group as is preferably an alkyl group. 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 tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Among these, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferred, a methyl group and an ethyl group are more preferred, and a methyl group is even more preferred. R a24 The number of carbon atoms in the alkoxy group as the aryl group is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, an isopentyloxy group, and a neopentyloxy group. Among these, a methoxy group, an ethoxy group, an n-propyloxy group, and an isopropyloxy group are preferred, a methoxy group and an ethoxy group are more preferred, and a methoxy group is even more preferred. R a24is a phenolic hydroxyl group protected by an acid-dissociable group, the acid-dissociable group is not particularly limited and can be appropriately selected from various known acid-dissociable groups, such as a tert-butyl group, a 1-ethylcyclopentan-1-yl group, a 1-ethylcyclohexan-1-yl group, a tert-butoxycarbonyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, a methoxymethyl group, a tetrahydropyran-2-yl group, and a tetrahydrofuran-2-yl group. na3 is preferably an integer of 0 or more and 3 or less, more preferably 0 or 1, and even more preferably 0. R a25 The divalent linking group as R in formula (a2) a2 The same applies to the divalent linking group as above. Preferred divalent linking groups include -Si(CH3)2-, -SiH(CH3)-, -Si(C6H5)(CH3)-, Si(C6H5)2-, - and -SiH(C6H5)-.

[0056] The structural unit (aiii-2) contained in the polysiloxane may be of one type or of two or more types. When the polysiloxane contains the structural unit (aiii-2) in addition to the structural unit (ai) and the structural unit (aii), the proportion of the structural unit (aiii-2) in the polysiloxane, relative to the total (100 mol%) of all structural units constituting the polysiloxane, is preferably 10 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 55 mol% or less, and even more preferably 30 mol% or more and 50 mol% or less.

[0057] (Structural unit (aiii-3)) The structural unit (aiii-3) is a structural unit represented by the following formula (a8). The structural unit (a8) is useful for improving lithography properties. The introduction of the structural unit (a8) makes it easy to control the dissolution rate. SiO 4 / 2 (a8)

[0058] When the polysiloxane contains the structural unit (aiii-3) in addition to the structural unit (ai) and the structural unit (aii), the proportion of the structural unit (aiii-3) within the polysiloxane, relative to the total (100 mol%) of all structural units constituting the polysiloxane, is preferably 10 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 55 mol% or less, and even more preferably 30 mol% or more and 50 mol% or less.

[0059] Specific examples of other structural units are shown below. [ka]

[0060] The silicon-containing resin (A) is a silicon-containing resin (A1) having a phenolic hydroxyl group and not having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid, and a silicon-containing resin (A2) having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid and not having a phenolic hydroxyl group; It contains a silicon-containing resin (A3) having a phenolic hydroxyl group and a group that can crosslink with an aromatic group having a phenolic hydroxyl group under the action of an acid.

[0061] Examples of the silicon-containing resin (A1) include resins consisting only of the structural unit (aii), and resins consisting of the structural unit (aii) and the other structural units described above.

[0062] Examples of the silicon-containing resin (A2) include resins consisting only of structural units that correspond to the structural unit (ai) and do not have a phenolic hydroxyl group, and resins consisting of structural units that correspond to the structural unit (ai) and do not have a phenolic hydroxyl group and the other structural units described above.

[0063] Examples of the silicon-containing resin (A3) include: 1) A resin consisting only of structural units that correspond to the structural unit (ai) and have a phenolic hydroxyl group; 2) A resin composed of a structural unit corresponding to the structural unit (ai) and having a phenolic hydroxyl group, and a structural unit corresponding to the structural unit (ai) and not having a phenolic hydroxyl group; 3) A resin composed of a structural unit corresponding to the structural unit (ai) and having a phenolic hydroxyl group, and a structural unit (aii); 4) A resin composed of a structural unit corresponding to the structural unit (ai) and having a phenolic hydroxyl group, a structural unit corresponding to the structural unit (ai) and not having a phenolic hydroxyl group, and a structural unit (aii); 5) A resin composed of a structural unit corresponding to the structural unit (ai) and having a phenolic hydroxyl group and the other structural units described above; 6) A resin composed of a structural unit corresponding to the structural unit (ai) and having a phenolic hydroxyl group, a structural unit corresponding to the structural unit (ai) and not having a phenolic hydroxyl group, and the other structural units described above; 7) A resin composed of a structural unit corresponding to the structural unit (ai) and having a phenolic hydroxyl group, a structural unit (aii), and the other structural units described above; 8) A resin composed of a structural unit corresponding to the structural unit (ai) and having a phenolic hydroxyl group, a structural unit corresponding to the structural unit (ai) and not having a phenolic hydroxyl group, a structural unit (aii), and the other structural units described above; 9) A resin composed of a structural unit that corresponds to the structural unit (ai) and does not have a phenolic hydroxyl group, and a structural unit (aii), and 10) Resins that correspond to the structural unit (ai) and do not have a phenolic hydroxyl group, and resins that are composed of the structural unit (aii) and the other structural units described above, are also included.

[0064] In the silicon-containing resin (A), the ratio of structural units having a phenolic hydroxyl group and having a hydrogen atom bonded to the carbon atom adjacent to the carbon atom to which the phenolic hydroxyl group is bonded on the aromatic hydrocarbon ring is preferably 10 mol % or more and 80 mol % or less, and more preferably 20 mol % or more and 70 mol % or less, based on the number of moles of all structural units in the silicon-containing resin (A).

[0065] In the silicon-containing resin (A), the ratio of structural units having a methylol group or an alkoxymethyl group to the total number of moles of structural units in the silicon-containing resin (A) is preferably 10 mol % or more and 60 mol % or less, and more preferably 20 mol % or more and 50 mol % or less.

[0066] The mass average molecular weight (Mw) (based on polystyrene equivalent determined by gel permeation chromatography (GPC)) of the silicon-containing resin (A) such as polysiloxane is not particularly limited, and is, for example, 1,000 or more, preferably 1,000 or more and 10,000 or less, and more preferably 2,000 or more and 6,000 or less. When the Mw of the silicon-containing resin (A) is equal to or less than the upper limit of the above-mentioned preferred range, the silicon-containing resin (A) has excellent solubility in organic solvents. On the other hand, when the Mw of the silicon-containing resin (A) is equal to or greater than the lower limit of the above-mentioned preferred range, a photosensitive composition with excellent lithography properties can be easily obtained, and a resin film with a well-shaped pattern can be easily formed.

[0067] The ratio of the mass of the silicon-containing resin (A) to the mass of the solid content of the photosensitive composition is preferably 10 mass% or more, more preferably 20 mass% or more, even more preferably 30 mass% to 75 mass% or less, particularly preferably 40 mass% to 70 mass% or less, and most preferably 50 mass% to 70 mass% or less.

[0068] <Photoacid generator (B)> The photosensitive composition contains the silicon-containing resin (A) and a photoacid generator (B). When the photosensitive composition is exposed to light, the photoacid generator (B) generates an acid, which causes crosslinking of the silicon-containing resin (A). The photoacid generator (B) contains a photoacid generator (B1) containing a sulfonium cation having a fluorine atom, which makes it easier to reduce the roughness of a pattern formed using the photosensitive composition.

[0069] [Photoacid generator (B1) containing a sulfonium cation having a fluorine atom] The photoacid generator (B1) is a sulfonium salt having a sulfonium cation containing a fluorine atom as the cation moiety. The anion moiety and the cation moiety in the photoacid generator (B1) are not particularly limited as long as the sulfonium cation as the cation moiety contains a fluorine atom.

[0070] A preferred example of the photoacid generator (B1) is a sulfonium salt represented by the following formula (b0-1). [ka] (In formula (b0-1), R b1 is an aryl group having a fluorine atom or an aryl group having a fluorinated alkyl group. b2 , and R b3 R are each independently an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. b1 ~R b3 Two of X may be bonded to each other to form a ring together with the sulfur atom in the formula. 01 is the counter anion.)

[0071] (Regarding the cation moiety in formula (b0-1)) In formula (b0-1), R b1 is an aryl group having a fluorine atom or an aryl group having a fluorinated alkyl group. R b1 The number of carbon atoms in the aromatic hydrocarbon ring constituting the aryl group having a fluorine atom and the aryl group having a fluorinated alkyl group as the aryl group is preferably 6 or more and 30 or less, more preferably 6 or more and 20 or less, still more preferably 6 or more and 15 or less, and particularly preferably 6 or more and 10 or less. R b1 As the aromatic hydrocarbon ring constituting the aryl group having a fluorine atom as the aryl group and the aryl group having a fluorinated alkyl group, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring are preferred, a benzene ring and a naphthalene ring are more preferred, and a benzene ring is even more preferred.

[0072] The fluorinated alkyl group constituting the aryl group having a fluorinated alkyl group includes a fluorinated alkyl group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 12, more preferably 1 to 8, even more preferably 1 to 5, and particularly preferably 1 to 3. The fluorinated alkyl group may be linear or branched.

[0073] Examples of the linear fluorinated alkyl group having from 1 to 12 carbon atoms include groups in which some or all of the hydrogen atoms of a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, or n-dodecyl group have been substituted with fluorine atoms.

[0074] Examples of branched fluorinated alkyl groups having from 1 to 12 carbon atoms include 1-methylethyl groups (isopropyl groups), 1-methylpropyl groups (sec-butyl groups), 2-methylpropyl groups (isobutyl groups), 1-methylbutyl groups (sec-pentyl groups), 2-methylbutyl groups, 3-methylbutyl groups (isopentyl groups), 1-ethylbutyl groups, 2-ethylbutyl groups, 1-methylpentyl groups, 2-methylpentyl groups, 3-methylpentyl groups, and 4-methylpentyl groups (isohexyl groups) in which some or all of the hydrogen atoms have been substituted with fluorine atoms.

[0075] Among the above fluorinated alkyl groups, a trifluoromethyl group is particularly preferred.

[0076] R b1 The aryl group having a fluorine atom as the aryl group and the aryl group having a fluorinated alkyl group as the aryl group may each have a substituent other than the fluorine atom or the fluorinated alkyl group on the aromatic hydrocarbon ring. Examples of other substituents include an alkyl group, a halogen atom other than a fluorine atom, a halogenated alkyl group other than a fluorinated alkyl group, an oxo group (=O), a cyano group, an amino group, an aryl group, groups represented by the following formulae (ca-r-1) to (ca-r-7), -SO2-R b0 Examples of such groups include groups represented by R b0 R is an alkyl group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. b0 The alkyl group may be linear or branched.

[0077] -OR ’201 (ca-r-1) -O-CH2-CO-OR ’201 (ca-r-2) -O-CO-R ’201 (ca-r-3) -O-CH2-OR ’201 (ca-r-4) -O-CO-CH2-O-CO-R ’201 (ca-r-5) -O-SO2-R ’201 (ca-r-6) -O-CH2-CO-O-CH2-CO-OR ’201 (ca-r-7)

[0078] In formulas (ca-r-1) to (ca-r-7), R ’201 are each independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted alkyl group, an optionally substituted aralkyl group, or an optionally substituted alkenyl group.

[0079] R ’201 The cyclic group constituting the cyclic group which may have a substituent as the above is not particularly limited. The cyclic group may be a cyclic hydrocarbon group or a heterocyclic group. The heterocyclic group may contain, for example, a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom as a ring-constituting atom. The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group.

[0080] The cyclic group is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cycloaliphatic hydrocarbon group. The cycloaliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. The cycloaliphatic hydrocarbon group may have one or more unsaturated bonds. The cycloaliphatic hydrocarbon group is preferably a saturated cycloaliphatic hydrocarbon group.

[0081] R ’201 The number of carbon atoms in the aromatic hydrocarbon ring constituting the aromatic hydrocarbon group which may have a substituent as the aromatic hydrocarbon group is preferably 6 or more and 30 or less, more preferably 6 or more and 20 or less, even more preferably 6 or more and 15 or less, and particularly preferably 6 or more and 12 or less. R ’201 As the aromatic hydrocarbon ring constituting the aromatic hydrocarbon group which may have a substituent as the aromatic hydrocarbon ring, a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring are preferred.

[0082] R ’201 As the aromatic hydrocarbon ring constituting the aralkyl group which may have a substituent as the above, a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring are preferred. R ’201 The alkylene group constituting the aralkyl group, which may have a substituent such as: is preferably an alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethane-1,2-diyl group (ethylene group), and even more preferably a methylene group.

[0083] R ’201 The number of carbon atoms in the aliphatic hydrocarbon ring constituting the alicyclic hydrocarbon group which may have a substituent as the cycloaliphatic hydrocarbon group is preferably 3 or more and 30 or less, more preferably 3 or more and 20 or less, and even more preferably 3 or more and 12 or less. The optionally substituted alicyclic hydrocarbon group may be a group in which one hydrogen atom has been removed from a monocycloalkane which may have a substituent, or may be a group in which one hydrogen atom has been removed from a polycycloalkane which may have a substituent.

[0084] The number of carbon atoms in the monocycloalkane which may have a substituent is preferably 3 or more and 6 or less. The number of carbon atoms in the substituent is not included in the number of carbon atoms in the monocycloalkane. As the monocycloalkane which may have a substituent, cyclopentane which may have a substituent and cyclohexane which may have a substituent are preferred.

[0085] The number of carbon atoms of the polycycloalkane, which may have a substituent, is preferably 7 or more and 30 or less. As the polycycloalkane, which may have a substituent, a polycycloalkane having a polycyclic skeleton of a bridged ring system, which may have a substituent, and a fused cyclic aliphatic hydrocarbon ring having a steroid skeleton, which may have a substituent, are preferred. Examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0086] R ’201 Examples of the heterocyclic group as the heterocyclic group include lactone-containing cyclic groups represented by the following formulae (a2-r-1) to (a2-r-7). [ka]

[0087] In formulas (a2-r1) to (a2-r7), Ra ’21 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -CO-OR", -O-CO-R", a hydroxyalkyl group, or a cyano group. R" is a hydrogen atom, an alkyl group which may have a substituent, a cyclic aliphatic hydrocarbon group which may have a substituent, a lactone-containing cyclic group, a carbonate-containing cyclic group, or an -SO2- containing cyclic group. A" is an oxygen atom, an alkylene group having from 1 to 5 carbon atoms which may be interrupted by a sulfur atom, an oxygen atom, or a sulfur atom. n' is an integer of from 0 to 2. m' is 0 or 1.

[0088] In formulas (a2-r-1) to (a2-r-7), Ra ’21 The number of carbon atoms in the alkyl group as Ra is preferably 1 or more and 6 or less. ’21 The alkyl group as may be linear or branched.

[0089] Ra ’21 Specific examples of the alkyl group as include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, etc. Among these, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0090] Ra ’21 The number of carbon atoms in the alkoxy group as Ra is preferably 1 or more and 6 or less. ’21 The alkoxy group as may be linear or branched.

[0091] Ra ’21 Specific examples of the alkoxy group as include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, an n-hexyloxy group, etc. Among these, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.

[0092] Ra ’21 Examples of the halogen atom as include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0093] Ra ’21 As the halogenated alkyl group, the above-mentioned Ra ’21 Examples of the halogenated alkyl group include a group in which some or all of the hydrogen atoms in the alkyl group have been substituted with halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferred, and a perfluoroalkyl group is more preferred.

[0094] Ra ’21 In the -CO-OR" and -O-CO-R" as the above, R" is a hydrogen atom, an alkyl group which may have a substituent, a cyclic aliphatic hydrocarbon group which may have a substituent, a lactone-containing cyclic group, a carbonate-containing cyclic group, or an -SO2- containing cyclic group.

[0095] The alkyl group represented by R" which may have a substituent may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 or more and 15 or less, more preferably 1 or more and 10 or less, even more preferably 1 or more and 5 or less, and particularly preferably 1 or 2. The number of carbon atoms in the alkyl group does not include the number of carbon atoms of the substituent. The alkyl group represented by R" is particularly preferably a methyl group or an ethyl group.

[0096] The number of carbon atoms in the alicyclic hydrocarbon group represented by R″, which may have a substituent, is preferably 3 or more and 30 or less, more preferably 3 or more and 15 or less, still more preferably 4 or more and 12 or less, and particularly preferably 5 or more and 10 or less. The number of carbon atoms in the alicyclic hydrocarbon group does not include the number of carbon atoms of the substituent.

[0097] Examples of the alicyclic hydrocarbon group which may have a substituent include a group in which one hydrogen atom has been removed from a monocycloalkane which may be substituted with a fluorine atom or a fluorinated alkyl group; and a group in which one hydrogen atom has been removed from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane. More specifically, examples of the alicyclic hydrocarbon group include groups in which one hydrogen atom has been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.

[0098] The lactone-containing cyclic group represented by R″ is a group represented by the above formula (a2-r-1) to formula (a2-r-7), and Ra ’21is -CO-OR" or -O-CO-R", where R" is not a lactone-containing cyclic group.

[0099] Suitable examples of the lactone-containing cyclic group represented by any one of formulae (a2-r-1) to (a2-r-7) include the following groups.

[0100] [ka]

[0101] [ka]

[0102] As the carbonate-containing cyclic group represented by R″, groups represented by the following formulae (ax3-r-1) to (ax3-r-3) are preferred. [ka]

[0103] In formulas (ax3-r-1) to (ax3-r-3), Ra ’x31 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -CO-OR", -O-CO-R", a hydroxyalkyl group, or a cyano group. R" is a hydrogen atom, an alkyl group which may have a substituent, a cyclic aliphatic hydrocarbon group which may have a substituent, a lactone-containing cyclic group, a carbonate-containing cyclic group, or an -SO2- containing cyclic group. A" is an oxygen atom, an alkylene group having from 1 to 5 carbon atoms which may be interrupted by a sulfur atom, an oxygen atom, or a sulfur atom. p' is an integer of from 0 to 3. q' is 0 or 1.

[0104] The alkylene group represented by A" in formulae (ax3-r-1) to (ax3-r-3) may be linear or branched. Examples of the alkylene group represented by A" include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, and a propane-1,2-diyl group. Of these alkylene groups, a methylene group is preferred.

[0105] The alkylene group represented by A" may be interrupted by an oxygen atom or a sulfur atom. Examples of the alkylene group interrupted by an oxygen atom or a sulfur atom include -CH2-O-CH2-, -CH2-O-CH2CH2-, -CH2-CH2-O-CH2-CH2-, -CH2-S-CH2-, -CH2-S-CH2CH2-, and -CH2-CH2-S-CH2-CH2-.

[0106] Ra ’x31 The alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -CO-OR", -O-CO-R", and hydroxyalkyl group as Ra in formulas (a2-r-1) to (a2-r-7) are ’21 The same applies to alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, -CO-OR", -O-CO-R", and hydroxyalkyl groups as the above. However, the carbonate-containing cyclic group represented by R″ is a group represented by the above formula (ax3-r-1) to formula (ax3-r-3), and Ra ’x31 is -CO-OR" or -O-CO-R", where R" is not a carbonate-containing cyclic group.

[0107] Suitable examples of the carbonate-containing cyclic group represented by any one of formulae (ax3-r-1) to (ax3-r-3) include the following groups. [ka]

[0108] As the -SO2- containing cyclic group represented by R'', groups represented by the following formulae (a5-r-1) to (a5-r-3) are preferred. [ka]

[0109] In formulas (a5-r-1) to (a5-r-3), Ra ’51 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -CO-OR", -O-CO-R", a hydroxyalkyl group, or a cyano group. R" is a hydrogen atom, an alkyl group which may have a substituent, a cyclic aliphatic hydrocarbon group which may have a substituent, a lactone-containing cyclic group, a carbonate-containing cyclic group, or an -SO2- containing cyclic group. A" is an oxygen atom, an alkylene group having from 1 to 5 carbon atoms which may be interrupted by a sulfur atom, an oxygen atom, or a sulfur atom. n' is an integer of from 0 to 2.

[0110] In formulae (a5-r-1) to (a5-r-3), the alkylene group optionally interrupted by an oxygen atom or a sulfur atom as A" is the same as the alkylene group optionally interrupted by an oxygen atom or a sulfur atom as A" in formulae (ax3-r-1) to (ax3-r-3).

[0111] Ra ’51 The alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -CO-OR", -O-CO-R", and hydroxyalkyl group as Ra in formulas (a2-r-1) to (a2-r-7) are ’21 The same applies to alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, -CO-OR", -O-CO-R", and hydroxyalkyl groups as the above. However, the -SO2- containing cyclic group represented by R" is a group represented by the above formula (a5-r-1) to formula (a5-r-3), and Ra ’51 is -CO-OR" or -O-CO-R", where R" is not a -SO2- containing cyclic group.

[0112] Suitable examples of the -SO2- containing cyclic group represented by any one of formulae (a5-r-1) to (a5-r-3) include the following groups: In the following formulae, Ac is an acetyl group.

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] Ra ’21 The number of carbon atoms in the hydroxyalkyl group as the hydroxyalkyl group is preferably 1 or more and 6 or less. The hydroxyalkyl group may be linear or branched. The number of hydroxy groups in the hydroxyalkyl group is not particularly limited, and is preferably 1 or 2, and more preferably 1. Suitable examples of the hydroxyalkyl group include a hydroxymethyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group.

[0117] In formulae (a2-r-2), (a2-r-3), and (a2-r-5), A" represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom. A″ in formula (a2-r-2), formula (a2-r-3), and formula (a2-r-5) is the same as A″ described above for formulas (ax3-r-1) to (ax3-r-3).

[0118] R ’201 Specific examples of the lactone-containing groups represented by Formulae (a2-r-1) to (a2-r-7) that are preferred as the heterocyclic group as R" are the same as the specific examples of the lactone-containing cyclic group as R" described for Formulae (a2-r-1) to (a2-r-7).

[0119] R ’201 The heterocyclic group as is also preferably the aforementioned carbonate-containing cyclic group or the aforementioned -SO2- containing cyclic group.

[0120] R ’201 As the heterocyclic group as above, heterocyclic groups represented by the following formulae (r-hr-1) to (r-hr-16) are also preferred. [ka]

[0121] R ’201 Examples of the substituent that the cyclic group may have include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide, a hydroxyl group, an oxo group (=O), and a nitro group.

[0122] R ’201 The alkyl group, which may have a substituent as described above, may be linear or branched. The number of carbon atoms in a linear alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The number of original atoms in a branched alkyl group is preferably 3 to 20, more preferably 3 to 15, and even more preferably 3 to 10.

[0123] R ’201 Specific examples of the alkyl group which may have a substituent as the substituent include a 1-methylethyl group (isopropyl group), a 1-methylpropyl group (sec-butyl group), a 2-methylpropyl group (isobutyl group), a 1-methylbutyl group (sec-pentyl group), a 2-methylbutyl group, a 3-methylbutyl group (isopentyl group), a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group (isohexyl group).

[0124] R ’201The number of carbon atoms in the aralkyl group, which may have a substituent as the substituent, is preferably 7 or more and 20 or less, and more preferably 7 or more and 12 or less. Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, a naphthalen-1-ylmethyl group, a naphthalen-2-ylmethyl group, a naphthalen-1-ylethyl group, and a naphthalen-2-ylmethyl group.

[0125] R ’201 The alkenyl group, which may have a substituent as described above, may be linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, and even more preferably 2 or more and 4 or less.

[0126] Examples of linear alkenyl groups include vinyl, 2-propenyl (allyl), 1-propenyl, 3-butenyl, 2-butenyl, and 1-butenyl groups. Examples of branched alkenyl groups include 1-methylvinyl, 1-methyl-2-propenyl, and 2-methyl-2-propenyl groups. The alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group, a 2-propenyl group, or a 1-propenyl group, and even more preferably a vinyl group.

[0127] R ’201 Examples of the substituents on the cyclic group, alkyl group, aralkyl group, and alkenyl group as the substituents include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxo group (═O), a cyano group, and a nitro group.

[0128] R in formula (b0-1) b1 as-SO2-R b0 In the group represented by b0 represents an alkyl group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent.

[0129] R b0The alkyl group, which may have a substituent, as R may be linear or branched. b0 Specific examples of the alkyl group which may have a substituent as the substituted group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group. Among these, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0130] R b0 Examples of the substituent in the alkyl group which may have a substituent as the substituent include a halogen atom, a halogen atom having from 1 to 5 carbon atoms, an alkoxy group having from 1 to 5 carbon atoms, a hydroxy group, an oxo group (═O), and a carboxy group.

[0131] R b0 The number of carbon atoms in the alicyclic hydrocarbon group which may have a substituent as the group is preferably 3 or more and 20 or less, and more preferably 3 or more and 12 or less. The alicyclic hydrocarbon group may be a monocyclic group or a polycyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane or a polycycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms. Specific examples of the monocycloalkane include cyclobutane, cyclopentane, and cyclohexane. The polycycloalkane preferably has 7 to 20 carbon atoms. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0132] R b0 Examples of the substituent in the alicyclic hydrocarbon group which may have a substituent as the group include -R P1 , -R P2 -OR P1 , -R P2 -CO-R P1 , -R P2 -CO-OR P1 , -R P2 -O-CO-RP1 , -R P2 -OH, -RP2-CN, and -R P2 -COOH and the like. R P1 is an alkyl group having 1 to 10 carbon atoms, a saturated cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms. R P2 is a single bond, an alkylene group having from 1 to 10 carbon atoms, a divalent saturated cyclic aliphatic hydrocarbon group having from 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having from 6 to 30 carbon atoms. R P1 , and R P2 The above groups as may have a substituent, and the substituent is preferably a fluorine atom.

[0133] R P1 Examples of the alkyl group having 1 to 10 carbon atoms as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0134] R P1 Examples of the saturated cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl groups; bicyclo[2.2.2]octyl, tricyclo[5.2.1.0]octyl, and the like. 2,6 ]decanyl group, tricyclo[3.3.1.1 3,7 ]decanyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 ] dodecanyl group, and adamantyl group, and other polycyclic saturated alicyclic hydrocarbon groups.

[0135] R P1Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms include a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, and a biphenyl group.

[0136] R P2 Examples of the alkylene group having 1 to 10 carbon atoms as the alkylene group include a methylene group, an ethane-1,2-diyl group (ethylene group), a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, and a butane-1,10-diyl group.

[0137] R P2 As the divalent saturated cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, the above-mentioned R P1 Examples of the alkyl group include a group in which one hydrogen atom has been removed from a saturated cycloaliphatic hydrocarbon group having 3 to 20 carbon atoms.

[0138] R P2 As the divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, the above-mentioned R P1 Examples of the aromatic hydrocarbon group include a group in which one hydrogen atom has been removed from an aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0139] R b0 Examples of the aromatic hydrocarbon group which may have a substituent as R include a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, and a biphenyl group. b0 The substituents that the aromatic hydrocarbon group may have are R b0 The substituents are the same as those that the alicyclic hydrocarbon group may have.

[0140] In formula (b0-1), R b2 , and R b3 are each independently an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. Rb2 , and R b3 The optionally substituted aryl group as R b1 The same applies to the aryl group which may have a substituent as R. b2 , and R b3 Specific preferred examples of the aryl group which may have a substituent as the substituent include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. Among these, a phenyl group and a naphthyl group are preferred, and a phenyl group is more preferred.

[0141] R b2 , and R b3 The alkyl group, which may have a substituent, as R may be linear or branched. b2 , and R b3 The alkyl group which may have a substituent as the group is preferably an alkyl group having 1 to 30 carbon atoms. R b2 , and R b3 The alkenyl group, which may have a substituent as R, may be linear or branched. b2 , and R b3 The alkenyl group which may have a substituent as the group is preferably an alkyl group having 2 to 30 carbon atoms.

[0142] R b2 , and R b3 The substituents that the aryl group, alkyl group, and alkenyl group may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, an oxo group (=O), a cyano group, an amino group, an aryl group, the groups represented by the above formulas (ca-r-1) to (ca-r-7), and the above -SO2-R b0 etc.

[0143] R b2 , and R b3Among the aryl group which may have a substituent, the alkyl group which may have a substituent, and the alkenyl group which may have a substituent, the aryl group which may have a substituent is preferred. When the aryl group has a substituent, the substituent may be a fluorine atom, a fluorinated alkyl group, or the aforementioned -SO2-R b0 A group represented by the following formula is preferred, and a fluorine atom, a fluorinated alkyl group, and a methanesulfonyl group (mesyl group) are more preferred. Therefore, R b2 , and R b3 Particularly preferred are an unsubstituted aryl group, an aryl group having a fluorine atom, an aryl group having a fluorinated alkyl group, and an aryl group having a methanesulfonyl group (mesyl group).

[0144] In formula (b0-1), R b1 ~R b3 Two of R may be bonded to each other to form a ring together with the sulfur atom. b1 ~R b3 If two of the bonds are bonded to each other, R b1 ~R b3 Two of them are heteroatoms such as sulfur, oxygen, and nitrogen atoms, or -SO-, -SO2-, -O-SO2-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, or -N(R N )- or other groups. R N is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0145] The ring formed is preferably a sulfur atom-containing monocyclic ring having 3 to 10 members, more preferably a 5 to 7 membered monocyclic ring. R b1 ~R b3 The monocyclic ring formed by bonding two of these may be condensed with two or more other rings. Examples of the other rings include a benzene ring, a cycloalkane ring, various aromatic heterocyclic rings, and various aliphatic heterocyclic rings, with a benzene ring being preferred.

[0146] R b1 ~R b3Specific examples of rings formed by bonding two of these rings together include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0147] R b1 ~R b3 The ring formed by bonding two of these may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, an oxo group (=O), a cyano group, and an amino group. Among these substituents, a halogen atom and a halogenated alkyl group are preferred, and a fluorine atom and a fluorinated alkyl group are more preferred.

[0148] The cation moiety in the sulfonium salt represented by formula (b0-1) is preferably a cation represented by the following formula (ca-b01-1). [ka]

[0149] In formula (ca-b01-1), R b2 , and R b3 R are each independently an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. b2 , and R b3 may be bonded to each other to form a ring together with the sulfur atom in the formula. 011 is a fluorine atom or a fluorinated alkyl group. 011 is a substituent. nb is an integer of 1 or greater. pb is an integer of 0 or greater. qb is an integer of 0 or greater and 3 or less, provided that nb + pb ≦ qb × 2 + 5.

[0150] In formula (ca-b01-1), R b2 , and R b3 is R in formula (b0-1) b2 , and R b3is the same as:

[0151] In formula (ca-b01-1), X 011 is a fluorine atom or a fluorinated alkyl group. 011 The fluorine atom and fluorinated alkyl group as are the same as the fluorine atom and fluorinated alkyl group that Rb1 in formula (b0-1) may have as a substituent.

[0152] In formula (ca-b01-1), R 011 is a substituent. Examples of the substituent include an alkyl group, a halogen atom other than a fluorine atom, a halogenated alkyl group other than a fluorinated alkyl group, an oxo group (=O), a cyano group, an amino group, an aryl group, the groups represented by the above formulas (ca-r-1) to (ca-r-7), and the above -SO2-R b0 etc. Among these substituents, -SO2-R b0 is preferred, and a methanesulfonyl group (mesyl group) is more preferred.

[0153] In formula (ca-b01-1), nb is an integer of 1 or more, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In formula (ca-b01-1), pb is an integer of 0 or more, and preferably an integer of 0 or more and 2 or less. In formula (ca-b01-1), qb is an integer of 0 or more and 3 or less.

[0154] As the cation moiety in the sulfonium salt represented by formula (b0-1), the following cations are particularly preferred. [ka]

[0155] [ka]

[0156] (Regarding the anion moiety in formula (b0-1)) In formula (b0-1), X 01 - is a counter anion for the cation as the cationic moiety. 01 - The anion as X is not particularly limited as long as the desired effect is not impaired. 01 - The anion as the cation can be appropriately selected from anions constituting onium salts that have been conventionally incorporated into various photosensitive compositions. X 01 - The anion represented by the formula (b0-1-an1) is an anion represented by the formula (b0-1-an1): Examples include anions represented by the following formula (b0-1-an2) and anions represented by the following formula (b0-1-an3).

[0157] [ka]

[0158] In the formulas (b0-1-an1), (b0-1-an2), and (b0-1-an3), R 101 , and R 104 ~R 108 R each independently represents an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 104 and R 105 may be bonded to each other to form a ring. 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 101 is a divalent linking group containing an oxygen atom or a single bond. 101 ~V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group. 101 , and L 102 are each independently a single bond or an oxygen atom. 103 ~L 105 are each independently a single bond, —CO—, or —SO2—.

[0159] Anion represented by the formula (b0-1-an1) In the formula (b0-1-an1), R 101 represents an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group.

[0160] R 101 The cyclic group as may be a cyclic hydrocarbon group or a heterocyclic group, and is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group. The cyclic aliphatic hydrocarbon group and the aliphatic heterocyclic group may have one or more unsaturated bonds. The cyclic aliphatic hydrocarbon group is preferably a saturated cyclic aliphatic hydrocarbon group. The aliphatic heterocyclic group is preferably a saturated aliphatic heterocyclic group.

[0161] R 101 The number of carbon atoms in the aromatic hydrocarbon group and aromatic heterocyclic group as defined above is preferably from 3 to 30, more preferably from 5 to 30, even more preferably from 5 to 20, and particularly preferably from 6 to 18. The number of carbon atoms in the aromatic hydrocarbon group and aromatic heterocyclic group does not include the number of carbon atoms of substituents. R 101 Examples of the aromatic hydrocarbon group include a phenyl group, a fluorenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, and a biphenyl group. R 101 Examples of heteroatoms that may be contained in the aromatic heterocyclic group include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0162] R 101 The alicyclic hydrocarbon group as the alkyl group preferably has 3 or more and 20 or less carbon atoms, and more preferably has 3 or more and 12 or less carbon atoms. The cycloaliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic cycloaliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms. Specific examples of the monocyclic cycloaliphatic hydrocarbon group include a cyclopentyl group and a cyclohexyl group. The polycyclic cycloaliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane. The polycycloalkane preferably has 7 to 30 carbon atoms. Suitable examples of the polycycloalkane include polycycloalkanes having a bridged ring polycyclic skeleton, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a fused ring polycyclic skeleton, such as a cyclic group having a steroid skeleton. Specific examples of the polycyclic cycloaliphatic hydrocarbon group include an adamantyl group and a norbornyl group.

[0163] The cyclic group represented by R101 may be a fused ring group containing a fused ring formed by condensing an aliphatic hydrocarbon ring with an aromatic ring. Examples of the fused ring include a fused ring formed by condensing one or more aromatic rings with a polycycloalkane having a bridged ring polycyclic skeleton. Specific examples of bridged ring polycycloalkanes include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. As the fused ring group, a group containing a fused ring in which two or three aromatic rings are fused to a bicycloalkane is preferred, and a group containing a fused ring in which two or three aromatic rings are fused to a bicyclo[2.2.2]octane is more preferred. R 101 Specific examples of the fused cyclic group as the condensed ring group include those represented by the following formulae (r-br-1) to (r-br-2). In the formulae, * represents Y in formula (b0-1-an1). 101 represents a bond bonded to

[0164] [ka]

[0165] R 101 The cyclic group as may be a lactone-containing cyclic group represented by the above formulae (a2-r-1) to (a2-r-7), an —SO2- containing cyclic group represented by the above formulae (a5-r-1) to (a5-r-4), or a heterocyclic group represented by the above formulae (r-hr-1) to (r-hr-16).

[0166] R 101 Examples of the substituent that the cyclic group may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxo group (=O), and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group. The alkoxy group as a substituent is preferably an alkoxy group having from 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, or a tert-butyloxy group, and still more preferably a methoxy group or an ethoxy group. As the halogen atom as a substituent, a bromine atom, an iodine atom, and a fluorine atom are preferred, and a bromine atom and an iodine atom are more preferred. Examples of halogenated alkyl groups as substituents include the aforementioned alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been substituted with halogen atoms.

[0167] R 101 The substituent that the cyclic group may have is preferably a hydroxyl group, an alkoxy group, a bromine atom, or an iodine atom, more preferably a hydroxyl group, a bromine atom, or an iodine atom.

[0168] R 101 The alkyl group as may be linear or branched.

[0169] The linear alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 15 or less carbon atoms, and particularly preferably 1 or more and 10 or less carbon atoms. Specific examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an icosyl group.

[0170] The branched alkyl group preferably has 3 or more and 20 or less carbon atoms, more preferably 3 or more and 15 or less carbon atoms, and particularly preferably 3 or more and 10 or less carbon atoms. Specific examples of branched alkyl groups include a 1-methylethyl group (isopropyl group), a 1-methylpropyl group (sec-butyl group), a 2-methylpropyl group (isobutyl group), a 1-methylbutyl group (sec-pentyl group), a 2-methylbutyl group, a 3-methylbutyl group (isopentyl group), a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group (isohexyl group).

[0171] R 101 The alkenyl group as may be straight-chain or branched.

[0172] R 101 The number of carbon atoms in the alkenyl group as the alkyl group is preferably 2 to 10, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Specific examples of linear alkenyl groups include vinyl, 2-propenyl (allyl), 1-propenyl, 3-butenyl, 2-butenyl, and 1-butenyl. Specific examples of branched alkenyl groups include 1-methylvinyl, 1-methyl-2-propenyl, and 2-methyl-2-propenyl. The alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group, a 2-propenyl group (allyl group), or a 1-propenyl group, and particularly preferably a vinyl group.

[0173] R 101 The substituents that the alkyl group and alkenyl group may have include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxo group (=O), a nitro group, an amino group, and the above-mentioned R 101 Examples of such cyclic groups include:

[0174] Among the groups described above, R 101 In addition, from the viewpoint of reducing roughness, R 101 is more preferably a polycyclic group which may have a substituent, and even more preferably a bridged ring polycyclic group which may have a substituent. The polycyclic group may be a polycyclic hydrocarbon group or a polycyclic heterocyclic group. In addition, from the viewpoint of improving sensitivity, R 101 is preferably a cyclic group having an iodine atom or a bromine atom, and more preferably an aromatic hydrocarbon group having an iodine atom or a bromine atom.

[0175] Examples of polycyclic hydrocarbon groups include groups in which one hydrogen atom has been removed from a polycycloalkane having a polycyclic skeleton, and groups in which one hydrogen atom has been removed from a fused ring in which an aromatic hydrocarbon ring is fused to a polycycloalkane. Examples of polycycloalkanes include polycycloalkanes having a bridged ring polycyclic skeleton such as adamantane, norbornane (bicycloheptane), and bicyclooctane; and polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton. Specific examples of suitable polycyclic aliphatic hydrocarbon groups include an adamantyl group and a norbornyl group.

[0176] Examples of the group in which one hydrogen atom has been removed from a fused ring in which an aromatic ring is fused to a polycycloalkane include groups in which one hydrogen atom has been removed from a fused ring in which the above-mentioned polycycloalkane is fused to a benzene ring.

[0177] As the polycyclic heterocyclic group, a bridged ring polycyclic heterocyclic group is preferred, and a bridged ring polycyclic group, i.e., an -SO2- containing cyclic group represented by the above formula (a5-r-1), is more preferred.

[0178] In the formula (b0-1-an1), Y 101 is a single bond or a divalent linking group containing an oxygen atom. Y 101 The divalent linking group containing an oxygen atom as the group may contain, in addition to carbon, hydrogen and oxygen atoms, heteroatoms other than oxygen atoms such as nitrogen atoms, sulfur atoms, phosphorus atoms and silicon atoms. Examples of the divalent linking group containing an oxygen atom include divalent oxygen atom-containing groups such as -O-, -CO-O-, -CO-NH-, -CO-, -O-CO-O-, and -SO2-; and combinations of one or more divalent oxygen atom-containing groups with one or more alkylene groups. Examples of the divalent linking group containing an oxygen atom include linking groups represented by the following formulae (y-al-1) to (y-al-7).

[0179] -V ’101 -CO-OV ’102 - (y-al-1) -V ’101 -CO-OV ’102 -O-CO- (y-al-2) -V ’101 -O-CO- (y-al-3) -V ’101 -O- (y-al-4) -V ’101 -OV ’102 -O-CO- (y-al-5) -V ’101 -SO2-OV ’102 - (y-al-6) -V ’101 -SO2-OV ’102 -O-CO- (y-al-7)

[0180] In formulas (y-al-1) to (y-al-7), V ’101is a single bond or an alkylene group having 1 to 5 carbon atoms. ’102 is a divalent saturated hydrocarbon group having from 1 to 30 carbon atoms.

[0181] V ’102 The divalent saturated hydrocarbon group as V is preferably an alkylene group having 1 to 30 carbon atoms. ’102 The alkylene group as the alkylene group preferably has 1 or more and 10 or less carbon atoms, and more preferably has 1 or more and 5 or less carbon atoms.

[0182] V ’101 an alkylene group as ’102 The alkylene group as may be linear or branched, and is preferably linear. V ’101 an alkylene group as ’102 Specific preferred examples of the alkylene group include a methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; an ethylene group [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)C Examples include alkylethylene groups such as H2-; trimethylene group (n-propylene group) [-CH2CH2CH2-]; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; tetramethylene group [-CH2CH2CH2CH2-]; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and pentamethylene group [-CH2CH2CH2CH2CH2-].

[0183] V ’101 , and V ’102Some methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having from 5 to 10 carbon atoms. Preferred aliphatic cyclic groups are a cyclohexylene group, an adamantane-1,5-diyl group, and an adamantane-2,6-diyl group.

[0184] Y 101 As the alkyl group, a single bond and an ester bond (—CO—O—) are preferred.

[0185] In the formula (b0-1-an1), V 101 is a single bond, an alkylene group, or a fluorinated alkylene group. 101 The alkylene group and fluorinated alkylene group represented by V preferably have 1 or more and 4 or less carbon atoms. 101 The fluorinated alkylene group as V 101 and groups in which some or all of the hydrogen atoms in the alkylene group have been substituted with fluorine atoms. V 101 is preferably a single bond or a fluorinated alkylene group having 1 to 3 carbon atoms.

[0186] In the formula (b0-1-an1), R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0187] Anion represented by the formula (b0-1-an2) In the formula (b0-1-an2), R 104 , and R 105 are each independently an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. R 104 , and R 105 The optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as R101 The same applies to the optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as the above-mentioned groups. However, R 104 , and R 105 may be bonded to each other to form a ring. R 104 , and R 105 As the alkyl group, an alkyl group which may have a substituent is preferable, and an alkyl group and a fluorinated alkyl group are more preferable. The alkyl group preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 7 or less carbon atoms, and even more preferably 1 or more and 3 or less carbon atoms. R 104 , and R 105 The number of carbon atoms in the alkyl group as a photoacid generator (B) is preferably as small as possible from the viewpoint of the solubility of the photoacid generator (B) in a solvent. R 104 , and R 105 When is a fluorinated alkyl group, the ratio of the number of fluorine atoms to the total number of fluorine atoms and the number of hydrogen atoms in the fluorinated alkyl group (fluorination rate) is preferably as high as possible in terms of the strength of the acid generated by the photoacid generator (B). The fluorination rate is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and even more preferably 100%. V in the formula (b0-1-an2) 102 , and V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group. V 102 , and V 103 The alkylene group and the fluorinated alkylene group are represented by V in formula (b0-1-an1). 101 The same applies to alkylene groups and fluorinated alkylene groups. In the formula (b0-1-an2), L 101 , and L 102 are each independently a single bond or an oxygen atom.

[0188] Anion represented by the formula (b0-1-an3) In the formula (b0-1-an3), R106 ~R 108 are each independently an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. R 106 ~R 108 The optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as R 101 The same applies to the optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as the above-mentioned groups. In the formula (b0-1-an3), L 103 ~L 105 are each independently a single bond, —CO—, or —SO2—.

[0189] X in formula (b0-1) 01 - Among the above anions, the anion represented by the formula (b0-1-an1) is preferred.

[0190] The anion represented by formula (b0-1-an1) is preferably the following anion. [ka]

[0191] X in formula (b0-1) 01 - From the viewpoint of improving sensitivity, the anion represented by the following formula (b0-1-an4) is preferred. [ka]

[0192] In the formula ((b0-1-an4), X 0 is a bromine atom or an iodine atom. mis a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 or more and 5 or less. nb2 is an integer of 0 or more and 4 or less. (nb1 + nb2) is an integer of 1 or more and 5 or less. Yb 0 is a divalent linking group or a single bond. 0 is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom.

[0193] In the formula (b0-1-an4), X 0 is a bromine atom or an iodine atom, and is preferably an iodine atom.

[0194] In the formula (b0-1-an4), R m R is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom, and is preferably a hydroxy group. m The number of carbon atoms in the alkyl group represented by R is preferably 1 or more and 5 or less. m As the alkyl group for , a methyl group and an ethyl group are preferred.

[0195] In the formula (b0-1-an4), nb1 is an integer of 1 or more and 5 or less. nb2 is an integer of 0 or more and 4 or less. (nb1+nb2) is 1 or more and 5 or less. nb1 is preferably an integer of 1 or more and 3 or less, more preferably 2 or 3, and even more preferably 3. nb2 is preferably an integer of 0 or more and 3 or less, more preferably 0 or 1, and even more preferably 0.

[0196] In the formula (b0-1-an4), Yb 0 is a divalent linking group or a single bond. 0 The divalent linking group as is preferably a divalent linking group containing an oxygen atom. Yb 0The divalent linking group containing an oxygen atom as the group may contain, in addition to carbon, hydrogen and oxygen atoms, heteroatoms other than oxygen atoms such as nitrogen atoms, sulfur atoms, phosphorus atoms and silicon atoms. Examples of the divalent linking group containing an oxygen atom include divalent oxygen atom-containing groups such as -O-, -CO-O-, -CO-NH-, -CO-, -O-CO-O-, and -SO2-; and combinations of one or more divalent oxygen atom-containing groups with one or more alkylene groups.

[0197] In the above formula (b0-1-an4), Vb 0 is an alkylene group, a fluorinated alkylene group, or a single bond. Vb 0 The number of carbon atoms in the alkylene group and fluorinated alkylene group represented by Vb is preferably 1 or more and 4 or less, and more preferably 1 or more and 3 or less. 0 The fluorinated alkylene group as mentioned above includes groups in which some or all of the hydrogen atoms in the alkylene group have been substituted with fluorine atoms. Vb 0 is preferably an alkylene group having from 1 to 4 carbon atoms, a fluorinated alkylene group having from 1 to 4 carbon atoms, or a single bond, and more preferably an alkylene group having from 1 to 3 carbon atoms in which some of the hydrogen atoms have been substituted with fluorine atoms, or a single bond.

[0198] In the formula (b0-1-an4), R 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. 0 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0199] X in formula (b0-1) 01 - From the viewpoint of improving sensitivity, anions represented by the following formula (b0-an0) are more preferred. [ka]

[0200] In the formula (b0-an0), X 0 is a bromine atom or an iodine atom. Rm is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 or more and 5 or less. nb2 is an integer of 0 or more and 4 or less. (nb1 + nb2) is an integer of 1 or more and 5 or less. L 01 , and L 02 each independently represents a single bond, an alkylene group, -O-, -CO-, -O-CO-, -SO2-, or -NR a -CO-, -NR a -, -C(R a )2-NR a - or -C(R a )(N(R a )2)-. R a are each independently a hydrogen atom or an alkyl group, and z is an integer of 0 or more and 10 or less. 0 is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom.

[0201] In the formula (b0-an0), X 0 , R m , nb1, nb2, Vb 0 , and R 0 are the X in formula (b0-1-an4), respectively. 0 , R m , nb1, nb2, Vb 0 , and R 0 is the same as:

[0202] In the formula (b0-an0), L 01 , and L 02 each independently represents a single bond, an alkylene group, -O-, -CO-, -O-CO-, -SO2-, or -NR a -CO-, -NR a -, -C(R a )2-NR a - or -C(R a )(N(R a )2)-. R aare each independently a hydrogen atom or an alkyl group. L 01 , and L 02 The number of carbon atoms in the alkylene group as R and the number of carbon atoms in the alkyl group as R are each preferably 1 or more and 4 or less, and more preferably 1 or more and 3 or less.

[0203] In the formula (b0-an0), L 01 , and L 02 Preferably, either one of L is —O—CO—; 01 is -O-CO-, and L 02 is more preferably a single bond or —O—CO—.

[0204] In the formula (b0-an0), -L 01 -(CH2) z -L 02 -Vb 0 -Is -CO-O-Vb 0 -, -O-CO-Vb 0 - or -CO-O-(CH2) z -CO-O-Vb 0 - is preferred.

[0205] In the above general formula (b0-an0), z is an integer of 0 or more and 10 or less, preferably an integer of 0 or more and 5 or less, and more preferably an integer of 0 or more and 3 or less.

[0206] Suitable examples of the anion represented by formula (b0-1-an4) include the following anions.

[0207] [ka]

[0208] The sulfonium salt represented by formula (b0-1) is preferably a sulfonium salt represented by the following formula (b0-1-1). [ka]

[0209] In formula (b0-1-1), R b2 , and R b3 R are each independently an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. b2 , and R b3 may be bonded to each other to form a ring together with the sulfur atom in the formula. 011 is a fluorine atom or a fluorinated alkyl group. 011 is a substituent. nb is an integer of 1 or more. pb is an integer of 0 or more. qb is an integer of 0 or more and 3 or less, provided that nb + pb ≦ qb × 2 + 5. X 01 - is the counter anion.

[0210] The anion moiety in formula (b0-1-1) is the same as the anion moiety in formula (b0-1). The cation moiety in formula (b0-1-1) is the same as the cation moiety in formula (ca-b01-1).

[0211] As specific examples of the sulfonium salt represented by formula (b0-1) explained above, the following sulfonium salts can be mentioned.

[0212] [ka]

[0213] [ka]

[0214] The photoacid generator (B) may contain, in addition to the photoacid generator (B1) containing a sulfonium cation having a fluorine atom, another photoacid generator (B2) that does not fall under the category of the photoacid generator (B1). The type of the other photoacid generator (B2) is not particularly limited as long as the desired effect is not impaired. Examples of other photoacid generators (B2) include various types of photoacid generators such as onium salt-based acid generators and oxime sulfonate-based acid generators that do not fall under the category of photoacid generator (B1); diazomethane-based acid generators such as bisalkyl- or bisarylsulfonyldiazomethanes and poly(bissulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.

[0215] The ratio of the mass of the photoacid generator (B1) to the mass of the photoacid generator (B) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0216] The amount of the photoacid generator (B) used is not particularly limited as long as the desired effect is not impaired, and is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 15 to 40 parts by mass, per 100 parts by mass of the silicon-containing resin (A).

[0217] <Crosslinking agent (C)> The photosensitive composition may contain a crosslinking agent (C) capable of crosslinking the silicon-containing resin (A) by the action of the acid generated by the photoacid generator (B). Examples of the crosslinking agent (C) include melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, glycoluril-based crosslinking agents, phenol-based crosslinking agents, and epoxy-based crosslinking agents. In the following description, "lower" means having 1 to 5 carbon atoms.

[0218] Examples of the melamine-based crosslinking agent include compounds in which some or all of the hydrogen atoms in the amino groups of melamine have been substituted with hydroxymethyl groups, and compounds in which some or all of the hydrogen atoms in the amino groups of melamine have been substituted with lower alkoxymethyl groups. Specifically, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine are preferred, with hexamethoxymethylmelamine being more preferred.

[0219] Examples of the urea-based crosslinking agent include a compound in which some or all of the hydrogen atoms in the amino groups of urea are substituted with hydroxymethyl groups, and a compound in which some or all of the hydrogen atoms in the amino groups of urea are substituted with lower alkoxymethyl groups. Specifically, bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea, etc. are preferred, and bismethoxymethylurea is more preferred.

[0220] The alkylene urea crosslinking agent may be a compound represented by the following formula (CA-1).

[0221] [ka] (In formula (CA-1), Rc 1 and Rc 2 Rc is independently a hydroxyl group or a lower alkoxy group. 3 and Rc 4 are each independently a hydrogen atom, a hydroxyl group, or a lower alkoxy group, and vc is an integer of 0 or more and 2 or less.

[0222] Rc 1 and Rc 2 When Rc is a lower alkoxy group, the lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The lower alkoxy group may be a linear alkoxy group or a branched alkoxy group. 1 and Rc 2and may be the same or different from each other, and are more preferably the same. Rc 3 and Rc 4 When Rc is a lower alkoxy group, the lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The lower alkoxy group may be a linear alkoxy group or a branched alkoxy group. 3 and Rc 4 and may be the same or different from each other, and are more preferably the same. vc is preferably 0 or 1. As the alkylene urea crosslinking agent, a compound in which vc is 0 (ethylene urea crosslinking agent) and / or a compound in which vc is 1 (propylene urea crosslinking agent) are particularly preferred.

[0223] Specific examples of the alkylene urea-based crosslinking agent include ethylene urea-based crosslinking agents such as monohydroxymethylated ethylene urea, dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, and dibutoxymethylated ethylene urea; propylene urea-based crosslinking agents such as monoethoxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monodibutoxymethylated propylene urea, and dibutoxymethylated propylene urea; 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0224] Examples of glycoluril crosslinking agents include glycoluril derivatives in which the N-position is substituted with one or both of a hydroxyalkyl group and an alkoxyalkyl group having from 1 to 4 carbon atoms. The glycoluril derivatives can be obtained by condensation reaction of glycoluril with formalin and then by reacting the product with a lower alcohol. Specific examples of glycoluril-based crosslinking agents include hydroxymethylated glycolurils such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, and tetrahydroxymethylated glycoluril; methoxymethylated glycolurils such as monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, and tetramethoxymethylated glycoluril; ethoxymethylated glycolurils such as monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, and tetraethoxymethylated glycoluril; propoxymethylated glycolurils such as monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, and tetrapropoxymethylated glycoluril; and butoxymethylated glycolurils such as monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril.

[0225] The phenol-based crosslinking agent is not particularly limited as long as it is a compound having multiple phenol nucleus structures in the same molecule, and the adjacent positions to the bonding position of the phenol-based hydroxyl group on the aromatic ring are substituted with methylol groups and / or alkoxyalkyl groups. The presence of multiple phenol nucleus structures improves crosslinking reactivity. The number of phenolic nucleus structures is preferably 2 or more and 5 or less, more preferably 2 or more and 4 or less, and even more preferably 2 or 3.

[0226] The epoxy-based crosslinking agent is not particularly limited as long as it has an epoxy group, and can be arbitrarily selected from known epoxy-based crosslinking agents. As the epoxy-based crosslinking agent, a crosslinking agent having two or more epoxy groups is preferred in terms of good crosslinking reactivity. The number of epoxy groups in one molecule of the epoxy-based crosslinking agent is preferably 2 or more, more preferably 2 or more and 4 or less, and most preferably 2.

[0227] The crosslinking agent (C) is preferably a crosslinking agent (C1) having a methylol group and / or an alkoxyalkyl group, and among them, a crosslinking agent selected from the group consisting of glycoluril crosslinking agents and phenolic crosslinking agents is more preferred. Suitable examples of such crosslinking agents include compounds represented by the following formula (c1-1): [ka] (In formula (c1-1), s1 is an integer of 1 or more and 10 or less. R C0 is a glycoluril structure or a polynuclear phenol structure. C1 is an alkyl group having 1 to 5 carbon atoms, or a hydrogen atom.

[0228] s1 is an integer of 1 or more and 10 or less, preferably an integer of 2 or more and 10 or less, and more preferably an integer of 4 or more and 9 or less. R C0 The glycoluril structure in C0 -1) refers to the structure represented by

[0229] [ka]

[0230] R C0 The polynuclear phenol structure as defined above is a structure containing two or more structures selected from the group consisting of a phenol structure and a naphthol structure.

[0231] Specific examples of suitable crosslinking agents (C) include the following compounds: [ka]

[0232] The crosslinking agent (C) may be used alone or in combination of two or more kinds. The amount of crosslinking agent (C) used is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 40 parts by mass or less, even more preferably 5 parts by mass or more and 30 parts by mass or less, and particularly preferably 5 parts by mass or more and 25 parts by mass or less, per 100 parts by mass of silicon-containing resin (A).

[0233] <Base component (D)> The photosensitive composition preferably further contains a base component (D) that traps the acid generated by exposure to light. By adding the base component (D) to the photosensitive composition, the diffusion of the acid generated by the photoacid generator (B) is controlled. Examples of the base component (D) include a photodegradable base (D1) (hereinafter referred to as "component (D1)") that decomposes upon exposure and loses its acid diffusion controllability, and a nitrogen-containing organic compound (D2) (hereinafter referred to as "component (D2)") that does not fall under the category of component (D1). Among these, the photodegradable base component (D1) is preferred because it is likely to enhance all of the properties of high sensitivity, reduced roughness, and suppressed occurrence of coating defects.

[0234] [Component (D1)] By including the component (D1) in the photosensitive composition, the contrast between exposed and unexposed areas can be improved when a patterned resin film is formed using the photosensitive composition. The component (D1) is not particularly limited as long as it is a compound that decomposes upon exposure and loses its acid diffusion controllability. Preferred examples of the component (D1) include a compound represented by the following formula (d1-1) (hereinafter referred to as "component (d1-1)"), a compound represented by the following formula (d1-2) (hereinafter referred to as "component (d1-2)"), and a compound represented by the following formula (d1-3) (hereinafter referred to as "component (d1-3)"). The components (d1-1), (d1-2), and (d1-3) lose their basicity in the exposed areas of the coating film of the photosensitive composition and therefore do not act as quenchers, whereas the components (d1-1), (d1-2), and (d1-3) act as quenchers in the unexposed areas of the coating film of the photosensitive composition.

[0235] [ka]

[0236] In formula (d1-1), Rd 1 represents an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group, which is bonded to the carbonyl group in formula (d1-1) via a single bond or a linking group represented by formula (y-al-1) to formula (y-al-5) described above.

[0237] In formula (d1-2), Rd 2 is a cyclic group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. 2 In this case, no fluorine atom is bonded to the carbon atom adjacent to the sulfur atom.

[0238] In formula (d1-3), Rd 3 , and Rd 4 each independently represents a cyclic group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. 1 is a single bond or a divalent linking group.

[0239] In formulas (d1-1) to (d1-3), m is an integer of 1 or more, and M m+ are each independently an m-valent organic cation.

[0240] (Component (d1-1)) Anion section In formula (d1-1), Rd 1represents an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group, which is bonded to the carbonyl group in formula (d1-1) via a single bond or a linking group represented by formula (y-al-1) to formula (y-al-5) described above. The cyclic group which may have a substituent, the alkyl group which may have a substituent, and the alkenyl group which may have a substituent in formula (d1-1) are the same as R ’201 The same applies to the optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as mentioned above. Road 1 As the alkyl group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aliphatic cyclic group, or an optionally substituted alkyl group, which is bonded to the carbonyl group in formula (d1-1) via a single bond or a linking group represented by formulas (y-al-1) to (y-al-5) described above, is preferred. Substituents that these groups may have include a hydroxyl group, an oxo group (=O), an alkyl group, an aryl group, a fluorine atom, an iodine atom, a bromine atom, a fluorinated alkyl group, and the lactone-containing cyclic groups represented by the above formulas (a2-r-1) to (a2-r-7). The aromatic hydrocarbon group includes a phenyl group and a naphthyl group. As the aliphatic cyclic group, a group in which one hydrogen atom has been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane is more preferred. The number of carbon atoms in the alkyl group is preferably from 1 to 10. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and branched alkyl groups such as 1-methylethyl (isopropyl), 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1-methylbutyl (sec-pentyl), 2-methylbutyl, 3-methylbutyl (isopentyl), 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl (isohexyl).

[0241] When the alkyl group is a fluorinated alkyl group having a fluorine atom as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0242] Examples of anions suitable for the anion moiety that constitutes the component (d1-1) include the following anions. [ka]

[0243] Cation part In formula (d1-1), M m+ is an m-valent organic cation. M m+ Suitable examples of organic cations as the cation include the following cations: [ka]

[0244] [ka]

[0245] [ka]

[0246] In the following formula, g2 and g3 are the number of repeating methylene groups, and g2 and g3 are each an integer of 0 to 20. [ka]

[0247] [ka]

[0248] [ka]

[0249] [ka]

[0250] [ka]

[0251] Among the above cations, cations corresponding to the cation moiety in formula (b0-1) are preferred. That is, the photosensitive composition preferably contains, as the base component (D), a sulfonium salt containing a sulfonium cation having a fluorine atom. For this reason, the following cations are preferred as the cationic moiety: [ka]

[0252] From the viewpoint of improving sensitivity, the component (d1-1) preferably contains a compound represented by the following formula (d0-1) (hereinafter also referred to as "component (D0)"): [ka]

[0253] In formula (d0-1), X 0 is a bromine atom or an iodine atom. Rm is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nd1 is an integer of 1 or more and 5 or less. nd2 is an integer of 0 or more and 4 or less. (nd1 + nd2) is an integer of 1 or more and 5 or less. Yd 0 is a divalent linking group or a single bond. Mm+ is an m-valent organic cation. m is an integer of 1 or greater.

[0254] Anion part of (D0) component In formula (d0-1), X 0 is a bromine atom or an iodine atom, and is preferably an iodine atom.

[0255] In formula (d0-1), R m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. m As the alkyl group, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group and an ethyl group are more preferred.

[0256] In formula (d0-1), nd1 is an integer of 1 or more and 5 or less. nd2 is an integer of 0 or more and 4 or less. (nd1+nd2) is 1 or more and 5 or less. nd1 is preferably an integer of 1 or more and 3 or less. From the viewpoint of radiation absorption, nd1 is more preferably 2 or 3, and even more preferably 3. nd2 is preferably an integer of 0 or more and 3 or less, more preferably 0 or 1, and even more preferably 0.

[0257] In formula (d0-1), Yd 0is a divalent linking group or a single bond. 0 The divalent linking group as is preferably a divalent linking group containing an oxygen atom. Yd 0 The divalent linking group containing an oxygen atom as the group may contain, in addition to carbon, hydrogen and oxygen atoms, heteroatoms other than oxygen atoms such as nitrogen atoms, sulfur atoms, phosphorus atoms and silicon atoms. Examples of the divalent linking group containing an oxygen atom include divalent oxygen atom-containing groups such as -O-, -CO-O-, -CO-NH-, -CO-, -O-CO-O-, and -SO2-; and combinations of one or more divalent oxygen atom-containing groups with one or more alkylene groups. Yd 0 is preferably a divalent linking group containing an oxygen atom or a single bond, and more preferably a single bond.

[0258] Suitable examples of the anion moiety in component (D0) include the following anions. [ka]

[0259] ·Cation part of component (D0) In formula (d0-1), M m+ is an m-valent organic cation. m+ A suitable example of is M in formula (d1-1). m+ This is similar to the preferred example of

[0260] Specific examples of suitable components (D0) include the following compounds: Component (D0) is not limited to the following compounds. [ka]

[0261] The component (d1-1) may be used alone or in combination of two or more.

[0262] (Component (d1-2)) Anion section In formula (d1-2), Rd 2 represents an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. Road 2 The optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as R ’201 The same applies to the optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as mentioned above. However, Rd 2 In this case, no fluorine atom is bonded to the carbon atom adjacent to the sulfur atom, which results in the anion of the (d1-2) component being a moderately weakly acidic anion, thereby improving the quenching ability of the (d1-2) component. Road 2 As the alkyl group, an alkyl group which may have a substituent and an aliphatic cyclic group which may have a substituent are preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 3 to 10. As the aliphatic cyclic group, groups in which one hydrogen atom has been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc., and groups in which one hydrogen atom has been removed from camphor, etc., are preferred. Such aliphatic cyclic groups may have a substituent. Road 2 The hydrocarbon group represented by may have a substituent. In formula (d1-1), Rd 1 Examples of the substituents that may be contained in the hydrocarbon group include the same groups as those that may be contained in the hydrocarbon group.

[0263] Specific examples of anions suitable for the anion moiety that constitutes the component (d1-2) include the following anions. [ka]

[0264] Cation part In formula (d1-2), M m+ is an m-valent organic cation.m+ is M in formula (d1-1) m+ is the same as:

[0265] The component (d1-2) may be used alone or in combination of two or more.

[0266] (Component (d1-3)) Anion section In formula (d1-3), Rd 3 represents an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. Road 3 The optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as R ’201 The same applies to the optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as mentioned above. Road 3 As the fluorine atom-containing alkyl group, a fluorine atom-containing cyclic group, an alkyl group which may have a substituent, and an alkenyl group which may have a substituent are preferable, and a fluorinated alkyl group is more preferable. 1 The same fluorinated alkyl groups as those mentioned above are preferred.

[0267] In formula (d1-3), Rd 4 represents an optionally substituted cyclic group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. Road 4 The optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as R ’201 The same applies to the optionally substituted cyclic group, optionally substituted alkyl group, and optionally substituted alkenyl group as mentioned above. Road 4 The number of carbon atoms in the alkyl group Rd is preferably 1 or more and 5 or less. 4The alkyl group may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group. Road 4 A part of the hydrogen atoms in the alkyl group may be substituted with a hydroxyl group, a cyano group, or the like.

[0268] Road 4 Preferred alkenyl groups as the alkyl group include a vinyl group, a 2-propenyl group (allyl group), a 1-propenyl group, a 1-methyl-2-propenyl group, and a 2-methyl-2-propenyl group.

[0269] Road 4 Preferred cyclic groups as the aryl group include monocycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, and alicyclic groups in which one hydrogen atom has been removed from a polycycloalkane; and aromatic groups such as a phenyl group and a naphthyl group.

[0270] In formula (d1-3), Yd 1 is a single bond or a divalent linking group. Yd 1 The divalent linking group as is not particularly limited, but examples thereof include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom, etc. The divalent hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a combination of an aromatic hydrocarbon group and an aliphatic hydrocarbon group. Yd 1 As the alkylene group, a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof is preferred. The alkylene group may be linear or branched. As the alkylene group, a methylene group and an ethylene group are preferred.

[0271] Specific examples of anions suitable for the anion moiety that constitutes the component (d1-3) include the following anions. [ka]

[0272] [ka]

[0273] Cation part In formula (d1-3), M m+ is an m-valent organic cation. m+ is M in formula (d1-1) m+ is the same as:

[0274] As the component (D1), any one of the components (d1-1), (d1-2), and (d1-3) may be used alone, or two or more of them may be used in combination. Of the components (d1-1), (d1-2), and (d1-3), the component (d1-1) is preferred.

[0275] [(D2) component] The photosensitive composition may contain, as the component (D), a nitrogen-containing organic compound component (hereinafter referred to as "component (D2)") that does not fall under the category of the component (D1). The component (D2) is not particularly limited as long as it acts as an acid diffusion controller and does not fall under the category of component (D1).

[0276] The component (D2) is preferably an aliphatic amine, and the aliphatic amine is preferably a secondary aliphatic amine or a tertiary aliphatic amine. Aliphatic amines are amines having one or more aliphatic groups, preferably having 1 to 12 carbon atoms. Aliphatic amines include amines in which at least one hydrogen atom of ammonia (NH3) is substituted with an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group having 1 to 12 carbon atoms, and cyclic amines.

[0277] Specific examples of alkylamines and alkanolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, and di-n-octylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine.

[0278] Among these, trialkylamines having one to three alkyl groups having from 5 to 10 carbon atoms are preferred, trialkylamines having three alkyl groups having from 5 to 10 carbon atoms are more preferred, and tri-n-pentylamine and tri-n-octylamine are even more preferred.

[0279] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compounds may be monocyclic or polycyclic compounds. Examples of the aliphatic monocyclic amine include piperidine, piperazine, and N-tert-butoxycarbonylpyrrolidine. The number of carbon atoms in the aliphatic polycyclic amine is preferably 6 or more and 10 or less. Specific examples of the aliphatic polycyclic amine include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0280] 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, and triethanolamine triacetate. Among these, triethanolamine triacetate is preferred.

[0281] Component (D2) may be an amine containing an aromatic group, such as 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole, and derivatives thereof; tribenzylamine; and 2,6-diisopropylaniline.

[0282] The component (D2) may be used alone or in combination of two or more.

[0283] When the photosensitive composition contains the base component (D), the content of the base component (D) in the photosensitive composition is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, and even more preferably 15 parts by mass or more and 45 parts by mass or less, per 100 parts by mass of the silicon-containing resin (A).

[0284] <At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxoacids and derivatives thereof> The photosensitive composition may contain, as an optional component, at least one compound (E) selected from the group consisting of organic carboxylic acids, and phosphorus oxoacids and derivatives thereof, for the purposes of preventing a decrease in sensitivity, forming a patterned silicon-containing resin film with a good pattern shape, and improving storage stability. Preferred organic carboxylic acids include, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid. As the phosphorus oxoacid, phosphoric acid, phosphonic acid, phosphinic acid, etc. are preferred, and phosphonic acid is more preferred. Derivatives of phosphorus oxoacids include, for example, ester compounds in which the hydrogen atoms of the oxoacids are substituted with hydrocarbon groups, such as alkyl groups having 1 to 5 carbon atoms and aryl groups having 6 to 15 carbon atoms. Examples of the derivatives of phosphoric acid include phosphoric acid esters such as di-n-butyl phosphoric acid ester and diphenyl phosphoric acid ester. Examples of the derivatives of phosphonic acid include phosphonic acid esters such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, and dibenzyl phosphonate. Examples of the derivatives of phosphinic acid include phosphinic acid esters and phenylphosphinic acid. The compound (E) may be used alone or in combination of two or more kinds. When the photosensitive composition contains the compound (E), the content of the compound (E) is generally in the range of 0.01 to 10 parts by mass per 100 parts by mass of the silicon-containing resin (A).

[0285] <Fluorine Additives (F)> The photosensitive composition may contain a fluorine additive (F) as a hydrophobic resin. The fluorine additive (F) is used to impart water repellency to the silicon-containing resin film formed using the photosensitive composition. When the fluorine additive (F) is used in the photosensitive composition as a resin separate from the silicon-containing resin (A), the lithography properties are improved. As the fluorine additive (F), for example, fluorine-containing polymer compounds described in JP-A Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569, and 2011-128226 can be used. More specifically, the fluorine additive (F) may be a polymer having a structural unit (f1) represented by the following formula (f1-1). This polymer is preferably a polymer (homopolymer) consisting solely of the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and a structural unit containing an acid-decomposable group whose polarity increases upon the action of acid; or a copolymer of a structural unit containing an acid-decomposable group whose polarity increases upon the action of acid, the structural unit (f1), and a structural unit derived from acrylic acid or methacrylic acid. Here, the structural unit containing an acid-decomposable group whose polarity increases upon the action of acid that is copolymerized with the structural unit (f1) is preferably a structural unit derived from 1-ethyl-1-cyclooctyl(meth)acrylate or a structural unit derived from 1-methyl-1-adamantyl(meth)acrylate.

[0286] [ka] In formula (f1-1), R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Rf 102 , and Rf 103 Rf each independently represents a hydrogen atom, a halogen atom, an alkyl group having from 1 to 5 carbon atoms, or a halogenated alkyl group having from 1 to 5 carbon atoms; 102 , and Rf 103 may be the same or different. 1 is an integer between 0 and 5, and Rf 101 is an organic group containing a fluorine atom.

[0287] R bonded to the carbon atom at the α-position is a hydrogen atom or an alkyl group having from 1 to 5 carbon atoms. R is preferably a hydrogen atom or a methyl group. Rf 102 , and Rf 103As the halogen atom for Rf, a fluorine atom is preferred. 102 , and Rf 103 As the alkyl group having 1 to 5 carbon atoms as Rf, a methyl group and an ethyl group are preferred. 102 , and Rf 103 Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms as Rf include groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. As the halogen atom, a fluorine atom is preferred. 102 , and Rf 103 As the alkyl group, a hydrogen atom, a fluorine atom, and an alkyl group having 1 to 5 carbon atoms are preferred, and a hydrogen atom, a fluorine atom, a methyl group, and an ethyl group are more preferred. 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.

[0288] Rf 101 is an organic group containing a fluorine atom. As the organic group containing a fluorine atom, a hydrocarbon group containing a fluorine atom is preferred. The structure of the fluorine atom-containing hydrocarbon group may be linear, branched, cyclic, or a combination of these structures. The number of carbon atoms in the fluorine atom-containing hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. Furthermore, in a 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, and particularly preferably 60% or more. Rf 101 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, and further preferably a trifluoromethyl group, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, and -CH2-CH2-CF2-CF2-CF2-CF3.

[0289] The weight average molecular weight (Mw) of the fluorine additive (F) (based on polystyrene conversion by gel permeation chromatography) is preferably 1,000 or more and 50,000 or less, more preferably 5,000 or more and 40,000 or less, and even more preferably 10,000 or more and 30,000 or less. The dispersity (Mw / Mn) of the fluorine additive (F) is preferably 1.0 or more and 5.0 or less, more preferably 1.0 or more and 3.0 or less, and even more preferably 1.0 or more and 2.5 or less.

[0290] The fluorine additive (F) may be used alone or in combination of two or more kinds. When the photosensitive composition contains a fluorine additive component (F), the content of the fluorine additive (F) is usually 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the silicon-containing resin (A).

[0291] <Organic solvent (S)> The photosensitive composition may contain an organic solvent (S), and preferably contains an organic solvent (S) for the purpose of adjusting the coating properties. The organic solvent (S) may be any solvent that can dissolve each component used and form a homogeneous solution, and any solvent can be appropriately selected from solvents that have been conventionally known as solvents for chemically amplified photosensitive compositions. Examples of the organic solvent (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; monoalkyl ethers of polyhydric alcohols or compounds having an ester bond such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether; and compounds having an ether bond such as monophenyl ether. Examples of suitable organic solvents include derivatives of hydric alcohols (among which, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene, and dimethyl sulfoxide (DMSO). The organic solvent (S) may be used alone or in a mixed solvent of two or more kinds. Among the above organic solvents (S), PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

[0292] The organic solvent (S) is preferably a mixed solvent of PGMEA and a polar solvent. The blending ratio (mass ratio) may be appropriately determined taking into consideration the compatibility of PGMEA with the polar solvent, and is preferably within the range of 1:9 to 9:1, more preferably 2:8 to 8:2. More specifically, when EL or cyclohexanone is blended as the polar solvent, the mass ratio of PGMEA:EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. When PGME is blended as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Furthermore, a mixed solvent of PGMEA, PGME, and cyclohexanone is also preferred. As another preferred organic solvent (S), a mixed solvent of at least one selected from PGMEA and EL with γ-butyrolactone is also preferred, in which the mass ratio of the former to the latter is preferably 70:30 to 95:5.

[0293] The amount of the organic solvent (S) used is not particularly limited, and is appropriately set depending on the coating film thickness within a range in which the solid content concentration of the photosensitive composition can be applied to a substrate or the like. The solid content concentration of the photosensitive composition is preferably in the range of 0.1% by mass to 10% by mass, more preferably 0.2% by mass to 5% by mass.

[0294] <Other ingredients> In addition to the components described above, the photosensitive composition may contain other components such as additional resins, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, and dyes, as appropriate. For example, in the photosensitive composition, a non-silicon-containing resin such as a hydroxystyrene resin or a novolak resin may be used as an additional resin in addition to the silicon-containing resin (A).

[0295] <Method for producing patterned silicon-containing resin film> The method for producing a patterned silicon-containing resin film includes forming a coating film made of a photosensitive composition on a support (hereinafter also referred to as a "coating film forming step"), position-selectively exposing the coating film (hereinafter also referred to as an "exposure step"), and developing the exposed coating film to form a patterned silicon-containing resin film (hereinafter also referred to as a "development step").

[0296] <Coating film formation process> First, the above-mentioned photosensitive composition is applied onto a support using a spinner or the like to form a coating film. The support is not particularly limited, and conventionally known supports can be used, such as substrates for electronic components and supports on which a predetermined wiring pattern is formed. More specifically, examples include silicon wafers, substrates made of metals such as copper, chromium, iron, and aluminum, and glass substrates. Metals such as copper, aluminum, nickel, and gold can be used as materials for the wiring pattern. The support may be a support having an inorganic and / or organic film provided on the substrate as described above. Examples of inorganic films include inorganic anti-reflective coatings (inorganic BARCs). Examples of organic films include organic anti-reflective coatings (organic BARCs) and organic films such as lower organic films in multilayer resist methods.

[0297] After application of the photosensitive composition, the film made of the photosensitive composition is subjected to a baking (post-apply bake (PAB)) treatment. The conditions for the baking treatment are not particularly limited as long as a patterned silicon-containing resin film having the desired shape and properties can be formed. Preferred baking conditions include, for example, heating at a temperature of 80°C to 150°C for 40 to 120 seconds, preferably 60 to 90 seconds.

[0298] <Exposure process> Next, the coating film is subjected to position-selective exposure using an exposure device such as an electron beam lithography device or an EUV (extreme ultraviolet) exposure device, either through a mask (mask pattern) on which a predetermined pattern is formed, or by direct irradiation with electron beams without using a mask pattern. The coating film is made of a photosensitive composition that hardens when exposed to light, and therefore a negative photomask is used as the mask, which is patterned so that the positions of the coating film that should be hardened are exposed to light.

[0299] The wavelength of the light used for exposure is not particularly limited, and radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, and soft X-ray can be used. In the above-mentioned method for producing a patterned silicon-containing resin film, the method is particularly useful in which the coated film is exposed to EUV (extreme ultraviolet) or EB (electron beam).

[0300] The exposure method for the coating film may be a normal exposure (dry exposure) carried out in air or an inert gas such as nitrogen, or may be liquid immersion lithography. After the exposure, the exposed coating film is optionally baked (post-exposure bake (PEB)). Preferred baking conditions include, for example, heating at a temperature of 80° C. to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds.

[0301] <Developing process> The regioselectively exposed coating film is then developed to obtain a patterned hardened film, typically by an alkaline development process or a solvent development process.

[0302] When development is carried out by an alkaline development process, an alkaline developer is used, such as an aqueous solution of tetramethylammonium hydroxide (TMAH) with a concentration of 0.1% by mass to 10% by mass.

[0303] When development is carried out by a solvent development process, a developer containing an organic solvent (organic developer) is used. The organic solvent contained in the organic developer used in the development treatment in the solvent development process may be any organic solvent that can dissolve component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specific examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents and halogenated hydrocarbon solvents. Ketone-based solvents are organic solvents that contain CC(=O)-C in their structure. Ester-based solvents are organic solvents that contain CC(=O)-OC in their structure. Alcohol-based solvents are organic solvents that contain an alcoholic hydroxyl group in their structure. "Alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. Nitrile-based solvents are organic solvents that contain a nitrile group in their structure. Amide-based solvents are organic solvents that contain a carboxylic acid amide group in their structure. Ether-based solvents are organic solvents that contain COC in their structure. Some organic solvents contain multiple types of functional groups that characterize the above-mentioned solvents in their structure, and in such cases, the term "organic solvent" refers to any solvent type containing the functional groups possessed by the organic solvent. For example, diethylene glycol monomethyl ether corresponds to both the alcohol-based solvent and the ether-based solvent in the above classification. A hydrocarbon solvent is a solvent made of hydrocarbon. A halogenated hydrocarbon solvent is a solvent made of hydrocarbon having only halogen atoms as substituents. The halogen atoms are preferably fluorine atoms. The organic solvent contained in the organic developer is preferably a polar solvent, and preferred are ketone-based solvents, ester-based solvents, and nitrile-based solvents.

[0304] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, and methyl amyl ketone (2-heptanone). Among these, methyl amyl ketone (2-heptanone) is preferred.

[0305] Examples of 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, and 2-ethoxybutyl acetate. 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, Examples of the ester solvent include 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, and γ-butyrolactone. Among these, butyl acetate is preferred as the ester solvent.

[0306] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0307] The organic developer may contain known additives as needed. Examples of such additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants.

[0308] Development can be carried out by a known developing method. Examples of such developing methods include a method of immersing a support in a developer for a certain period of time (dip method), a method of piling up a developer on the surface of a support by surface tension and leaving it standing for a certain period of time (puddle method), a method of spraying a developer onto the surface of a support (spray method), and a method of continuously dispensing a developer by scanning a developer dispensing nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method).

[0309] After development, the patterned silicon-containing resin film is preferably rinsed. In the case of an alkaline development process, rinsing with pure water is preferred. In the case of a solvent development process, rinsing with a rinse solution containing an organic solvent is preferred. The rinsing treatment can be carried out by a known rinsing method, such as a method of continuously applying a rinsing liquid onto a support rotating at a constant speed (spin coating method), a method of immersing a support in a rinsing liquid for a certain period of time (dipping method), or a method of spraying a rinsing liquid onto the surface of the support (spray method). In the case of a solvent development process, after development or after development and rinsing treatment, a treatment may be carried out to remove the developer or rinsing liquid adhering to the patterned silicon-containing resin film using a supercritical fluid. Typically, the patterned silicon-containing resin film is dried after development or rinsing. If necessary, the patterned silicon-containing resin film may be subjected to a baking treatment (post-baking) after the development.

[0310] As described above, the present inventors provide the following (1) to (9). (1) A composition comprising a silicon-containing resin (A) and a photoacid generator (B), The silicon-containing resin (A) is a silicon-containing resin (A1) having a phenolic hydroxyl group and not having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid, and a silicon-containing resin (A2) having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid and not having a phenolic hydroxyl group; a silicon-containing resin (A3) having a phenolic hydroxyl group and a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid, A photosensitive composition, wherein the photoacid generator (B) comprises a sulfonium salt (B1) containing a sulfonium cation having a fluorine atom. (2) The silicon-containing resin (A) is represented by the following formula (a1): R a1 -SiO 3 / 2 (a1) (In formula (a1), R a1 is an organic group having a methylol group or an alkoxymethyl group, The methylol group or alkoxymethyl group is bonded to an aromatic hydrocarbon group or a nitrogen atom. The photosensitive composition according to (1), having a structural unit represented by the following formula: (3) The silicon-containing resin (A) contains, as the structural unit represented by formula (a1), the structural unit represented by formula (a2): (R a3 ) n1 (OH) n2 Ar a1 -R a2 -SiO 3 / 2 (a2) (In formula (a2), R a2 is a divalent aliphatic group that does not contain a single bond or an aromatic group, Ar a1 represents an (n1+n2+1)-valent aromatic hydrocarbon group which may have a substituent, R a3is an organic group selected from a methylol group, an alkoxymethyl group, a hydrocarbon group having from 1 to 6 carbon atoms, and an alkoxy group having from 1 to 6 carbon atoms, R a3 The organic group is Ar a1 and bonded to an aromatic hydrocarbon group as n1 is an integer between 1 and 6, (OH) n2 Ar a1 n2 hydroxyl groups bonded to an aromatic hydrocarbon group as n2 is an integer between 0 and 4, R between 1 and 6 a3 At least one of the organic groups is a methylol group or an alkoxymethyl group. The structural unit (ai-1) represented by the following formula (a3): R a6 -R a5 -Ar a2 -R a4 -SiO 3 / 2 (a3) (In formula (a3), R a4 is a divalent linking group that does not contain a single bond or an aromatic group, Ar a2 represents a divalent aromatic hydrocarbon group which may have a substituent, R a5 is a single bond or a divalent linking group, R a6 is an aromatic hydrocarbon group having a methylol group or an alkoxymethyl group, or a nitrogen-containing group having a methylol group or an alkoxymethyl group, The methylol group and the alkoxymethyl group are bonded to an aromatic hydrocarbon group or a nitrogen atom, respectively. and a structural unit (ai-2) represented by the following formula (a4): R a8 -R a7 -SiO 3 / 2 (a4) (In formula (a4), R a7 is a divalent linking group that does not contain an aromatic group, R a8 is a nitrogen-containing group having a methylol group or an alkoxymethyl group, The methylol group-containing group and the alkoxymethyl group-containing group are each bonded to a nitrogen atom. and (ai-3) represents at least one structural unit selected from the group consisting of structural units represented by the formula: The structural unit (ai-2) represented by formula (a3) ​​is a structural unit that does not fall under the category of the structural unit (ai-1) represented by formula (a2), The photosensitive composition according to (2), wherein the structural unit (ai-3) represented by formula (a4) is a structural unit that does not fall under the category of the structural unit (ai-1) represented by formula (a2) or the structural unit (ai-3) represented by formula (a3). (4) The sulfonium salt (B1) is represented by the following formula (b0-1): [ka] (In formula (b0-1), R b1 is an aryl group having a fluorine atom or an aryl group having a fluorinated alkyl group. b2 , and R b3 R are each independently an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. b1 ~R b3 Two of X may be bonded to each other to form a ring together with the sulfur atom in the formula. 01 is the counter anion.) The photosensitive composition according to any one of (1) to (3), wherein the sulfonium salt is represented by the following formula: (5) The photosensitive composition according to any one of (1) to (4), which contains a base component (D) that controls the diffusion of the acid generated by the photoacid generator (B) upon exposure. (6) The photosensitive composition according to (5), wherein the base component (D) comprises a sulfonium salt containing a sulfonium cation having a fluorine atom. (7) The photosensitive composition according to any one of (1) to (6), wherein the ratio of the mass of the silicon-containing resin (A) to the mass of the solid content of the photosensitive composition is 10 mass % or more. (8) Coating a support with the photosensitive composition according to any one of (1) to (7) to form a coating film; position-selectively exposing the coating film; and developing the exposed coating film. (9) The method for forming a patterned silicon-containing resin film according to (8), wherein the coating film is exposed by being irradiated with extreme ultraviolet light in a position-selective manner. [Example]

[0311] The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[0312] [Examples 1 to 33 and Comparative Examples 1 to 6] In the examples and comparative examples, the following A-1 to A-10 were used as the silicon-containing resin (A) (component (A)). In the following formula, the number attached to each structural unit indicates the molar ratio of each structural unit when the amount of all structural units is taken as 1.

[0313] [ka]

[0314] The weight average molecular weight Mw and dispersity of silicon-containing resins A-1 to A-4 are as shown in Table 1. The weight average molecular weight Mn is a value measured by gel permeation chromatography (GPC) in terms of polystyrene. The dispersity is a value calculated from the weight average molecular weight Mw and the number average molecular weight Mn. The number average molecular weight Mn is a value measured by GPC in terms of polystyrene.

[0315] [Table 1]

[0316] In the examples and comparative examples, the following B-1 to B-6 were used as the photoacid generator (B) (component (B)). [ka]

[0317] In the examples and comparative examples, the following C-1 was used as the crosslinking agent (C) (component (C)).

[0318] [ka]

[0319] In the examples and comparative examples, the following D-1 to D-6 were used as the base component (D) (component (D)).

[0320] [ka]

[0321] In the examples and comparative examples, the following E-1 was used as the compound (E) (component (E)). E-1: Salicylic acid

[0322] In the examples and comparative examples, the following organic solvents S-1 and S-2 were used as the organic solvent (S). S-1: Propylene glycol monomethyl ether S-2: Propylene glycol monomethyl ether acetate

[0323] The types and amounts of each component shown in Table 2 were mixed uniformly to obtain photosensitive compositions of Examples 1 to 33 and Comparative Examples 1 to 6. In Table 2, the numbers in parentheses indicate parts by mass of each component. [Table 2]

[0324] The photosensitive compositions obtained in Examples 1 to 33 and Comparative Examples 1 to 6 were evaluated for optimum exposure (Eop), line width roughness (LWR), and residual film ratio according to the following methods. The evaluation results are shown in Table 3.

[0325] <Formation of patterned silicon-containing resin film (cured film)> A resist organic underlayer film composition "AL412" (manufactured by Brewer Science) was applied to a 12-inch silicon wafer using a spin coater, and the applied film was baked on a hot plate at 205°C for 60 seconds to form an organic underlayer film with a thickness of 22 nm. The photosensitive composition of each Example and Comparative Example was applied onto the organic underlayer film using a spin coater, and the coating film was subjected to a pre-baking (PAB) treatment at 90°C for 60 seconds on a hot plate to form a coating film with a thickness of 22 nm.

[0326] Next, the coating film was irradiated with EUV light (13.5 nm) through a photomask using an EUV exposure system NXE3400 (manufactured by ASML, NA (numerical aperture) = 0.33, illumination conditions: annular σ-in = 0.60, σ-out = 0.82). Thereafter, post-exposure baking (PEB) was performed at 90° C. for 60 seconds.

[0327] Next, alkaline development was carried out at 23° C. for 10 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thereafter, the substrate was rinsed with pure water for 30 seconds, and then shaken off and dried. As a result, a line and space pattern (LS pattern) with a line width of 14 nm was formed.

[0328] <Evaluation of optimal exposure (Eop) (evaluation of sensitivity)> The optimal exposure dose Eop (mJ / cm) for forming an LS pattern with a line width of 14 nm by forming the above-mentioned patterned silicon-containing resin film. 2 ) was sought.

[0329] <Evaluation of LWR (Line-Wise Roughness)> For the LS pattern with a line width of 14 nm formed by forming the above-patterned cured film, 3σ, which is a measure indicating LWR, was determined. "3σ" means three times the standard deviation (σ) (unit: nm) obtained from the measurement results by measuring the line positions at 400 locations in the longitudinal direction of the line using a scanning electron microscope (acceleration voltage: 800 V, trade name: S-9380, manufactured by Hitachi High-Technologies Corporation). The results are shown in Table 2. The smaller the value of 3σ, the smaller the roughness of the line sidewall, meaning that an LS pattern with a more uniform width was obtained.

[0330] <Evaluation of Residual Film Ratio> In the formation of the above-patterned silicon-containing resin film, the film thickness T1 of the coated film after PAB treatment and the film thickness T2 of the silicon-containing resin film after water rinsing were each measured using an electron microscope (trade name: SU8000, manufactured by Hitachi High-Tech), and the residual film ratio (%) was calculated according to the following formula. Residual film ratio (%) = T2 / T1 × 100

[0331]

Table 3

[0332] According to Examples 1 to 33, it can be seen that the photosensitive composition of the example containing the silicon-containing resin (A) having a combination of a phenolic hydroxyl group and a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group by the action of an acid, and the sulfonium salt (B1) containing a sulfonium cation having a fluorine atom as the photoacid generator (B) is excellent in sensitivity, has reduced roughness, and gives a patterned silicon-containing resin film that is less likely to have a film thickness reduction even after development and rinsing.

Claims

1. A composition comprising a silicon-containing resin (A) and a photoacid generator (B), The silicon-containing resin (A) is a silicon-containing resin (A1) having a phenolic hydroxyl group but not having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid, and a silicon-containing resin (A2) having a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid but not having a phenolic hydroxyl group; a silicon-containing resin (A3) having a phenolic hydroxyl group and a group capable of crosslinking with an aromatic group having a phenolic hydroxyl group under the action of an acid, The photosensitive composition, wherein the photoacid generator (B) comprises a sulfonium salt (B1) containing a sulfonium cation having a fluorine atom.

2. The silicon-containing resin (A) is represented by the following formula (a1): R ａ１ -SiO ３／２ ・・・(a1) (In formula (a1), R ａ１ is an organic group having a methylol group or an alkoxymethyl group, The methylol group or the alkoxymethyl group is bonded to an aromatic hydrocarbon group or a nitrogen atom. The photosensitive composition according to claim 1 , which has a structural unit represented by the formula:

3. The silicon-containing resin (A) contains, as the structural unit represented by formula (a1), a structural unit represented by the following formula (a2): (R) ａ３ ) ｎ１ (OH) ｎ２ Ar ａ１ -R ａ２ -SiO ３／２ ・・・(a2) (In formula (a2), R ａ２ is a divalent aliphatic group that does not contain a single bond or an aromatic group, Ar ａ１ represents an (n1+n2+1)-valent aromatic hydrocarbon group which may have a substituent, R ａ３ is an organic group selected from a methylol group, an alkoxymethyl group, a hydrocarbon group having from 1 to 6 carbon atoms, and an alkoxy group having from 1 to 6 carbon atoms, R ａ３ The organic group as Ar ａ１ and is bonded to the aromatic hydrocarbon group as n1 is an integer of 1 to 6, (OH) ｎ２ is Ar ａ１ n2 hydroxyl groups bonded to the aromatic hydrocarbon group as n2 is an integer of 0 to 4, R between 1 and 6 ａ３ At least one of the organic groups is a methylol group or an alkoxymethyl group. and structural units (ai-1) represented by the following formula (a3): R ａ６ -R ａ５ -Ar ａ２ -R ａ４ -SiO ３／２ ・・・(a3) (In formula (a3), R ａ４ is a divalent linking group that does not contain a single bond or an aromatic group, Ar ａ２ represents a divalent aromatic hydrocarbon group which may have a substituent, R ａ５ is a single bond or a divalent linking group, R ａ６ is an aromatic hydrocarbon group having a methylol group or an alkoxymethyl group, or a nitrogen-containing group having a methylol group or an alkoxymethyl group, The methylol group and the alkoxymethyl group are bonded to an aromatic hydrocarbon group or a nitrogen atom, respectively. and a structural unit (ai-2) represented by the following formula (a4): R ａ８ -R ａ７ -SiO ３／２ ・・・ (a4) (In formula (a4), R ａ７ is a divalent linking group that does not contain an aromatic group, R ａ８ is a nitrogen-containing group having a methylol group or an alkoxymethyl group, The methylol group-containing group and the alkoxymethyl group-containing group are each bonded to a nitrogen atom. and (ai-3) represents at least one structural unit selected from the group consisting of structural units represented by the formula: The structural unit (ai-2) represented by the formula (a3) ​​is a structural unit that does not fall under the category of the structural unit (ai-1) represented by the formula (a2), The photosensitive composition according to claim 2, wherein the structural unit (ai-3) represented by formula (a4) is a structural unit that does not fall under the category of the structural unit (ai-1) represented by formula (a2) or the structural unit (ai-3) represented by formula (a3).

4. The sulfonium salt (B1) is represented by the following formula (b0-1): 【Chemistry 1】 (In formula (b0-1), R ｂ１ is an aryl group having a fluorine atom or an aryl group having a fluorinated alkyl group. ｂ２ , and R ｂ３ R are each independently an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. ｂ１ ~R ｂ３ Two of X may be bonded to each other to form a ring together with the sulfur atom in the formula. ０１ is the counter anion.) 2. The photosensitive composition according to claim 1, wherein the sulfonium salt is represented by the formula:

5. 2. The photosensitive composition according to claim 1, further comprising a base component (D) that controls the diffusion of the acid generated by the photoacid generator (B) upon exposure.

6. 6. The photosensitive composition according to claim 5, wherein the basic component (D) comprises a sulfonium salt (D1) containing a sulfonium cation having a fluorine atom.

7. 2. The photosensitive composition according to claim 1, wherein the ratio of the mass of the silicon-containing resin (A) to the mass of the solid content of the photosensitive composition is 10 mass% or more.

8. Coating a support with the photosensitive composition according to any one of claims 1 to 7 to form a coating film; exposing the coating film to position-selective light; and developing the exposed coating film.

9. 9. The method for forming a patterned silicon-containing resin film according to claim 8, wherein the coating film is exposed by being irradiated with extreme ultraviolet light in a position-selective manner.

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