Negative-type photosensitive composition and pattern forming method

Abstract

To provide a negative photosensitive composition that has good sensitivity and can enhance the rectangularity of a pattern shape.SOLUTION: There is provided a negative photosensitive composition containing a novolak type polyfunctional aromatic epoxy resin (Ap), a trifunctional epoxy monomer (Am), and a sulfonium salt represented by formula (I0). The mass ratio (Am) / (Ap) is 5 / 5 to 8 / 2. In the formula (I0), R3 to R5 are an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, a hydroxy(poly)alkyleneoxy group or a halogen atom. L is -S-, -O-, -SO-, -SO2- or -CO-. X- represents a monovalent polyatomic anion.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative-type photosensitive composition and a pattern-forming method. [Background technology]

[0002] In recent years, with the miniaturization and increased density of electronic components, there has been a growing demand for photosensitive materials used in electronic components with hollow sealing structures, such as surface acoustic wave (SAW) filters. In forming the hollow sealing structure of these electronic components, photosensitive materials are used as spacers (wall materials) between the semiconductor wafer and the transparent substrate, or as roofing material for the top plate. For example, a photosensitive film is formed on the surface of a semiconductor wafer using a negative-type photosensitive composition. The photosensitive film is then selectively exposed to radiation such as light or electron beams, and a development process is performed to form a pattern. After this, it is pressed against a transparent substrate (e.g., a glass substrate) to form a spacer. In this photosensitive film, it is necessary that when developed using the photolithography method, a film of the required thickness for the spacer is formed, and that high-resolution patterning with a good shape and no residue is possible.

[0003] Conventionally, photosensitive compositions have been proposed that contain an epoxy group-containing resin having two or more epoxy groups in one molecule, and various cationic polymerization initiators, as photosensitive materials for forming the aforementioned photosensitive film (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2022-15071 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] As electronic components become increasingly miniaturized and denser, forming fine-dimensional patterns is crucial in creating hollow encapsulation structures. However, with conventional photosensitive materials, such as those described in Patent Document 1, when attempting to miniaturize the pattern dimensions by increasing the reactivity between epoxy groups, there is a problem in that the area near the semiconductor wafer interface tends to harden insufficiently, resulting in defects in the pattern shape.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a negative-type photosensitive composition that has good sensitivity and can enhance the rectangularity of the pattern shape, and a pattern formation method using the same. [Means for solving the problem]

[0007] To solve the above problems, the present invention employs the following configuration. In other words, a first aspect of the present invention is a negative-type photosensitive composition comprising (A) component: epoxy group-containing compound and (I) component: cationic polymerization initiator, wherein (A) component comprises (Ap) component: novolac-type polyfunctional aromatic epoxy resin and (Am) component: trifunctional epoxy monomer, and (I) component comprises (I0) component: sulfonium salt represented by the following general formula (I0), and the mixing ratio of (Ap) component to (Am) component is a mass ratio expressed as (Am) component / (Ap) component, which is 5 / 5 to 8 / 2, characterized in that the negative-type photosensitive composition is a negative-type photosensitive composition.

[0008] [ka] [In formula (I0), R1 and R2 each represent an aryl group having 6 to 30 carbon atoms, a heterocyclic hydrocarbon group having 4 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms, and some of the hydrogen atoms of these aryl groups, heterocyclic hydrocarbon groups, or alkyl groups may be substituted with substituents (t). These substituents (t) may be alkyl groups having 1 to 18 carbon atoms, hydroxyl groups, alkoxy groups having 1 to 18 carbon atoms, alkylcarbonyl groups having 2 to 18 carbon atoms, arylcarbonyl groups having 7 to 11 carbon atoms, acyloxy groups having 2 to 19 carbon atoms, arylthio groups having 6 to 20 carbon atoms, alkylthio groups having 1 to 18 carbon atoms, aryl groups having 6 to 10 carbon atoms, heterocyclic hydrocarbon groups having 4 to 20 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, HO(-R 6 O)q-{R 6 O represents an ethylene oxy group and / or a propylene oxy group, and q represents an integer from 1 to 5. R3 to R5 are each an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, a hydroxy(poly)alkylene oxy group, or a halogen atom. k, m, and n represent the number of R3, R4, and R5, where k is an integer from 0 to 4, m is an integer from 0 to 3, and n is an integer from 1 to 4. If k, m, and n are each 2 or more, the multiple R3, R4, and R5 may be the same or different from each other. L is a group represented by -S-, -O-, -SO-, -SO2-, or -CO-, where O is an oxygen atom, S is a sulfur atom, and X - This represents a monovalent polyatomic anion.

[0009] A second aspect of the present invention is a pattern forming method characterized by comprising the steps of: forming a photosensitive film on a support using a negative-type photosensitive composition according to the first aspect; exposing the photosensitive film to light; and developing the exposed photosensitive film with a developer containing an organic solvent to form a negative-type pattern. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a negative-type photosensitive composition that has good sensitivity and can enhance the rectangularity of the pattern shape, and a pattern formation method using the same. [Modes for carrying out the invention]

[0011] In this specification and in the claims, "aliphatic" is defined as a concept relative to aromatic, meaning a group that does not possess aromaticity, a compound that does not possess aromaticity, etc. Unless otherwise specified, "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups within alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is a group in which some or all of the hydrogen atoms of an alkyl group are replaced by halogen atoms, and examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. A "fluorinated alkyl group" refers to a group in which some or all of the hydrogen atoms of an alkyl group are replaced with fluorine atoms. "Constituent unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer). When it is stated that a group "may have substituents," this includes both cases where a hydrogen atom (-H) is substituted with a monovalent group and cases where a methylene group (-CH2-) is substituted with a divalent group. "Exposure" is a concept that includes all forms of radiation exposure.

[0012] (Negative-type photosensitive composition) The negative-type photosensitive composition of this embodiment contains (A) a compound containing an epoxy group and (I) a cationic polymerization initiator. When a photosensitive film is formed using such a photosensitive composition and selectively exposed to light, in the exposed areas of the photosensitive film, the cation portion of component (I) decomposes to generate acid. This acid causes ring-opening polymerization of the epoxy group in component (A), reducing the solubility of component (A) in a developer containing an organic solvent. In contrast, in the unexposed areas of the photosensitive film, the solubility of component (A) in a developer containing an organic solvent remains unchanged. As a result, a difference in solubility in a developer containing an organic solvent occurs between the exposed and unexposed areas of the photosensitive film. Therefore, when the photosensitive film is developed with a developer containing an organic solvent, the unexposed areas are dissolved and removed, forming a negative-type pattern.

[0013] <(A) Component: Epoxy group-containing compound> In the negative-type photosensitive composition of this embodiment, component (A) is used to include component (Ap): a novolac-type polyfunctional aromatic epoxy resin and component (Am): a trifunctional epoxy monomer. The mixing ratio of component (Ap) to component (Am) is a mass ratio expressed as component (Am) / component (Ap), which is 5 / 5 to 8 / 2.

[0014] (Ap) Component: Novolac-type polyfunctional aromatic epoxy resin The (Ap) component is a novolac-type polyfunctional aromatic epoxy resin that has enough epoxy groups to form a negative pattern upon exposure. As the (Ap) component, a resin represented by the following general formula (Ap-1) is preferred.

[0015] [ka] [In formula (Ap-1), R p1 and R p2 Each of these is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p1 These may be identical or different from one another. p2 n1 may be identical or different from each other. n1 is an integer between 1 and 5. EP It is an epoxy group-containing group. Multiple REP may be the same as or different from each other.

[0016] In the formula (Ap-1), R p1 , R p2 alkyl groups having 1 to 5 carbon atoms are, for example, linear, branched or cyclic alkyl groups having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. Examples of the cyclic alkyl group include cyclobutyl group, cyclopentyl group, etc. Among them, R p1 , R p2 is preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, and particularly preferably a hydrogen atom or a methyl group. In the formula (Ap-1), a plurality of R p1 may be the same as or different from each other. A plurality of R p2 may be the same as or different from each other.

[0017] In the formula (Ap-1), n1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

[0018] In the formula (Ap-1), R EP is a group containing an epoxy group. R EP The group containing an epoxy group is not particularly limited, and examples include a group consisting only of an epoxy group; a group consisting only of an alicyclic epoxy group; a group having an epoxy group or an alicyclic epoxy group and a divalent linking group. The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a 3-membered ring ether, and specifically, it is a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group forming the basic skeleton of an alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups. Furthermore, the hydrogen atoms of these alicyclic groups may be substituted with alkyl groups, alkoxy groups, hydroxyl groups, etc. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable that the epoxy group or alicyclic epoxy group is bonded via the divalent linking group bonded to the oxygen atom (-O-) in the formula.

[0019] Here, the divalent linking group is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have substituents, a divalent linking group which contains a heteroatom, and so on.

[0020] Regarding divalent hydrocarbon groups that may have substituents: Such a divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated. More specifically, examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0021] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. A linear alkylene group is preferred as the linear aliphatic hydrocarbon group, specifically including methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], and the like. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6, even more preferably 2 to 4, and most preferably 2 or 3 carbon atoms. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0022] Examples of aliphatic hydrocarbon groups containing a ring in the aforementioned structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is one obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, and the like. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0023] In divalent hydrocarbon groups, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system with (4n+2) π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of aromatic hydrocarbon groups include groups obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); groups obtained by removing two hydrogen atoms from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of an aryl group or heteroaryl group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) is substituted with an alkylene group (e.g., groups obtained by removing one more hydrogen atom from an aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0024] The divalent hydrocarbon group may have substituents. The divalent hydrocarbon group, a linear or branched aliphatic hydrocarbon group, may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0025] Alicyclic hydrocarbon groups in aliphatic hydrocarbon groups containing a ring in their structure, as divalent hydrocarbon groups, may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and the like. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. As the alkoxy group used as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy groups being preferred, and methoxy and ethoxy groups being the most preferred. Examples of halogen atoms used as substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like, with fluorine atoms being preferred. Examples of halogenated alkyl groups as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. The alicyclic hydrocarbon group may have some of the carbon atoms constituting its ring structure replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0026] As a divalent hydrocarbon group, the aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the alkoxy group, halogen atom, and alkyl halogenated group used as substituents include those that substitute for the hydrogen atoms of the alicyclic hydrocarbon group.

[0027] Regarding divalent linking groups containing heteroatoms: In a divalent linking group containing a heteroatom, the heteroatom is an atom other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and halogen atoms.

[0028] In a divalent linking group containing a heteroatom, preferred linking groups include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted with substituents such as alkyl groups or acyl groups); -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 ,-[Y 21 -C(=O)-O] m” -Y 22 - or -Y 21 -OC(=O)-Y 22 - is represented by the base [wherein Y 21 and Y 22 Each of these is a divalent hydrocarbon group which may have substituents independently, O is an oxygen atom, and m'' is an integer from 0 to 3. When the divalent linking group containing the heteroatom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, the H may be substituted with substituents such as alkyl groups or acyl groups. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. Formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -,-[Y 21 -C(=O)-O] m” -Y 22 - or -Y 21 -OC(=O)-Y 22 - Middle, Y 21 and Y 22 These are, independently, divalent hydrocarbon groups which may have substituents. Examples of such divalent hydrocarbon groups are the same as the "divalent hydrocarbon groups which may have substituents" mentioned in the above description of divalent linking groups. Y 21 Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. Y 22 The group is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula - [Y 21 -C(=O)-O] m” -Y 22 In the base represented by -, m'' is an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and particularly preferably 1. That is, in the formula -[Y 21 -C(=O)-O] m” -Y 22 As a base represented by -, formula -Y21 -C(=O)-OY 22 Groups represented by - are particularly preferred. Among them, the group represented by formula -(CH2) a’ -C(=O)-O-(CH2) b’ A base represented by - is preferred. In the formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0029] Among them, R EP A glycidyl group is preferred as the epoxy group-containing group in this product.

[0030] Furthermore, as the (Ap) component, resins having a constituent unit represented by the following general formula (anv1) are also preferred.

[0031] [ka] [In the formula, R EP R is an epoxy group-containing group. a22 and R a23 These are, independently, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0032] In the above equation (anv1), R a22 , R a23 The alkyl group having 1 to 5 carbon atoms is R in formula (Ap-1) p1 , R p2 This is similar to alkyl groups with 1 to 5 carbon atoms. R a22 , R a23 The halogen atom is preferably a chlorine atom or a bromine atom. In the above equation (anv1), R EP R in the above formula (Ap-1) is EP Similar to the above, a glycidyl group is preferred.

[0033] The following are specific examples of the constituent units represented by the above formula (anv1).

[0034] [ka]

[0035] The (Ap) component may be a resin consisting only of the aforementioned structural unit (anv1), or it may be a resin having structural unit (anv1) and other structural units. Other constituent units include, for example, the constituent units represented by the following general formulas (anv2) to (anv3).

[0036] [ka] [In the formula, R a24 R is a hydrocarbon group which may have substituents. a25 ~R a26 , R a28 ~R a30 Each of these is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. a27 This is an epoxy group-containing group or a hydrocarbon group which may have substituents.

[0037] In the above equation (anv2), R a24 This is a hydrocarbon group which may have substituents. Examples of hydrocarbon groups which may have substituents include linear or branched alkyl groups, or cyclic hydrocarbon groups. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2 carbon atoms. Specifically, examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, methyl group, ethyl group, or n-butyl group is preferred, and methyl group or ethyl group is more preferred.

[0038] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0039] R a24 When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic aliphatic hydrocarbon group is preferably a polycycloalkane from which one hydrogen atom has been removed, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically including adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0040] R a24 When the cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. R a24Specific examples of aromatic hydrocarbon groups in this context include: a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0041] In the above equations (anv2) and (anv3), R a25 ~R a26 , R a28 ~R a30 Each of these is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. C1-C5 alkyl groups and halogen atoms are, respectively, R a22 , R a23 It is similar to that.

[0042] In the above equation (anv3), R a27 R is an epoxy group-containing group or a hydrocarbon group which may have substituents. a27 The epoxy group-containing group is R in formula (Ap-1) above. EP It is similar to R. a27 The hydrocarbon group which may have substituents is R in formula (anv2). a24 It is similar to that.

[0043] The following are specific examples of the constituent units represented by the above formulas (anv2) to (anv3).

[0044] [ka]

[0045] If component (Ap) has other constituent units in addition to constituent unit (anv1), the proportion of each constituent unit in component (Ap) is not particularly limited, but the total amount of constituent units having epoxy groups is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol% relative to the total amount of all constituent units of component (Ap).

[0046] Examples of commercially available products containing component (Ap) include jER-152, jER-154, jER-157S70, jER-157S65 (all manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON HP5000 (all manufactured by DIC Corporation), and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).

[0047] The (Ap) component may be used alone or in combination of two or more types. In the negative-type photosensitive composition of this embodiment, the content of component (Ap) is preferably 50% by mass or less, more preferably 20 to 50% by mass, and even more preferably 30 to 50% by mass, based on the total mass (mass%) of component (A). When the content of component (Ap) is below the upper limit of the preferred range described above, it becomes easier to form a pattern with a good shape and high rectangularity during pattern formation. On the other hand, when it is above the lower limit of the preferred range described above, it becomes easier to achieve high sensitivity during pattern formation.

[0048] (Am) Ingredient: Trifunctional epoxy monomer The (Am) component uses an epoxy monomer having three epoxy groups in its molecule. Examples of the (Am) component include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, monomers represented by the following general formula (Am-1), and the like.

[0049]

Chemical formula

[0050] In the above formula (Am-1), the alkyl group having 1 to 5 carbon atoms of R p3 , R p4 and R p5 is, for example, a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. Examples of the cyclic alkyl group include cyclobutyl group, cyclopentyl group, etc. Among them, R p3 , R p4 and R p5 are each preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, still more preferably a hydrogen atom or a methyl group, and particularly preferably all methyl groups.

[0051] In the above formula (Am-1), Rm EP is a group containing an epoxy group, which is the same as R EP in the above formula (Ap-1), and a glycidyl group is preferred. The plurality of Rm EP may be the same as or different from each other.

[0052] The following are specific examples of monomers represented by the above formula (Am-1).

[0053] [ka]

[0054] The (Am) component may be used alone or in combination of two or more types. Among the components (Am), epoxy monomers having a structure in which the distance between the three epoxy groups within the molecule is large are preferred because intramolecular crosslinking reactions do not proceed easily, tris(4-hydroxyphenyl)methane triglycidyl ether and the monomer represented by the above general formula (Am-1) are more preferred, and the monomer represented by the above general formula (Am-1) is particularly preferred.

[0055] In the negative-type photosensitive composition of this embodiment, the content of component (Am) is preferably 50% by mass or more, more preferably 50-80% by mass, and even more preferably 50-70% by mass, based on the total mass (mass%) of component (A). If the content of component (Am) is above the lower limit of the preferred range mentioned above, the pattern formation process becomes less susceptible to influences from lithography processes such as bake temperature conditions, making it easier to form a pattern with a good, highly rectangular shape. On the other hand, if it is below the upper limit of the preferred range mentioned above, it becomes easier to achieve high sensitivity during pattern formation.

[0056] In the negative-type photosensitive composition of this embodiment, the mixing ratio of component (Ap) to component (Am) is a mass ratio expressed as component (Am) / component (Ap), which is 5 / 5 to 8 / 2, preferably 5 / 5 to 7 / 3. If the mass ratio expressed as (Am) component / (Ap) component is above the lower limit of the range, the pattern formation process will be less affected by factors such as bake temperature, resulting in the formation of a highly rectangular and well-shaped pattern. In addition, undercuts at the substrate interface will be less likely to occur. On the other hand, if it is below the upper limit of the range, the sensitivity during pattern formation will be increased.

[0057] <<Other epoxy group-containing compounds>> In the negative-type photosensitive composition of this embodiment, in addition to components (Ap) and (Am), other epoxy group-containing compounds may be used as component (A). Other epoxy group-containing compounds include, for example, bisphenol-type epoxy resins (bisphenol A type epoxy resins, bisphenol F type epoxy resins), acrylic resins, and aliphatic epoxy resins.

[0058] Examples of bisphenol-type epoxy resins include epoxy resins represented by the following general formula (abp1).

[0059] [ka] [In the formula, R EP It is an epoxy group containing R a31 , R a32 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and na 31 [This is an integer between 1 and 50.]

[0060] In formula (abp1), R a31 , R a32 The alkyl group having 1 to 5 carbon atoms is R in formula (Ap-1) p1 , R p2 This is similar to alkyl groups with 1 to 5 carbon atoms. Among them, R a31 , R a32 A hydrogen atom or a methyl group is preferred as the element. R EP R in the above formula (Ap-1) is EP Similar to the above, a glycidyl group is preferred.

[0061] Examples of acrylic resins include resins having epoxy group-containing units represented by the following general formulas (a1-1) to (a1-2).

[0062] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Va 41 This is a divalent hydrocarbon group which may have substituents. 41 R is an integer between 0 and 2. a41 , R a42 It is an epoxy group-containing group. 42 It is either 0 or 1. 41 wa (na 43 It is a +1) valent aliphatic hydrocarbon group. 43 [This is an integer between 1 and 2.]

[0063] In the above formula (a1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. The alkyl group of R having 1 to 5 carbon atoms is preferably linear or branched, and specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. The C1-C5 alkyl halide of R is a group in which some or all of the hydrogen atoms of the C1-C5 alkyl group are substituted with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, with a hydrogen atom or a methyl group being the most preferred due to their industrial availability.

[0064] In the above formula (a1-1), Va 41 R is a divalent hydrocarbon group which may have substituents, and R in formula (Ap-1)EP Examples include groups similar to the divalent hydrocarbon groups that may have substituents, as described above. Among the above, Va 41 The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, even more preferably a linear aliphatic hydrocarbon group, and particularly preferably a linear alkylene group.

[0065] In formula (a1-1), na 41 is an integer between 0 and 2, preferably 0 or 1.

[0066] In formulas (a1-1) and (a1-2), R a41 , R a42 is an epoxy group containing R in formula (Ap-1). EP It is similar to that.

[0067] In equation (a1-2), Wa 41 (na 43 A +1) valency aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, but is usually preferred to be saturated. Examples of such aliphatic hydrocarbon groups include linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing a ring in their structure, or groups that combine a linear or branched aliphatic hydrocarbon group with an aliphatic hydrocarbon group containing a ring in its structure.

[0068] Furthermore, the acrylic resin in component (A) above may have constituent units derived from other polymerizable compounds for the purpose of appropriately controlling its physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having carboxyl groups and ester bonds such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; hydroxyalkyl (meth)acrylate esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Examples include aryl (meth)acrylates such as phenyl(meth)acrylate and benzyl(meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and polymerizable compounds containing amide bonds such as acrylamide and methacrylamide.

[0069] As an aliphatic epoxy resin, compounds containing a substructure represented by the following general formula (m1) (hereinafter also referred to as "component (m1)") are also preferred.

[0070] [ka] [In the formula, n² is an integer between 1 and 4. * indicates a combination.]

[0071] In formula (m1), n2 is an integer between 1 and 4, preferably between 1 and 3, and more preferably 2.

[0072] Component (m1) includes compounds in which multiple substructures represented by the general formula (m1) are bonded together via divalent linking groups or single bonds. Among these, compounds in which multiple substructures represented by the general formula (m1) are bonded together via divalent linking groups are preferred. The divalent linking group here is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. For divalent hydrocarbon groups which may have substituents and divalent linking groups which contain heteroatoms, R in formula (Ap-1) above is used. EP Similar to the divalent hydrocarbon groups and divalent linking groups containing heteroatoms described in (epoxy group-containing groups), which may have substituents, among these, divalent linking groups containing heteroatoms are preferred, -Y 21 The base represented by -C(=O)-O-, -C(=O)-OY 21 -A base represented by Y is more preferable. 21 Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.

[0073] The polystyrene-based mass-average molecular weight of component (A) is preferably 100 to 300,000, more preferably 200 to 200,000, and even more preferably 300 to 200,000. By setting the mass-average molecular weight in this manner, delamination from the support becomes less likely, and the strength of the formed cured film is sufficiently increased.

[0074] Furthermore, it is preferable that component (A) has a dispersion degree of 1.05 or higher. By achieving such a dispersion degree, the lithography characteristics are further improved during pattern formation. In this context, dispersion refers to the value obtained by dividing the mass-average molecular weight by the number-average molecular weight.

[0075] The content of component (A) in the negative-type photosensitive composition of the embodiment may be adjusted according to the thickness of the photosensitive film to be formed.

[0076] <(I) Component: Cationic polymerization initiator> In the negative-type photosensitive composition of this embodiment, component (I) is used which contains component (I0): a sulfonium salt represented by the following general formula (I0).

[0077] [ka] [In formula (I0), R1 and R2 each represent an aryl group having 6 to 30 carbon atoms, a heterocyclic hydrocarbon group having 4 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms, and some of the hydrogen atoms of these aryl groups, heterocyclic hydrocarbon groups, or alkyl groups may be substituted with substituents (t). These substituents (t) may be alkyl groups having 1 to 18 carbon atoms, hydroxyl groups, alkoxy groups having 1 to 18 carbon atoms, alkylcarbonyl groups having 2 to 18 carbon atoms, arylcarbonyl groups having 7 to 11 carbon atoms, acyloxy groups having 2 to 19 carbon atoms, arylthio groups having 6 to 20 carbon atoms, alkylthio groups having 1 to 18 carbon atoms, aryl groups having 6 to 10 carbon atoms, heterocyclic hydrocarbon groups having 4 to 20 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, HO(-R 6 O)q-{R 6O represents an ethylene oxy group and / or a propylene oxy group, and q represents an integer from 1 to 5. R3 to R5 are each an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, a hydroxy(poly)alkylene oxy group, or a halogen atom. k, m, and n represent the number of R3, R4, and R5, where k is an integer from 0 to 4, m is an integer from 0 to 3, and n is an integer from 1 to 4. If k, m, and n are each 2 or more, the multiple R3, R4, and R5 may be the same or different from each other. L is a group represented by -S-, -O-, -SO-, -SO2-, or -CO-, where O is an oxygen atom, S is a sulfur atom, and X - This represents a monovalent polyatomic anion.

[0078] ≪(I0) component≫ In the above formula (I0), examples of alkyl groups among R3 to R5 include linear alkyl groups having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl, etc.), branched alkyl groups having 3 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and isooctadecyl), and cycloalkyl groups having 3 to 18 carbon atoms (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and 4-decylcyclohexyl, etc.).

[0079] Among R3 to R5, examples of alkoxy groups include linear or branched alkoxy groups having 1 to 18 carbon atoms (such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy).

[0080] Among R3 to R5, examples of alkylcarbonyl groups include linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms (such as acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanol, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, and octadecanoyl).

[0081] Among R3 to R5, examples of arylcarbonyl groups include arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

[0082] Among R3 to R5, examples of acyloxy groups include linear or branched acyloxy groups having 2 to 19 carbon atoms (such as acetoxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, octyl carbonyloxy, tetradecyl carbonyloxy, and octadecyl carbonyloxy).

[0083] Of R3 to R5, the arylthio groups include arylthio groups with 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio] Examples include phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4-(4-methylthiobenzoyl)phenylthio, 4-(2-methylthiobenzoyl)phenylthio, 4-(p-methylbenzoyl)phenylthio, 4-(p-ethylbenzoyl)phenylthio, 4-(p-isopropylbenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio, etc.

[0084] Among R3 to R5, examples of alkylthio groups include linear or branched alkylthio groups having 1 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio, etc.).

[0085] Among R3 to R5, examples of aryl groups include aryl groups with 6 to 10 carbon atoms (phenyl, tolyl, dimethylphenyl, and naphthyl, etc.).

[0086] Among R3 to R5, examples of heterocyclic hydrocarbon groups include heterocyclic hydrocarbon groups having 4 to 20 carbon atoms (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl, etc.).

[0087] Among R3 to R5, examples of aryloxy groups include aryloxy groups with 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

[0088] Among R3 to R5, examples of hydroxy(poly)alkylene oxy groups include the hydroxy(poly)alkylene oxy group represented by formula (2). HO(-R A O)q- (2) R A O represents an ethylene oxy group and / or a propylene oxy group, and q represents an integer from 1 to 5.

[0089] Among R3 to R5, examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0090] R3 to R5 may be the same, different, or partially different. When k, m, and n are each 2 or greater, multiple R3s may be identical or different from each other. Multiple R4s may be identical or different from each other. Multiple R5s may be identical or different from each other.

[0091] k represents the number of R3, and is an integer between 0 and 4, preferably between 0 and 2, more preferably 0 or 1, and particularly preferably 0. Furthermore, m represents the number of R4 and is an integer between 0 and 3, preferably 0 or 1, and particularly preferably 0. Furthermore, n represents the number of R5s and is an integer from 1 to 4, preferably 1 or 2 from the viewpoint of obtaining industrial raw materials, and more preferably 2 from the viewpoint of solubility.

[0092] R5 is preferably an alkyl group, with linear alkyl groups having 1 to 18 carbon atoms being more preferred, and branched alkyl groups having 3 to 18 carbon atoms being more preferred. There are no restrictions on the binding site of R5, but CS + The photosensitivity of the sulfonium salt is better when it is in the ortho position relative to the bond.

[0093] In the above formula (I0), L is a group represented by -O-, -S-, -SO-, -SO2-, or -CO-, preferably -S-.

[0094] In the above formula (I0), R1 and R2 are selected from an aryl group having 6 to 30 carbon atoms, a heterocyclic hydrocarbon group having 4 to 30 carbon atoms, and an alkyl group having 1 to 30 carbon atoms, respectively, and some of the hydrogen atoms of these aryl groups, heterocyclic hydrocarbon groups, and alkyl groups may be substituted with substituents (t). This substituent (t) is at least one selected from the group consisting of C1-C18 alkyl groups, hydroxyl groups, C1-C18 alkoxy groups, C2-C18 alkylcarbonyl groups, C7-C11 arylcarbonyl groups, C2-C19 acyloxy groups, C6-C20 arylthio groups, C1-C18 alkylthio groups, C6-C10 aryl groups, C4-C20 heterocyclic hydrocarbon groups, C6-C10 aryloxy groups, hydroxy(poly)alkyleneoxy groups, and halogen atoms. This substituent (t) is the same as the substituents described for R3-R5.

[0095] Among R1 and R2, aryl groups having 6 to 30 carbon atoms include monocyclic aryl groups and fused polycyclic aryl groups. Examples of monocyclic aryl groups include phenyl, hydroxyphenyl, toluyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, n-propoxyphenyl, isopropoxyphenyl, n-butoxyphenyl, isobutoxyphenyl, sec-butoxyphenyl, tert-butoxyphenyl, acetylphenyl, benzoylphenyl, naphthoylphenyl, phenylthiophenyl, naphthylthiophenyl, biphenylyl, phenoxyphenyl, naphthoxyphenyl, nitrophenyl, fluorophenyl, chlorophenyl, and bromophenyl.

[0096] Examples of condensed polycyclic aryl groups include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, crisenyl, naphthacenyl, benzoanthracenyl, anthraquinolyl, fluorenyl, naphthoquinolyl, hydroxynaphthyl, methylnaphthyl, ethylnaphthyl, methoxynaphthyl, ethoxynaphthyl, acetylnaphthyl, benzoylnaphthyl, phenylthionaphthyl, phenylnaphthyl, phenoxynaphthyl, nitronaphthyl, fluoronaphthyl, chloronaphthyl, bromonaphthyl, hydroxyanthracenyl, methylanthracenyl, ethylanthracenyl, methoxyanthracenyl, ethoxyanthracenyl, acetylanthracenyl, benzoylanthracenyl, phenylthioanthracenyl, phenoxyanthracenyl, nitroanthracenyl, fluoroanthracenyl, chloroanthracenyl, and bromoanthracenyl.

[0097] Among R1 and R2, heterocyclic hydrocarbon groups having 4 to 30 carbon atoms include cyclic hydrocarbon groups containing 1 to 3 heteroatoms (such as oxygen, nitrogen, and sulfur atoms) within the ring, and include monocyclic heterocyclic hydrocarbon groups and condensed polycyclic heterocyclic hydrocarbon groups.

[0098] Examples of monocyclic and heterocyclic hydrocarbon groups include thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, hydroxythienyl, methylthienyl, ethylthienyl, methoxythienyl, acetylthienyl, benzoylthienyl, phenylthiothienyl, phenoxythienyl, nitrothienyl, fluorothienyl, chlorothienyl, bromothienyl, hydroxyfuranyl, methylfuranyl, ethylfuranyl, methoxyfuranyl, acetylfuranyl, benzoylfuranyl, phenylthiofuranyl, phenoxyfuranyl, nitrofuranyl, fluorofuranyl, chlorofuranyl, and bromofuranyl.

[0099] Examples of condensed polycyclic heterocyclic hydrocarbon groups include indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl, hydroxyxanthenyl, and methylxanthenyl. Ethylxanthenyl, Methoxyxanthenyl, Acetylxanthenyl, Benzoylxanthenyl, Phenylthioxanthenyl, Phenoxyxanthenyl, Nitroxanthenyl, Fluoroxanthenyl, Chloroxanthenyl, Bromoxanthenyl, Hydroxythianthenyl, Methylthianthenyl, Ethylthianthenyl, Methoxythianthenyl, Benzoylthianthenyl, Phenylthiothianthenyl, Phenoxythianthenyl, Nitrothianthenyl, Fluoroxanthenyl Examples include chlorothianthrenyl, bromothiantrenyl, hydroxyxanthonyl, methylxanthonyl, dimethylxanthonyl, ethylxanthonyl, diethylxanthonyl, n-propylxanthonyl, isopropylxanthonyl, methoxyxanthonyl, acetylxanthonyl, benzoylxanthonyl, phenylthiooxanthonyl, phenoxyxanthonyl, acetoxyxanthonyl, nitroxanthonyl, fluoroxanthonyl, chloroxanthonyl, hydroxythiooxanthonyl, methylthiooxanthonyl, dimethylthiooxanthonyl, ethylthiooxanthonyl, diethylthiooxanthonyl, n-propylthiooxanthonyl, isopropylthiooxanthonyl, methoxythiooxanthonyl, acetylthiooxanthonyl, benzoylthiooxanthonyl, phenylthiooxanthonyl, phenoxythiooxanthonyl, acetoxythiooxanthonyl, nitrothiooxanthonyl, fluorothiooxanthonyl, chlorothiooxanthonyl, and bromothioxanthonyl.

[0100] Examples of alkyl groups having 1 to 30 carbon atoms among R1 and R2 include linear alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, ocdadecyl, benzyl, diphenylmethyl, naphthylmethyl, anthracenylmethyl, phenacyl (-CH2COC6H5), naphthoylmethyl, antholmethyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl, etc.), and cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, etc.).

[0101] R1 and R2 are preferably aryl groups having 6 to 30 carbon atoms, in which some of the hydrogen atoms may be substituted with substituents (t). More preferably, at least R2 is an aryl group having 6 to 30 carbon atoms in which some of the hydrogen atoms are substituted with substituents (t). Even more preferably, both R1 and R2 are aryl groups having 6 to 30 carbon atoms in which some of the hydrogen atoms are substituted with substituents (t). Particularly preferably, one of R1 or R2 is a benzoylphenyl group. Most preferably, from the viewpoint of photosensitivity and solubility, R1 is a benzoylphenyl group and R2 is an aryl group having 6 to 30 carbon atoms substituted with substituents (t).

[0102] The substituent (t) is preferably an alkyl group having 1 to 18 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 18 carbon atoms, or an arylcarbonyl group having 7 to 11 carbon atoms, more preferably an alkyl group or an alkoxy group, and particularly preferably a methyl group, an ethyl group, a propyl group (n-propyl, isopropyl), a butyl group (n-butyl, isobutyl, sec-butyl, tert-butyl), a methoxy group, or an ethoxy group.

[0103] In the (I0) component, the cation portion is preferably a cation in which L in the general formula (I0) is a group represented by -S- or -O-, k and m are 0, and n is an integer from 1 to 4. Alternatively, the cation portion in component (I0) is preferably a cation in which R1 or R2 in the general formula (I0) is an aryl group having 6 to 30 carbon atoms (some of the hydrogen atoms of this aryl group may be substituted with the substituent (t)). Alternatively, the cation portion in component (I0) is preferably a cation in which R1 in the general formula (I0) is a benzoylphenyl group, R2 is an aryl group having 6 to 30 carbon atoms substituted with substituent (t), k and m are 0, n is 1 or 2, and L is a group represented by -S-.

[0104] Specifically, the following cations can be considered as the cation portion in component (I0).

[0105] [ka]

[0106] In the above equation (I0), X - This refers to any monovalent polyatomic anion, and is the anion corresponding to the acid (HX) generated by irradiating sulfonium salts (I0) with active energy rays (visible light, ultraviolet light, electron beams, and X-rays, etc.). X - As for MY a - , (Rf) b PF 6-b - , R 6 c BY 4-c - , R 6 c Gay 4-c - , R 7 SO3 - , (R 7 SO2)3C - or (R 7 SO2)2N - An example of anion represented by [this formula] is [this formula].

[0107] M represents a phosphorus atom, a boron atom, or an antimony atom. Y represents a halogen atom, and a fluorine atom is preferred.

[0108] Rf represents an alkyl group in which 80 mol% or more of the hydrogen atoms are substituted with fluorine atoms. As the alkyl group that is fluorine-substituted to form Rf, an alkyl group having 1 to 8 carbon atoms is preferred, and examples include linear alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl, and octyl), branched-chain alkyl groups (such as isopropyl, isobutyl, sec-butyl, and tert-butyl), and cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl). In Rf, the ratio of the hydrogen atoms of these alkyl groups being substituted with fluorine atoms is preferably 80 mol% or more, more preferably 90% or more, and particularly preferably 100% based on the number of moles of the hydrogen atoms that the original alkyl group had. When the substitution ratio by fluorine atoms is within these preferred ranges, the photosensitivity of the sulfonium salt becomes even better. Particularly preferred Rf includes CF3-, CF3CF2-, (CF3)2CF-, CF3CF2CF2-, CF3CF2CF2CF2-, (CF3)2CFCF2-, CF3CF2(CF3)CF-, and (CF3)3C-. The b Rf groups are independent of each other and may be the same or different from each other.

[0109] P represents a phosphorus atom, and F represents a fluorine atom.

[0110] R 6 represents a phenyl group in which a part of the hydrogen atoms are substituted with at least one element or electron-withdrawing group. Examples of such an element include halogen atoms, such as fluorine atoms, chlorine atoms, and bromine atoms. Examples of electron-withdrawing groups include trifluoromethyl groups, nitro groups, and cyano groups. Among these, a phenyl group in which one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferred. The c Rs 6 are independent of each other and may be the same or different from each other.

[0111] B represents a boron atom, and Ga represents a gallium atom.

[0112] R 7 represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The alkyl group and perfluoroalkyl group may be linear, branched, or cyclic, and the alkyl group or aryl group may be unsubstituted or have substituents.

[0113] S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.

[0114] 'a' represents an integer between 4 and 6. b is preferably an integer from 1 to 5, more preferably from 2 to 4, and particularly preferably 2 or 3. c is preferably an integer between 1 and 4, and more preferably 4.

[0115] MY a - An anion represented by SbF6 - PF6 - and BF4 - Examples include anions represented by [the formula shown].

[0116] (Rf) b PF 6-b - The anion represented by (CF3CF2)2PF4 - (CF3CF2)3PF3 - , ((CF3)2CF)2PF4 - , ((CF3)2CF)3PF3 - (CF3CF2CF2)2PF4 - (CF3CF2CF2)3PF3 - , ((CF3)2CFCF2)2PF4 - , ((CF3)2CFCF2)3PF3 - (CF3CF2CF2CF2)2PF4 - and (CF3CF2CF2CF2)3PF3 -Examples of anions represented by (CF3CF2)3PF3 include the following. - (CF3CF2CF2)3PF3 - , ((CF3)2CF)3PF3 - , ((CF3)2CF)2PF4 - , ((CF3)2CFCF2)3PF3 - and ((CF3)2CFCF2)2PF4 - An anion represented by is preferred.

[0117] R 6 c BY 4-c - The anion represented by (C6F5)4B is - ,((CF3)2C6H3)4B - (CF3C6H4)4B - (C6F5)2BF2 - , C6F5BF3 - and (C6H3F2)4B - Anions represented by (C6F5)4B are examples of these. - and ((CF3)2C6H3)4B - An anion represented by is preferred.

[0118] R 6 c Gay 4-c - The anion represented by (C6F5)4Ga - , ((CF3)2C6H3)4Ga - (CF3C6H4)4Ga - , (C6F5)2GaF2 - , C6F5GaF3 - and (C6H3F2)4Ga - Examples of anions represented by include (C6F5)4Ga. - and ((CF3)2C6H3)4Ga - An anion represented by is preferred.

[0119] R 7 SO3 -Examples of anions represented by include trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutanesulfonic acid anion, pentafluorophenylsulfonic acid anion, p-toluenesulfonic acid anion, benzenesulfonic acid anion, camphorsulfonic acid anion, methanesulfonic acid anion, ethanesulfonic acid anion, propanesulfonic acid anion, and butanesulfonic acid anion. Of these, trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, butanesulfonic acid anion, camphorsulfonic acid anion, benzenesulfonic acid anion, and p-toluenesulfonic acid anion are preferred.

[0120] (R 7 SO2)3C - The anion represented by (CF3SO2)3C is - (C2F5SO2)3C - , (C3F7SO2)3C - and (C4F9SO2)3C - Examples include anions represented by [the formula shown].

[0121] (R 7 SO2)2N - The anion represented by (CF3SO2)2N is - (C2F5SO2)2N - (C3F7SO2)2N - and (C4F9SO2)2N - Examples include anions represented by [the formula shown].

[0122] As monovalent polyatomic anions, MY a - , (Rf) b PF 6-b - , R 6 c BY 4-c - , R 6 c Gay 4-c - , R7 SO3 - , (R 7 SO2)3C - or (R 7 SO2)2N - In addition to the anion represented by (ClO4), there is also the perhalate ion (ClO4 - , BrO4 - (etc.), halogenated sulfonate ions (FSO3) - ClSO3 - (etc.), sulfate ions (CH3SO4) - CF3SO4 - HSO4 - (etc.), carbonate ions (HCO3) - CH3CO3 - (etc.), aluminate ion (AlCl4) - AlF4 - (etc.), hexafluorobismuth ion (BiF6) - ), carboxylate ion (CH3COO - CF3COO - , C6H5COO - CH3C6H4COO - , C6F5COO - CF3C6H4COO - (etc.), arylborate ion (B(C6H5)4 - CH3CH2CH2CH2B(C6H5)3 - (etc.), thiocyanate ion (SCN - ) and nitrate ions (NO3 - ) and others can be used.

[0123] These X - Of these, MY a - , (Rf) b PF 6-b - , R 6 c BY 4-c - , R 6 c Gay 4-c - , R 7 SO3 - , (R 7 SO2)3C - or (R7 SO2)2N - An anion represented by is preferred.

[0124] For example, SbF6 has high cationic polymerizability. - PF6 - (CF3CF2)3PF3 - (C6F5)4B - ,((CF3)2C6H3)4B - (C6F5)4Ga - , ((CF3)2C6H3)4Ga - It is preferable. Furthermore, (CF3CF2)3PF3 offers improved resist resolution and pattern shape. - (C6F5)4B - ,((CF3)2C6H3)4B - (C6F5)4Ga - , ((CF3)2C6H3)4Ga - Trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, (CF3SO2)3C - and (CF3SO2)2N - It is preferable. Furthermore, (CF3CF2)3PF3 has good compatibility with cationic polymerizable compounds and resist compositions. - , nonafluorobutanesulfonate anion, (C6F5)4B - and ((CF3)2C6H3)4B - (CF3SO2)3C - That is particularly preferable. Also, (C6F5)4Ga - This is even more preferable in that it has excellent heat resistance and transparency.

[0125] In particular, in the negative-type photosensitive composition of this embodiment, the anion portion (X) of component (I0) - As such, borate anions are preferable because they allow for easier improvement in sensitivity, pattern shape, and resolution. As such borate anions, R 6c BY 4-c - is preferred, and (C6F5)4B - , ((CF3)2C6H3)4B - is particularly preferred.

[0126] Specific examples of the preferred (I0) component are given below.

[0127]

Chemical formula

[0128]

Chemical formula

[0129]

Chemical formula

[0130]

Chemical formula

[0131]

Chemical formula

[0132]

Chemical formula

[0133]

Chemical formula

[0134]

Chemical formula

[0135]

Chemical formula

[0136] Component (I0) may be used alone or in combination of two or more types. The (I0) component is preferably at least one selected from the group consisting of compounds (I0-01) to (I0-54), more preferably at least one selected from the group consisting of compounds (I0-25) to (I0-36), and even more preferably at least one selected from the group consisting of compounds (I0-25) to (I0-30). In the negative-type photosensitive composition of this embodiment, the content of component (I0) is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of component (A). If the content of component (I0) is above the lower limit of the preferred range described above, sufficient sensitivity is obtained, and the resolution of the pattern is further improved. In addition, the strength of the cured film is further increased. On the other hand, if it is below the upper limit of the preferred range described above, the sensitivity is moderately controlled, and it becomes easier to obtain a pattern with a good shape that is highly rectangular.

[0137] [Method for producing sulfonium salt (I0)] The sulfonium salt (I0) in this embodiment can be produced by the manufacturing method described below.

[0138] The method shown in the reaction equation below (for example, the method described in JP-A-7-329399, JP-A-8-165290, JP-A-10-212286, or JP-A-10-7680, etc., 4th edition of Experimental Chemistry Course, Vol. 24, 1992, published by Maruzen Co., Ltd., p. 376).

[0139] [ka]

[0140] In the above reaction equation, R1 to R5, L, S, O, X - k, m, and n are R1 to R5, L, S, O, and X in the above general formula (I0).- The definitions of k, m, and n are the same. H represents a hydrogen atom. HX' represents the conjugate acid of a monovalent polyatomic anion. From the viewpoint of availability, acid stability, and reaction yield, methanesulfonic acid, perfluoromethanesulfonic acid, and sulfuric acid are preferred as HX'. Dehydrating agents include, for example, anhydrous phosphoric acid, anhydrous acetic acid, or concentrated sulfuric acid. Monovalent polyatomic anion (X' - ) is, for example, broken down into other anions (X) by a double decomposition reaction as described above. - It can be replaced with ). MX is an alkali metal (lithium, sodium, potassium, etc.) cation and the other anions {for example, MY}. a - , (Rf) b PF 6-b - , R 6 c BY 4-c - , R 6 c Gay 4-c - , R 7 SO3 - , (R 7 SO2)3C - or (R 7 SO2)2N - It represents a salt with the anion shown by, etc.

[0141] In the above reaction equation, the first step may be carried out without a solvent, or, if necessary, in an organic solvent (acetonitrile, tetrahydrofuran, dioxane, ethanol, acetone, etc.). The reaction temperature is approximately 20 to 105°C.

[0142] The second reaction may proceed immediately following the first reaction, or a reaction intermediate may be formed. <g2>It may be performed after isolating (and purifying, if necessary) the substance. reaction intermediate <g2>The aqueous solution of the alkali metal cation and the salt (MX) of the other anion is mixed and stirred to carry out a double decomposition reaction, and the precipitated solid is filtered off, or the separated oily substance is extracted with an organic solvent to remove the organic solvent, thereby obtaining the sulfonium salt (I0) as a solid or viscous liquid. The obtained solid or viscous liquid can be washed with a suitable organic solvent as needed, or purified by recrystallization or column chromatography.

[0143] The chemical structure of sulfonium salts (I0) can be determined using common analytical methods (for example, 1 H-, 11 B-, 13 C-, 19 F-, 31 It can be identified by P-nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, and / or elemental analysis, etc.

[0144] ≪Cational polymerization initiators other than component (I0)≫ In the negative-type photosensitive composition of this embodiment, in addition to component (I0), a cationic polymerization initiator other than component (I0) may also be used as component (I). Other cationic polymerization initiators besides component (I0) are not particularly limited, and examples include cationic polymerization initiators with different cationic moieties in component (I0).

[0145] Suitable cations that differ from the cation portion in component (I0) above include sulfonium cations and iodonium cations, and organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred.

[0146] [ka] [In the formula, R 201 ~R 207 , and R 211 ~R 212 Each of these independently represents an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 These atoms may bond to each other to form a ring with the sulfur atom in the formula. 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 This represents -C(=O)- or -C(=O)-O-. 201 Each of these independently represents an arylene group, an alkylene group, or an alkenylene group. x is either 1 or 2. W 201 This represents a linking group with (x+1) valence.

[0147] R 201 ~R 207 , and R 211 ~R 212 Examples of aryl groups in this compound include substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 201 ~R 207 , and R 211 ~R 212 Examples of heteroaryl groups include those in which some of the carbon atoms constituting the aryl group are replaced by heteroatoms. Examples of these heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Examples of such heteroaryl groups include a group obtained by removing one hydrogen atom from 9H-thioxanthene; and examples of substituted heteroaryl groups include a group obtained by removing one hydrogen atom from 9H-thioxanthene-9-one. R 201 ~R 207 , and R 211 ~R 212 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 , and R 211 ~R 212 The alkenyl group in this compound preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 ~R 212 Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, oxo groups (=O), aryl groups, and groups represented by the following formulas (ca-r-1) to (ca-r-10).

[0148] [ka] [In the formula, R' 201 Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0149] Cyclic groups which may have substituents: The aforementioned R' 201 The cyclic group in is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0150] R' 201 The aromatic hydrocarbon group in this formula is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R' 201 Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups, etc. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R' 201 Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, anthracenyl groups, etc.), groups in which one of the hydrogen atoms of the aromatic ring is substituted with an alkylene group (for example, arylalkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, 2-naphthylethyl groups, etc.), groups obtained by removing one hydrogen atom from a ring in which some of the hydrogen atoms constituting the aromatic ring are substituted with oxo groups, etc. (for example, anthraquinones, etc.), and groups obtained by removing one hydrogen atom from an aromatic heterocycle (for example, 9H-thioxanthene, 9H-thioxanthene-9-one, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0151] R' 201 In this context, cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, polycycloalkanes having a bridging ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a fused ring polycyclic skeleton such as a steroid skeleton are more preferred.

[0152] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, with adamantyl and norbornyl groups being particularly preferred, and the adamantyl group being the most preferred.

[0153] The linear or branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0154] Chain-like alkyl groups which may have substituents: The aforementioned R' 201 The linear alkyl group in this can be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, henicosyl group, docosyl group, and the like. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0155] A chain-like alkenyl group which may have substituents: The aforementioned R' 201 The linear alkenyl group in this compound may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3 carbon atoms. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0156] R' 201 Substituents in the cyclic group, linear alkyl group, or alkenyl group include, for example, an alkoxy group, a halogen atom, an alkyl halide, a hydroxyl group, a carbonyl group, a nitro group, an amino group, an oxo group, and the above R' 201 Examples include cyclic groups, alkylcarbonyl groups, and thienylcarbonyl groups in this material.

[0157] Among them, R' 201 The preferably substituted cyclic group and the preferably substituted linear alkyl group are both cyclic and linear alkyl groups.

[0158] R 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 When these atoms bond to each other and form a ring with the sulfur atom in the formula, they may be heteroatoms such as sulfur, oxygen, or nitrogen atoms, or carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(applicable R N is an alkyl group having 1 to 5 carbon atoms. ) may be bonded via functional groups such as ). The formed ring is preferably a 3 to 10-membered ring, and particularly preferably a 5 to 7-membered ring, including the sulfur atom in its ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthlene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthlene ring, a phenoxatiyine ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium ring, and the like.

[0159] In the above formula (ca-3), R 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. If an alkyl group is formed, it may bond to each other to form a ring.

[0160] In the above formula (ca-3), R 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 Examples of aryl groups in this compound include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 210 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in this compound preferably has 2 to 10 carbon atoms.

[0161] In the above equations (ca-4) and (ca-5), Y 201 Each of these independently represents an arylene group, an alkylene group, or an alkenylene group. Y 201 The arylene group in this case is R' 201 An example of an aromatic hydrocarbon group in this context is the aryl group exemplified above, with one hydrogen atom removed. Y 201 In this context, the alkylene group and alkenylene group are R' 201 Examples of the chain-like alkyl groups and chain-like alkenyl groups mentioned above include groups obtained by removing one hydrogen atom from the exemplified groups.

[0162] In equations (ca-4) and (ca-5) above, x is either 1 or 2. W 201 This is a (x+1) valence, i.e., a divalent or trivalent linking group. W 201 In the above formula (Ap-1), the divalent linking group is preferably a divalent hydrocarbon group which may have substituents, and R EP A group similar to the divalent hydrocarbon group which may have substituents as exemplified is preferred. 201 The divalent linking group in this compound may be linear, branched, or cyclic, with cyclic being preferred. Among these, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting only of an arylene group, is preferred. Examples of arylene groups include phenylene groups and naphthylene groups, with phenylene groups being particularly preferred. W 201 The trivalent linking group in is the aforementioned W 201 Examples include a group obtained by removing one hydrogen atom from a divalent linking group, and a group in which another divalent linking group is bonded to the aforementioned divalent linking group. 201 In this compound, a trivalent linking group is preferably a group in which two carbonyl groups are bonded to an arylene group.

[0163] As for the anionic portion of the cationic polymerization initiator other than component (I0), a sulfonic acid anion is preferred. For example, the above R is an example of this sulfonic acid anion. 7 SO3 - Examples of anions include those represented by , with the camphor sulfonate anion being particularly preferred.

[0164] In the negative-type photosensitive composition of this embodiment, when a cationic polymerization initiator other than component (I0) is used in combination, the content of the cationic polymerization initiator other than component (I0) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 2 parts by mass, per 100 parts by mass of component (A).

[0165] <Other ingredients> The negative-type photosensitive composition of this embodiment may contain other components as needed, in addition to the components (A) and (I) described above. The negative-type photosensitive composition of the embodiment may optionally contain miscible additives, such as silane coupling agents, sensitizer components, metal oxides (M), solvents, additional resins for improving film performance, dissolution inhibitors, basic compounds, plasticizers, stabilizers, colorants, and anti-halation agents.

[0166] ≪Silane coupling agents≫ The negative-type photosensitive composition of this embodiment may further contain an adhesion aid to improve adhesion to the substrate. A silane coupling agent is preferred as this adhesion aid. That is, the negative-type photosensitive composition of this embodiment may further contain a silane coupling agent. Examples of silane coupling agents include those having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Silane coupling agents may be used individually or in combination of two or more types. If a silane coupling agent is included, its content is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 3 parts by mass, per 100 parts by mass of component (A). When the silane coupling agent content is within the preferred range described above, the strength of the cured film is further enhanced. In addition, the adhesion between the cured film and the substrate is further strengthened.

[0167] ≪Sensitizing ingredients≫ The negative-type photosensitive composition of this embodiment may further contain a sensitizer component. The sensitizing agent component is not particularly limited as long as it can absorb the energy from exposure and transfer that energy to other substances. Specifically, the sensitizing agents that can be used include benzophenone-based photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone; carbazole-based photosensitizers; acetophene-based photosensitizers; naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene; phenol-based photosensitizers; anthracene-based photosensitizers such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 9-ethoxyanthracene; and known photosensitizers such as biacetyl, eosin, rose bengal, pyrene, phenothiazine, and anthrone. The sensitizing agent component may be used alone or in combination of two or more types. If a sensitizer component is included, the content is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of component (A). When the content of the sensitizer component is within the aforementioned preferred range, sensitivity and resolution are further enhanced.

[0168] ≪Metal Oxides (M)≫ The negative-type photosensitive composition of this embodiment may further contain a metal oxide (M) (hereinafter also referred to as "component (M)") because it is easy to obtain a hardened film with increased strength. Furthermore, by including component (M), it is possible to form a high-resolution pattern with a good shape. Examples of component (M) include metal oxides such as silicon (metallic silicon), titanium, zirconium, and hafnium. Among these, silicon oxide is preferred, and among these, silica is particularly preferred. Furthermore, the shape of component (M) is preferably particulate. The particulate (M) component is preferably composed of a group of particles with a volume-average particle diameter of 5 to 40 nm, more preferably composed of a group of particles with a volume-average particle diameter of 5 to 30 nm, and even more preferably composed of a group of particles with a volume-average particle diameter of 10 to 20 nm. If the volume-average particle size of component (M) is above the lower limit of the preferred range mentioned above, the strength of the cured film is more easily increased. On the other hand, if it is below the upper limit of the preferred range mentioned above, less residue is generated during pattern formation, and a higher-resolution pattern is more easily formed. In addition, the transparency of the resin film is improved. The particle size of component (M) can be appropriately selected depending on the exposure light source. Generally, particles with a particle size of 1 / 10 or less of the wavelength of light are considered to have virtually no effect on light scattering. For this reason, when forming a microstructure by photolithography using the i-line (365 nm), for example, it is preferable to use a group of particles with a primary particle size (volume mean) of 10 to 20 nm (particularly preferably a group of silica particles) as component (M). (M) Component may be used alone or in combination of two or more types. If component (M) is included, its content is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of component (A). If the content of component (M) is above the lower limit of the preferred range described above, the strength of the cured film is further increased. On the other hand, if it is below the upper limit of the preferred range described above, the transparency of the resin film is further increased.

[0169] Solvents The negative-type photosensitive composition of this embodiment may further contain a solvent (hereinafter sometimes referred to as "component (S)"). (S) Component may include, for example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), 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 ester bonds such as 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the polyhydric alcohols or compounds having ester bonds; or Examples include derivatives of polyhydric alcohols such as compounds having ether bonds, such as nophenyl ether [among these, 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, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, and dimethyl sulfoxide (DMSO). Component (S) may be used alone or as a mixture of two or more solvents.

[0170] The amount used when component (S) is included is not particularly limited and is set appropriately according to the coating thickness, at a concentration that allows the photosensitive composition to be applied to a substrate or the like without dripping. For example, the (S) component may be used so that the solid content concentration is 50% by mass or more, or the (S) component may be used so that the solid content concentration is 60% by mass or more, or even more so that the solid content concentration is 70% by mass or more. Furthermore, embodiments that substantially do not contain component (S) (i.e., embodiments in which the solid content concentration is 100% by mass) can also be adopted.

[0171] In the negative-type photosensitive composition of this embodiment described above, a novolac-type polyfunctional aromatic epoxy resin (component (Ap)) and a trifunctional epoxy monomer (component (Am)) are used in combination in a specific mass ratio (component (Am) / component (Ap) = 5 / 5 to 8 / 2). Therefore, intermolecular polymerization is promoted by exposure. Furthermore, in the negative-type photosensitive composition of this embodiment, an epoxy group-containing compound using both (Ap) and (Am) components is combined with a specific sulfonium salt represented by the general formula (I0). This specific sulfonium salt is a sulfonium cation S + Because the nearby benzene ring has a substituent (R5), the photodegradation rate and developer solubility are increased without increasing absorbance. In addition, because this particular sulfonium salt has a benzoyl group, light absorption is moderately suppressed, allowing light to easily reach the substrate interface. According to the negative-type photosensitive composition of this embodiment, the synergistic effect of the (Ap) component and the (Am) component used in combination in a specific mass ratio with a specific sulfonium salt allows for high sensitivity in pattern formation and the formation of a well-shaped pattern with high rectangularity. Furthermore, according to the negative-type photosensitive composition of this embodiment, undercuts at the substrate interface are less likely to occur during pattern formation, and a high-resolution negative-type pattern can be formed.

[0172] (Laminated film) The laminated film of this embodiment is formed by laminating a photosensitive composition layer, which is composed of the negative-type photosensitive composition of the embodiment described above, with a support film. Furthermore, the laminated film may have a cover film positioned on the side of the photosensitive composition layer formed using a negative-type photosensitive composition that is opposite to the side where the support film exists.

[0173] The laminated film of this embodiment can be manufactured, for example, by applying the negative-type photosensitive composition of the above-described embodiment onto a support film, drying it to form a photosensitive composition layer, and then laminating a cover film on the photosensitive composition layer. The negative-type photosensitive composition can be applied to the substrate film using an appropriate method such as a blade coater, lip coater, comma coater, or film coater. The thickness of the photosensitive composition layer is preferably 100 μm or less, and more preferably 5 to 50 μm.

[0174] A known support film can be used, such as a thermoplastic resin film. Examples of thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 to 150 μm. A known cover film can be used, such as polyethylene film or polypropylene film. The cover film is preferably one that has less adhesion to the photosensitive composition layer than the support film. The thickness of the cover film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and even more preferably 5 to 50 μm. The support film and the cover film may be made of the same film material, or they may be made of different film materials.

[0175] (Pattern formation method) The pattern formation method of this embodiment comprises the steps of: forming a photosensitive film on a support using the negative-type photosensitive composition of the embodiment described above (hereinafter referred to as the "film formation step"); exposing the photosensitive film to light (hereinafter referred to as the "exposure step"); and developing the exposed photosensitive film with a developer solution containing an organic solvent to form a negative-type pattern (hereinafter referred to as the "development step"). The pattern formation method of this embodiment can be carried out, for example, as follows.

[0176] [Film formation process] First, the negative-type photosensitive composition of the above-described embodiment is applied to a support by a known method such as spin coating, roll coating, or screen printing, and a bake (post-application bake (PAB)) treatment is performed for 2 to 60 minutes at a temperature of, for example, 50 to 150°C to form a photosensitive film. Furthermore, the film formation process can also be carried out by placing the photosensitive composition layer of the aforementioned laminated film onto a support.

[0177] The support material is not particularly limited and can be any conventionally known material, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern has been formed. More specifically, examples include metal substrates such as silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO3), niobium, lithium niobate (LiNbO3), palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates. For the wiring pattern material, for example, copper, aluminum, nickel, and gold can be used.

[0178] The pattern formation method of this embodiment is useful, for example, for lithium tantalate (LiTaO3) substrates and lithium niobate (LiNbO3) substrates used in SAW devices mounted on communication terminals.

[0179] The thickness of the photosensitive film formed by the negative-type photosensitive composition is not particularly limited, but is preferably about 10 to 100 μm. The negative-type photosensitive composition of the above embodiment can also obtain good properties even when a thick film is formed.

[0180] [Synthesis process] Next, the formed photosensitive film is subjected to selective exposure using a known exposure apparatus, either through exposure via a mask (mask pattern) with a predetermined pattern formed on it, or by drawing by direct irradiation with an electron beam without using a mask pattern. Then, if necessary, a bake (post-exposure bake (PEB)) treatment is performed for 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds, at a temperature of, for example, 80 to 150°C.

[0181] The wavelength used for exposure is not particularly limited; radiation, such as ultraviolet light with a wavelength of 300-500 nm, i-rays (wavelength 365 nm), or visible light, is selectively irradiated (exposed). Suitable radiation sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. Here, radiation refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc., but for example, when using an ultra-high pressure mercury lamp, it is 100 to 2000 mJ / cm². 2 That is the case.

[0182] The exposure method for the photosensitive film may be conventional exposure in an inert gas such as air or nitrogen (dry exposure), or it may be liquid immersion lithography.

[0183] The photosensitive film after the exposure process has high transparency, and for example, the haze value when irradiated with i-line light (wavelength 365 nm) is preferably 3% or less, more preferably 1.0 to 2.5%. As described above, the photosensitive film formed using the negative-type photosensitive composition of the embodiment has high transparency. Therefore, during exposure in pattern formation, light transmittance is increased, making it easier to obtain a negative-type pattern with good lithography characteristics. The haze value of the photosensitive film after such exposure process is measured using a method compliant with JIS K 7136 (2000).

[0184] [Development process] Next, the photosensitive film after exposure is developed with a developer containing an organic solvent (organic developer). After development, a rinsing treatment is preferably performed. A bake treatment (post-bake) may be performed if necessary.

[0185] The organic solvent contained in the organic developer solution can be any solvent capable of dissolving component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0186] 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, propylene carbonate, γ-butyrolactone, and methyl amyl ketone (2-heptanone). Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0187] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate (PGMEA), 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 monoethyl 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, pro Pyrene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, milk Examples include ethyl acid, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like.Among these, butyl acetate or PGMEA is preferred as the ester solvent.

[0188] Examples of nitrile solvents include acetonitrile, propionitol, valeronitrile, and butyronitrile.

[0189] Organic developers may contain known additives as needed. Examples of such additives include surfactants. While not particularly limited, surfactants such as ionic or nonionic fluorine-based and / or silicone-based surfactants can be used. As the surfactant, a nonionic surfactant is preferred, and a nonionic fluorine-based surfactant or a nonionic silicone-based surfactant is more preferred. When a surfactant is added, the amount added is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total amount of the organic developer.

[0190] The development process can be carried out by known development methods, such as the dipping method, which involves immersing the support in a developer solution for a certain period of time; the paddle method, which involves piling the developer solution onto the surface of the support using surface tension and leaving it still for a certain period of time; the spray method, which involves spraying the developer solution onto the surface of the support; and the dynamic dispensing method, which involves continuously dispensing the developer solution onto a support rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed.

[0191] Rinsing (cleaning) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously applying the rinsing solution onto a support rotating at a constant speed (rotary coating method), immersing the support in the rinsing solution for a certain period of time (dip method), and spraying the rinsing solution onto the surface of the support (spray method). For the rinsing process, it is preferable to use a rinsing solution containing an organic solvent.

[0192] A negative-type pattern can be formed by the film formation process, exposure process, and development process described above.

[0193] In the pattern formation method of the embodiment described above, since the negative-type photosensitive composition of the first embodiment described above is used, it is possible to form a pattern with high sensitivity and a good shape with high rectangularity. In addition, according to the pattern formation method of the embodiment, undercuts at the substrate interface are less likely to occur during pattern formation, and a negative-type pattern with high resolution can be formed. As a result, for example, metal deposition in a subsequent process can be performed well.

[0194] (cured film) The cured film of this embodiment is obtained by curing the negative-type photosensitive composition of the embodiment described above.

[0195] (Method for manufacturing a hardened film) The method for manufacturing a cured film according to this embodiment comprises the steps of (i) forming a photosensitive film on a support using the negative-type photosensitive composition of the above-described embodiment, and (ii) curing the photosensitive film to obtain a cured film. The operation in step (i) can be carried out in the same manner as the [film formation step] described above. The baking process can be carried out, for example, at a temperature of 80 to 150°C for 40 to 600 seconds. The curing treatment in step (ii) can be carried out, for example, under conditions of a temperature of 100 to 250°C for 0.5 to 2 hours. The method for manufacturing the cured film of the embodiment may include other steps besides steps (i) and (ii). For example, the above-described [exposure step] may be included between step (i) and step (ii), and the photosensitive film formed in step (i) may be selectively exposed, and if necessary, the photosensitive film (pre-cured film) which has undergone bake (PEB) treatment may be cured to obtain a cured film. According to the method for manufacturing a cured film of the embodiment described above, a cured film that faithfully reproduces the mask pattern can be easily manufactured. [Examples]

[0196] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0197] <Preparation of Negative-Type Photosensitive Composition> (Examples 1-5, Comparative Examples 1-11) Each component shown in Table 1 was dissolved in methyl ethyl ketone, and filtered using a PTFE filter (pore size 1 μm, manufactured by PALL) to prepare negative-type photosensitive compositions (solids content 70-85% by mass) for each example.

[0198] [Table 1]

[0199] In Table 1, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount of each component (parts by mass; on a solid content basis). (A)-1: A novolac-type epoxy resin represented by the following chemical formula (Ap-1-1). Trade name "jER157S70", manufactured by Mitsubishi Chemical Corporation. (A)-2: A monomer represented by the following chemical formula (Am-1-1).

[0200] [ka]

[0201] (A)-3: A monomer represented by the following chemical formula (A-3). (A)-4: An epoxy resin represented by the following chemical formula (A-4). (A)-5: An epoxy resin represented by the following chemical formula (A-5).

[0202] [ka]

[0203] (I)-1: A sulfonium salt represented by the following chemical formula (I0-1).

[0204] [ka]

[0205] (I)-2: A sulfonium salt represented by the following chemical formula (I1-1). (I)-3: Sulfonium salt represented by the following chemical formula (I1-2). (I)-4: Sulfonium salts represented by the following chemical formulas (I1-3).

[0206] [ka]

[0207] (Add)-1: A compound represented by the following chemical formula (Add-1). (Add)-2: A compound represented by the following chemical formula (Add-2).

[0208] [ka]

[0209] <Formation of negative patterns> Film formation process: Each negative-type photosensitive composition was applied to a silicon (Si) substrate using a spinner at 1500 rpm. A pre-bake (PAB) treatment was then performed on a hot plate at 90°C for 300 seconds, followed by drying to form a photosensitive film with a thickness of 20 μm.

[0210] Exposure process: Next, the photosensitive film was exposed to ghi broadband light using a Suss MA / BA8pro aligner. Subsequently, the sample was exposed to light and heated on a 110°C hot plate for 300 seconds.

[0211] Development process: Next, a negative pattern was formed by developing the film for 90 seconds using propylene glycol monomethyl ether acetate (PGMEA).

[0212] [Sensitivity evaluation] The optimal exposure dose Eop for forming a hole pattern of the target size (diameter 30 μm) was determined by the above <formation of a negative pattern>. This was expressed as "Sensitivity Eop (mJ / cm²)". 2 )" is shown in Table 2.

[0213] [Evaluation of Rectangularity] The cross-sectional shape of the hole pattern at the optimal exposure dose (Eop), formed in the above-described <Formation of Negative Pattern>, was observed using a scanning electron microscope (product name S4500; manufactured by Hitachi, Ltd.) and evaluated based on the following evaluation criteria. The results are shown in Table 2 as "Rectangularity (angle °)". Criteria for evaluating rectangularness ○: The angle between the resist wall and the silicon substrate was 85° or greater. ×: The angle in question was less than 85°.

[0214] [Undercut evaluation] The cross-sectional shape of the hole pattern formed by the above-described "Formation of Negative Pattern" was observed using a scanning electron microscope (product name S4500; manufactured by Hitachi, Ltd.), and the occurrence of undercuts (cuts at the peripheral edge of the negative pattern image (residual film) in contact with the silicon substrate) was evaluated based on the following evaluation criteria. The results are shown in Table 2. Criteria for evaluating undercuts ○: The angle between the silicon substrate surface and the cut surface of the residual film is 80° or greater, in the notch state of the peripheral edge of the negative pattern image (residual film) in contact with the silicon substrate. ×: The angle in question was less than 80°.

[0215] [Resolution evaluation] The critical resolution (μm) of the lines formed in the above-described <Negative Pattern Formation> at the optimal exposure Eop was measured using a scanning electron microscope (product name S4500; Hitachi, Ltd.) to evaluate the resolution. The results are shown in Table 2 as "Resolution (μm)".

[0216] [Table 2]

[0217] As shown in Table 2, the negative-type photosensitive compositions of Examples 1 to 5 to which the present invention was applied exhibited good sensitivity and improved rectangularity of the pattern shape compared to the negative-type photosensitive compositions of Comparative Examples 1 to 11. Furthermore, it was found that the negative-type photosensitive compositions of Examples 1 to 5 can form negative-type patterns that are less prone to undercutting and have higher resolution.

Claims

1. A negative-type photosensitive composition containing (A) an epoxy group-containing compound and (I) a cationic polymerization initiator, The aforementioned component (A) comprises component (Ap): a novolac-type polyfunctional aromatic epoxy resin and component (Am): a trifunctional epoxy monomer. The aforementioned component (I) includes component (I0): a sulfonium salt represented by the following general formula (I0), The (Am) component is a monomer represented by the following general formula (Am-1), A negative-type photosensitive composition in which the mixing ratio of component (Ap) and component (Am) is a mass ratio expressed as component (Am) / component (Ap) of 5 / 5 to 7 / 3. 【Chemistry 1】 [In formula (I0), R1 and R2 each represent an aryl group having 6 to 30 carbon atoms, a heterocyclic hydrocarbon group having 4 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms, and some of the hydrogen atoms of these aryl groups, heterocyclic hydrocarbon groups, or alkyl groups may be substituted with substituents (t). These substituents (t) are alkyl groups having 1 to 18 carbon atoms, hydroxyl groups, alkoxy groups having 1 to 18 carbon atoms, alkylcarbonyl groups having 2 to 18 carbon atoms, arylcarbonyl groups having 7 to 11 carbon atoms, acyloxy groups having 2 to 19 carbon atoms, arylthio groups having 6 to 20 carbon atoms, alkylthio groups having 1 to 18 carbon atoms, aryl groups having 6 to 10 carbon atoms, heterocyclic hydrocarbon groups having 4 to 20 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, HO(-R ６ O) q-{R ６ O represents an ethylene oxy group and / or a propylene oxy group, and q represents an integer from 1 to 5. R3 to R5 are each an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, a hydroxy (poly)alkylene oxy group, or a halogen atom. k, m, and n represent the number of R3, R4, and R5, where k is an integer from 0 to 4, m is an integer from 0 to 3, and n is an integer from 1 to 4. When k, m, and n are each 2 or more, the multiple R3, R4, and R5 may be the same or different from each other. L is -S-, -O-, -SO-, -SO ２ This group is represented by - or -CO-, where O is an oxygen atom, S is a sulfur atom, and X- represents a monovalent polyatomic anion. 【Chemistry 2】 [In formula (Am-1), R p3, R p4, and R p5 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Rm EP is an epoxy group-containing group. Multiple Rm EPs may be identical or different from one another.]

2. The negative-type photosensitive composition according to claim 1, wherein R2 in the general formula (I0) is an aryl group having 6 to 30 carbon atoms, substituted with the substituent (t).

3. X in the above general formula (I0) － The negative-type photosensitive composition according to claim 1, wherein is a borate anion.

4. The negative-type photosensitive composition according to claim 1, wherein the (Ap) component is a resin represented by the following general formula (Ap-1). 【Transformation 3】 [In formula (Ap-1), R ｐ１ and R ｐ２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A plurality of R ｐ１ may be the same as or different from each other. A plurality of R ｐ２ may be the same as or different from each other. n １ is an integer of 1 to 5. R ＥＰ is an epoxy group-containing group. A plurality of R ＥＰ may be the same as or different from each other.]

5. The negative-type photosensitive composition according to claim 1, wherein the content of component (I0) is 0.1 to 5 parts by mass per 100 parts by mass of component (A).

6. Furthermore, the negative-type photosensitive composition according to claim 1 further contains a silane coupling agent.

7. A step of forming a photosensitive film on a support using the negative-type photosensitive composition according to any one of claims 1 to 6, The process of exposing the photosensitive film, The process involves developing the photosensitive film after exposure with a developer containing an organic solvent to form a negative-type pattern. A pattern forming method having the following characteristics.

8. A laminated film comprising a photosensitive composition layer composed of a negative-type photosensitive composition according to any one of claims 1 to 6, and a support film.

9. A laminated film in which a cover film is disposed on the side opposite to the side where a support film exists, of a photosensitive composition layer formed using the negative-type photosensitive composition according to any one of claims 1 to 6.

10. A method for manufacturing a laminated film, comprising forming a photosensitive composition layer by applying a negative-type photosensitive composition according to any one of claims 1 to 6 onto a support film.

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