TW201307997A - Actinic ray-sensitive or radiation-sensitive resin composition, resist film and pattern forming method each using the composition, manufacturing method of electronic device and electronic device - Google Patents

Abstract

An actinic ray-sensitive or radiation-sensitive resin composition, includes: (A) a compound represented by the following formula (I); and (B) a resin: wherein X represents an oxygen atom, a sulfur atom or -N(Rx)-; each of R1 to R8 and Rx independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylcarbonyloxy group, an aryl group, an aryloxy group, an aryloxycarbonyl group or an arylcarbonyloxy group; and R1 to R8 may combine with each other to form a ring, provided that at least two members out of R1 to R8 represent a structure represented by the following formula (II) as defined in the specification.

Description

Photosensitive ray-sensitive or radiation-sensitive resin composition, resist film and pattern-forming method using the same, electronic component manufacturing method, and electronic component

The present invention relates to a sensitizing ray-sensitive or radiation-sensitive resin composition capable of changing its properties by a reaction after actinic ray or radiation irradiation, and the present invention relates to a resist film using the composition separately And pattern forming method. More particularly, the present invention relates to a sensitized ray- or radiation-sensitive resin composition for use in a semiconductor (such as IC) process, a liquid crystal cell or a circuit board (such as a thermal head), and other photographic processing processes, Or a lithographic printing plate or an acid curable composition; a resist film and a pattern forming method using the composition, respectively; and a method of manufacturing an electronic component and an electronic component.

The chemical amplification resist composition is a pattern forming substance which is formed by irradiating radiation such as far ultraviolet light to produce an acid in an exposed region, and changing the irradiated radiation irradiation region by using a reaction using the acid as a catalyst The irradiation area is soluble in the developer, and a pattern is formed on the substrate.

In the case of using KrF excimer electroluminescence as an exposure light source, a resin having a small absorption in a wavelength region of 248 nm and having a poly(hydroxystyrene) as a basic backbone is mainly used as a main component, and thus In the conventional naphthoquinone-diazide/novolak system, it is an excellent system capable of forming an excellent pattern with high sensitivity and high resolution.

On the other hand, since the compound having an aromatic group has substantially a large absorption in a region of 193 nm, the wavelength of the light source emitting light is higher. In a short case, for example, when an ArF excimer laser (193 nm) is used as an exposure light source, a satisfactory pattern cannot be formed even by the above chemical amplification system. To solve this problem, various resist compositions which are used together with an ArF excimer laser and which contain a resin having an alicyclic hydrocarbon structure have been developed.

Further, various compounds have been developed in view of the main constituent components (photoacid generators) of the above chemically amplified resist composition. For example, JP-A-2005-308969 (the term "JP-A" as used herein means an unexamined Japanese patent application) is a light consisting of a sulfonium salt having a sulfhydryl group or a similar substance. An acid generator, a photoacid generator composed of an aromatic sulfonium salt compound having a carbazole structure, and a resist composition described in JP-A-2006-99024, as described in JP-A-2010-235579 Compound of matter (which contains a plurality of ruthenium structures).

However, from the viewpoint of the overall performance of the resist, it is actually very difficult to find a suitable combination of a resin, a photoacid generator, a basic compound, an additive, a solvent, and the like, and nowadays Technology is still inefficient. For example, there is a need to develop a resist composition that ensures excellent exposure sensitivity and few development defects.

In view of the above, an object of the present invention is to provide a sensitized ray-sensitive or radiation-sensitive resin composition which ensures excellent exposure sensitivity and low development defects, a resist film and pattern forming method using the same, and an electronic component. Manufacturing method and electronic components.

[1] A photosensitive ray-sensitive or radiation-sensitive resin composition comprising: a compound (A) represented by the following formula (I); and a resin (B):

Wherein X represents an oxygen atom, a sulfur atom or -N(Rx)-; R ₁ to R ₈ and R _X each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group or an alkane group. a carbonyloxy group, an aryl group, an aryloxy group, an aryloxycarbonyl group or an arylcarbonyloxy group; and R ₁ to R ₈ may be bonded to each other to form a ring; the limitation is that at least two are from R ₁ to R ₈ The selected members represent the structure represented by the following formula (II):

Wherein when X is an oxygen atom or a sulfur atom, R ₉ and R ₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group; and when X is -N(Rx)-, R ₉ and R ₁₀ each independently represent an alkane. or a cycloalkyl group; and each R ₉ and each R ₁₀ may be the same or different from each other and each of the other R ₉ R _10; R ₉ and R ₁₀ may be bonded to each other to form a ring; and Z ^- Representing a non-nucleophilic anion, each Z ^- may be the same or different from each other Z ^- and a plurality of Z ^- may be combined to form a multivalent non-nucleophilic anion.

[2] A photosensitive ray-sensitive or radiation-sensitive resin composition as described in [1] above, wherein Z ^- in the formula (II) is a sulfonate anion.

[3] The photosensitive ray-sensitive or radiation-sensitive resin composition as described in the above [2], wherein Z ^- in the formula (II) is an anion represented by the following formula (III):

Wherein each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom; and R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom, and when a plurality of R _{When 11} and a plurality of R ₁₂ are present, each R ₁₁ and each R ₁₂ may be the same as or different from each of the other R ₁₁ and each of the other R ₁₂ ; L represents a divalent linking group, and when a plurality of L When present, each L may be the same or different from each other L; A represents a cyclic organic group; and x represents an integer from 1 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

[4] The photosensitive ray-sensitive or radiation-sensitive resin composition described in any one of the above [1] to [3], wherein R ₉ and R ₁₀ in the formula (II) are each independently an alkyl group. Or a cycloalkyl group, and R ₉ and R ₁₀ may be bonded to each other to form a ring.

[5] The sensitized ray-sensitive or radiation-sensitive resin composition described in any one of [1] to [4] above, wherein R ₉ and R ₁₀ in the formula (II) are combined to form a ring.

[6] The photosensitive ray-sensitive or radiation-sensitive resin composition described in any one of [1] to [5] above, wherein X represents -N(Rx)-, and Rx in the formula (I) is The alkyl group, the cycloalkyl group or the aryl group each having a structure represented by the formula (II) as a substituent, and at least one member selected from R ₁ to R ₈ is a structure represented by the formula (II).

[7] The photosensitive ray-sensitive or radiation-sensitive resin composition as described in any one of the above [1] to [6] wherein the resin (B) is decomposed by an action of an acid to increase the resin ( B) A resin that is soluble in an alkaline developer.

[8] A resist film formed by using a photosensitive ray-sensitive or radiation-sensitive resin composition as described in any one of the above [1] to [7].

[9] A pattern forming method comprising: exposing the resist film described in the above [8], thereby forming an exposed resist film; and developing the exposed resist film .

[10] The pattern forming method as described in [9] above, wherein the method of exposing is immersion exposure.

[11] A method of producing an electronic component, comprising: the pattern forming method as described in [9] or [10] above.

[12] An electronic component manufactured by the method of manufacturing an electronic component as described in the above [11].

The present invention preferably further includes the following configurations.

[13] The photosensitive ray-sensitive or radiation-sensitive resin composition as described in any one of the above [1] to [7] wherein the resin (B) comprises a lactone structure or a sultone structure. Repeat unit.

[14] The sensitizing ray-sensitive or radiation-sensitive resin composition described in any one of the above [1] to [7] and [13], further comprising: a hydrophobic resin (HR).

[15] The photosensitive ray-sensitive or radiation-sensitive resin composition as described in [14] above, wherein the hydrophobic resin (HR) is a hydrophobic resin having at least one of a fluorine atom or a ruthenium atom.

[16] The pattern forming method as described in [9] or [10] above, wherein the exposure is an ArF excimer laser type exposure.

In the present specification, when a group (atomic group) is represented by a substituent or a substitution thereof, the group includes both a group having no substituent and a group having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, the term "actinic ray" or "radiation" means For example, a bright line spectrum of a mercury lamp, a far-ultraviolet light represented by an excimer laser, an extreme ultraviolet light (EUV light), an X-ray or an electron beam (EB). In the present specification, "light" means actinic rays or radiation.

In the present invention, unless otherwise indicated, "exposure" includes not only exposure with a mercury lamp, far-ultraviolet light typified by a excimer laser, X-ray, EUV light, or the like, but also includes, for example, an electron beam. Or exposure by lithography of the particle beam of the ion beam.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention comprises: a compound (A) represented by the following formula (I) which is capable of generating an acid upon irradiation with actinic rays or radiation (hereinafter, sometimes referred to as " Compound (A)" or "Photoacid generator (A)"), and resin (B): Wherein in formula (I), X represents an oxygen atom, a sulfur atom or -N(Rx)-; R ₁ to R ₈ and Rx each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxy group. a carbonyl group, a fluorenyl group, an alkylcarbonyloxy group, an aryl group, an aryloxy group, an aryloxycarbonyl group or an arylcarbonyloxy group; and R ₁ to R ₈ may be bonded to each other to form a ring; the limitation is that at least two The member selected from R ₁ to R ₈ represents a structure represented by the following formula (II):

Wherein in formula (II), when X is an oxygen atom or a sulfur atom, R ₉ and R ₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group; and when X is -N(Rx)-, R ₉ And R ₁₀ each independently represents an alkyl or cycloalkyl group; and each R ₉ and each R ₁₀ may be the same or different from each other R ₉ and each other R ₁₀ ; R ₉ and R ₁₀ may be bonded to each other To form a ring; and Z ^- represents a non-nucleophilic anion, each Z ^- may be the same or different from each other Z ^- and may combine a plurality of Z ^- to form a multivalent non-nucleophilic anion.

By including the compound (A), the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention can secure excellent high exposure sensitivity and low development defects. Although the reason is not very clear, it is presumed that the cleavage of the CS ⁺ bond after absorption of light and the excitation with high efficiency contribute to the improvement of sensitivity; and the compound is in alkaline development due to the multivalent ionic compound. The agent exhibits excellent solubility and is less likely to become dross after development, which helps to reduce defects in development.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is, for example, a positive type composition or a typical positive resist composition.

The individual components of this composition are described below.

[1] A compound represented by the formula (I) (A)

As described above, the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains the compound (A) represented by (I). The compound (A) represented by the formula (I) is a compound capable of generating an acid upon irradiation with actinic rays or radiation.

The compound (A) capable of generating an acid after irradiation with actinic rays or radiation represented by the formula (I) will be described in detail below.

The alkyl group such as R ₁ to R ₁₀ and Rx may have a substituent, and is preferably a linear or branched alkyl group having a carbon number of 1 to 20, and the alkyl chain thereof may contain an oxygen atom, a sulfur atom or a nitrogen atom. . The alkyl group specifically includes a linear alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl and n-octadecyl. And branched alkyl groups such as: isopropyl, isobutyl, tert-butyl, neopentyl group and 2-ethylhexyl group.

Examples of the alkyl group having a substituent of Rx include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, and an ethoxycarbonylmethyl group.

The alkyl group having a substituent of R ₉ and R ₁₀ includes a methoxyethyl group.

Other examples include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantyl group, a cyclohexylethyl group, and a camphor residue).

The cycloalkyl group as R ₁ to R ₁₀ and Rx may have a substituent and is preferably a cycloalkyl group having a carbon number of 3 to 20, and the cycloalkyl group may contain an oxygen atom in the ring. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

The alkoxy group as R ₁ to R ₈ and Rx may have a substituent and is preferably an alkoxy group having a carbon number of 1 to 20. Specific examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, and a cyclohexyloxy group.

The alkoxycarbonyl group as R ₁ to R ₈ and Rx may have a substituent and is preferably an alkoxycarbonyl group having a carbon number of 2 to 20. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a cyclohexyloxycarbonyl group.

The fluorenyl group as R ₁ to R ₈ and Rx may have a substituent and is preferably a fluorenyl group having a carbon number of 2 to 10. Specific examples thereof include an ethenyl group, a propiony group, and an isobutyryl group.

The alkylcarbonyloxy group as R ₁ to R ₈ and Rx may have a substituent and is preferably an alkylcarbonyloxy group having a carbon number of 2 to 20. Specific examples thereof include a methylcarbonyloxy group, an ethylcarbonyloxy group, an isopropylcarbonyloxy group, and a cyclohexylcarbonyloxy group.

The aryl group as R ₁ to R ₁₀ and Rx may have a substituent and is preferably an aryl group having a carbon number of 6 to 14, and examples thereof include a phenyl group and a naphthyl group.

The aryloxy group as R ₁ to R ₈ and Rx may have a substituent and is preferably an aryloxy group having a carbon number of 6 to 14, and examples thereof include a phenoxy group and a naphthyloxy group.

The aryloxycarbonyl group as R ₁ to R ₈ and Rx may have a substituent and is preferably an aryloxycarbonyl group having a carbon number of 7 to 15, and examples thereof include a phenoxycarbonyl group and a naphthyloxycarbonyl group.

The arylcarbonyloxy group as R ₁ to R ₈ and Rx may have a substituent and is preferably an arylcarbonyloxy group having a carbon number of 7 to 15, and examples thereof include a phenylcarbonyloxy group and a naphthylcarbonyloxy group. .

As R ₁ to R ₁₀ and the cycloalkyl group Rx as R ₁ to R ₈ and the alkoxy group Rx as R ₁ to R ₈ and Rx of the alkoxycarbonyl group as R ₁ to R ₈ and the Rx alkylcarbonyloxy group, as R ₁ to R ₁₀ and the aryl group Rx as R ₁ to R ₈ and Rx of the aromatic group, as R ₁ to R ₈ and Rx of the aryloxycarbonyl group, and R ₁ to a Examples of the substituent on each of the arylcarbonyloxy group of R ₈ and Rx include an alkyl group (which may be a linear type, a branched form, or a cyclic form, preferably a carbon number of 1 to 12), and an aryl group (compared a preferred carbon number is 6 to 14), a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), a cycloalkyl group (preferably carbon) The number is 3 to 15), and the thiol group (preferably having a carbon number of 2 to 12).

In particular, Rx may be an alkyl group, a cycloalkyl group or an aryl group each having a structure represented by the formula (II) as a substituent.

In the present invention, at least two members selected from R ₁ to R ₈ represent a structure represented by the formula (II). However, in the case where Rx is an alkyl group, a cycloalkyl group or an aryl group each having a structure represented by the formula (II) as a substituent, at least one of R ₁ to R ₈ may be a structure represented by the formula (II) .

In the present invention, it is preferred to combine R ₉ and R ₁₀ to form a ring.

The ring structure which can be formed by combining R ₉ and R ₁₀ with each other is a divalent R ₉ and R ₁₀ (for example, an exoethyl, a propyl or a 1,2-cyclohexyl group and the like) and a formula The 5-membered or 6-membered ring formed by the sulfur atom in (II) is preferably a 5-membered ring (i.e., a tetrahydrothiophene ring).

The ring structure formed by combining any two or more members selected from R ₁ to R ₈ with each other is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring.

When X is an oxygen atom or a sulfur atom, R ₉ and R ₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group, and when X is -N(Rx)-, R ₉ and R ₁₀ each independently represent an alkyl group. Or a cycloalkyl group.

In each case where X in the formula (I) is an oxygen atom, a sulfur atom or -N(Rx)-, it is preferred that R ₉ and R ₁₀ in the formula (II) are each independently an alkyl group or a cycloalkyl group. And R ₉ and R ₁₀ may be bonded to each other to form a ring.

Particularly preferred examples of R ₁ to R ₈ include an alkyl group which may have a substituent and a hydrogen atom. However, in the case of using, for example, an ArF resist, from the viewpoint of the absorption strength of 193 nm, a hydrogen atom is more preferable.

Rx is preferably an alkyl group.

Z ^- represents a non-nucleophilic anion (an anion having a very low nucleophilic reaction promoting ability), each Z ^- may be the same as or different from each other Z ^- , and a plurality of Z ^- may be combined to form a multivalent (for example, at least a divalent) non-nucleophilic anion.

Examples of Z- include sulfonate anions (such as aliphatic sulfonate anions, aromatic sulfonate anions, and camphor sulfonate anions), carboxylate anions (such as aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylates). Anion), sulfonium imine anion, bis(alkylsulfonyl) quinone anion and tris(alkylsulfonyl)methide anion.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having a carbon number of 1 to 30 or a carbon number of 3 to 30 cycloalkyl.

An example of a case where a plurality of Z ^- bonds are combined to form a multivalent non-nucleophilic anion includes an embodiment in which two aliphatic sulfonate anions are bonded in an aliphatic group moiety to form an alkylene group or a cycloalkyl group.

Aroma of aromatic sulfonate anion and aromatic carboxylate anion The group group is preferably an aryl group having a carbon number of 6 to 14, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The above alkyl group, cycloalkyl group and aryl group may have a substituent. Specific examples of the substituent include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3) To 15), an aryl group (preferably having a carbon number of 6 to 14), an alkoxycarbonyl group (preferably having a carbon number of 2 to 7), a mercapto group (preferably having a carbon number of 2 to 12), an alkoxycarbonyloxy group a base (preferably having a carbon number of 2 to 7), an alkylthio group (preferably having a carbon number of 1 to 15), an alkylsulfonyl group (preferably having a carbon number of 1 to 15), and an alkylimidosulfonyl group. (preferably having a carbon number of 2 to 15), an aryloxysulfonyl group (preferably having a carbon number of 6 to 20), an alkylaryloxysulfonyl group (preferably having a carbon number of 7 to 20), a cycloalkyl group An aryloxysulfonyl group (preferably having a carbon number of 10 to 20), an alkoxyalkoxy group (preferably having a carbon number of 5 to 20), a cycloalkyl alkoxyalkoxy group (preferably having a carbon number of 8) To 20). The aryl group and ring structure in each group may further have an alkyl group (preferably having a carbon number of 1 to 15) as a substituent.

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

Examples of the sulfonium imine anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl)phosphonium anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms.

The two alkyl groups in the bis(alkylsulfonyl) quinone imine anion can be combined to form an alkylene group (preferably having a carbon number of 2 to 4) and can be combined with an imido group and two sulfonates. The sulfhydryl groups together form a ring. Bis(alkylsulfonyl) The ring structure formed by the quinone imine anion is preferably a 5-membered ring to a 7-membered ring, more preferably a 6-membered ring.

Examples of the alkyl group formed by combining two alkyl groups in the bis(alkylsulfonyl) quinone imine anion and the substituent on the alkyl group include a halogen atom, an alkyl group substituted by a halogen atom, and an alkoxy group. The alkyl group, the alkylthio group, the alkoxysulfonyl group, the aryloxysulfonyl group and the cycloalkylaryloxysulfonyl group are preferably a fluorine atom and an alkyl group substituted with a fluorine atom.

Other examples of Z ^- include phosphorus fluoride (e.g., PF ₆ ^- ), boron fluoride (e.g., BF ₄ ^- ), and cesium fluoride (e.g., SbF ₆ ^- ).

Z ^{- is} preferably an aliphatic sulfonate anion substituted with a fluorine atom at least in the α position of the sulfonic acid, an aromatic sulfonate anion substituted with a fluorine atom or a fluorine atom-containing group, and a double alkyl group substituted by a fluorine atom A (alkylsulfonyl) anthracene anion or a tris(alkylsulfonyl)methide anion having an alkyl group substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom, more preferably a nonafluorobutanesulfonate anion or a perfluorooctanesulfonate. An acid anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion.

In terms of acid strength, the pKa of the acid produced is preferably -1 or -1 or less, thereby improving sensitivity.

Particularly preferred Z ^- includes the following anionic structures.

In the formula (III), each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom, and when a plurality of R ₁₁ and a plurality of R ₁₂ are present, each R ₁₁ and each R ₁₂ may be respectively Same or different from each other R ₁₁ and each other R ₁₂ .

L represents a divalent linking group, and when a plurality of L are present, each L may be the same as or different from each other L.

A represents a cyclic organic group.

X represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The anion of formula (III) is described in detail below.

Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom, and the alkyl group in the alkyl group substituted by a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. alkyl. Further, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having a carbon number of 1 to 4. Specific examples include fluorine atoms CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ is preferably a fluorine atom or CF ₃ . In particular, it is preferred that both Xf are fluorine atoms.

R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and the alkyl group may have a substituent (preferably a fluorine atom) and is preferably an alkyl group having a carbon number of 1 to 4, more preferably a carbon number. It is a 1 to 4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent of R ₁₁ and R ₁₂ include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ are preferably CF ₃ .

L represents a divalent linking group, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, -N(Ri)- (where Ri represents A hydrogen atom or an alkyl group, an alkyl group, a cycloalkyl group, an alkenyl group, and a divalent linking group formed by combining a plurality of these members. Among them, preferred are -COO-, -OCO-, -CO-, -SO ₂ -, -CON(Ri)-, -SO ₂ N(Ri)-, CON(Ri)-alkylene- and -COO -alkyl-, and more preferably -COO-, -OCO-, -SO ₂ -, -CON(Ri)-, and -SO ₂ N(Ri)-. In the case where multiple Ls exist, each L may be the same as or different from each other L.

Specific examples and preferred examples of the alkyl group of Ri are the same as the specific examples and preferred examples of the above R ₁ to R ₁₀ and Rx.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (including not only those having an aromatic character but also those having no aromatic character, For example, it includes a tetrahydropyran ring and a lactone ring structure).

The alicyclic group may be monocyclic or polycyclic, and is preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a cyclooctyl group, or a fluorenyl group, a norbornenyl group, a tricyclic ring. Tricyclodecanyl (for example, tricyclo [5.2.1.0 ^2,6 ] fluorenyl), tetracyclic fluorenyl, tetracyclododecyl, and adamantyl polycyclic cycloalkyl. Also preferred are nitrogen atom-containing alicyclic groups such as piperididine group, decahydro quinoline group and decahydroisoquinoline group. Among them, from the standpoint of suppressing the diffusibility in the film in the post exposure baking (PEB) step and increasing the exposure latitude, it is preferably a large volume having a carbon number of 7 or more. A structural alicyclic group such as a norbornyl group, a tricyclodecyl group, a tetracyclic fluorenyl group, a tetracyclododecyl group, an adamantyl group, a decahydroquinolyl group, and a decahydroisoquinolyl group.

The aryl group includes a benzene ring, a naphthalene ring, a phenanthrene ring, and an onion ring. Among these aryl groups, naphthalene having a low absorbance is preferred from the viewpoint of the absorbance of light of 193 nm.

The heterocyclic group includes a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and pyridine ( Pyridine) ring. Among these heterocyclic groups, a furan ring, a thiophene ring, and a pyridine ring are preferred.

The above cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be a linear type, a branched type or a cyclic form, preferably a carbon number of 1 to 12), and an aryl group (preferably having a carbon number of 6) To 14), hydroxy, alkoxy, ester, amido group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonate Acid ester group.

Incidentally, the carbon constituting the cyclic organic group (the carbon contributing to the formation of the ring) may be a carbonyl carbon.

x is preferably from 1 to 8, more preferably from 1 to 4, still more preferably 1. y is preferably from 0 to 4, more preferably from 0 to 1, still more preferably 0. z is preferably 0 to 8, More preferably 0 to 4, still more preferably 1.

A preferred embodiment of the sulfonate anion structure of the compound (A) (as exemplified by the sulfonic acid structure to which hydrogen is added) includes the following formula (IIIa). In the formula (IIIa), Xf, R ₁₁ , R ₁₂ , L, A, y and z have the same meanings as those of the formula (III).

Preferred specific examples of the compound (A) represented by the formula (I) are shown below, but the invention is not limited thereto. In the formula, Me represents a methyl group.

The sulfonate anion represented by the formula (III) or a salt thereof (for example, a phosphonium salt or a metal salt) can be synthesized by a general sulfonation reaction or a sulfonylation reaction. For example, the foregoing compound can be obtained by reacting a sulfonium halide moiety of a bis-sulfonyl halide compound selectively with an amine, an alcohol, a guanamine compound or the like. a method of forming a sulfonamide bond, a sulfonate bond or a sulfonium imide bond, and then hydrolyzing other sulfonium halide moieties; or a method of ring-opening a cyclic sulfonic anhydride by an amine, an alcohol or a guanamine compound .

The salts of the sulfonic acid represented by the formula (III) include metal salts of sulfonic acids and phosphonium sulfonates. Examples of the metal in the metal salt of a sulfonic acid include Na ⁺ , Li ^{+ ,} and K ⁺ . Examples of the phosphonium cation in the phosphonium sulfonate salt include an ammonium cation, a phosphonium cation, a phosphonium cation, a phosphonium cation, and a diazonium cation.

The sulfonate anion represented by the formula (III) or a salt thereof can be used for the synthesis of the compound (A) represented by the formula (I).

The compound (A) can be synthesized by a salt exchange method of a sulfonate anion represented by the formula (III) with a photoactive sulfonium salt such as a phosphonium salt corresponding to the phosphonium cation in the formula (I).

In the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention, as the compound (A), one type of compound may be used alone or two or more types of compounds may be used in combination. The content of the compound (A) in the composition of the present invention is preferably from 0.1% by mass to 30% by mass, more preferably from 0.5% by mass to 25% by mass, even more preferably 5% by mass based on the total solid content of the composition. % to 20% by mass.

The compound (A) can be used in combination with an acid generator other than the compound (A) (hereinafter, abbreviated as the compound (A') in some cases).

The compound (A') is not particularly limited, but is preferably a compound represented by the following formula (ZI'), formula (ZII') or formula (ZIII'):

In the formula (ZI'), each of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ independently represents an organic group.

The organic group as R ₂₀₁ , R ₂₀₂ and R _{203 has} a carbon number of usually 1 to 30, preferably 1 to 20.

Two members selected from R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring structure may include an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group. The group formed by combining two members selected from R ₂₀₁ to R ₂₀₃ includes an alkyl group (e.g., a butyl group, a pentyl group).

The organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ includes, for example, a corresponding group in the compound (ZI'-1) described later.

The compound may be a compound having a plurality of structures represented by the formula (ZI'). For example, the compound may be bonded to another compound represented by the formula (ZI') by bonding at least one of R ₂₀₁ to R _{203 in} the compound represented by the formula (ZI') via a single bond or a linking group. A compound of the structure of at least one of R ₂₀₁ to R ₂₀₃ .

Z ^- represents a non-nucleophilic anion (an anion having a very low nucleophilic reaction promoting ability).

Examples of Z ^- include sulfonate anions (such as aliphatic sulfonate anions, aromatic sulfonate anions, and camphor sulfonate anions), carboxylate anions (such as aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylates) Anion), sulfonium imine anion, bis(alkylsulfonyl) quinone imine anion, and tris(alkylsulfonyl)methide anion.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having a carbon number of 1 to 30, or a carbon number of a cycloalkyl group of 3 to 30.

Aroma of aromatic sulfonate anion and aromatic carboxylate anion The group group is preferably an aryl group having a carbon number of 6 to 14, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The above alkyl group, cycloalkyl group and aryl group may have a substituent. Specific examples of the substituent include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3) To 15), an aryl group (preferably having a carbon number of 6 to 14), an alkoxycarbonyl group (preferably having a carbon number of 2 to 7), a mercapto group (preferably having a carbon number of 2 to 12), an alkoxycarbonyloxy group a base (preferably having a carbon number of 2 to 7), an alkylthio group (preferably having a carbon number of 1 to 15), an alkylsulfonyl group (preferably having a carbon number of 1 to 15), and an alkylimidosulfonyl group. (preferably having a carbon number of 2 to 15), an aryloxysulfonyl group (preferably having a carbon number of 6 to 20), an alkylaryloxysulfonyl group (preferably having a carbon number of 7 to 20), a cycloalkyl group An aryloxysulfonyl group (preferably having a carbon number of 10 to 20), an alkoxyalkoxy group (preferably having a carbon number of 5 to 20), a cycloalkyl alkoxyalkoxy group (preferably having a carbon number of 8) To 20). The aryl group and ring structure in each group may further have an alkyl group (preferably having a carbon number of 1 to 15) as a substituent.

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

Examples of the sulfonium imine anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl)phosphonium anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms.

Two alkyl groups in the bis(alkylsulfonyl) quinone imine anion may be combined to form an alkylene group (preferably having a carbon number of 2 to 4) and may be formed together with a quinone imine group and two sulfonyl groups. ring.

Examples of the alkyl group formed by combining two alkyl groups in the bis(alkylsulfonyl) quinone imine anion and the substituent on the alkyl group include a halogen atom, an alkyl group substituted by a halogen atom, and an alkoxy group. The alkyl group, the alkylthio group, the alkoxysulfonyl group, the aryloxysulfonyl group, and the cycloalkylaryloxysulfonyl group are preferably a fluorine atom and an alkyl group substituted with a fluorine atom.

Other examples of Z ^- include phosphorus fluoride (e.g., PF ₆ ^- ), boron fluoride (e.g., BF ₄ ^- ), and cesium fluoride (e.g., SbF ₆ ^- ).

Z ^{- is} preferably an aliphatic sulfonate anion substituted with a fluorine atom at the α position of the sulfonic acid, an aromatic sulfonate anion substituted with a fluorine atom or a fluorine atom-containing group, and a double substituted with an alkyl group via a fluorine atom. Alkylsulfonyl) anthracene anion or a tris(alkylsulfonyl)methide anion having an alkyl group substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom, more preferably a nonafluorobutanesulfonate anion or a perfluorooctanesulfonate. An acid anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion.

In terms of acid strength, the pKa of the acid produced is preferably -1 or -1 or less, thereby improving sensitivity.

A more preferred component (ZI') is the compound (ZI'-1) described below.

The compound (ZI'-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in the formula (ZI') is an aryl group, that is, a compound having an arylsulfonium as a cation.

In the aryl hydrazine compound, R ₂₀₁ to R ₂₀₃ may be all aryl groups, or R ₂₀₁ to R ₂₀₃ may be partially aryl and the remainder being alkyl or cycloalkyl, but preferably R ₂₀₁ to R _{203 are} all Aryl.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an arylbicycloalkylsulfonium compound as a triaryl group. Anthraquinone compounds are preferred.

The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure (containing an oxygen atom, a nitrogen atom, a sulfur atom or the like). Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. In the case where the aryl hydrazine compound has two or more aryl groups, these two or more aryl groups may be the same or different.

The alkyl group or the cycloalkyl group contained in the aryl hydrazine compound is preferably a linear or branched alkyl group having a carbon number of 1 to 15, or a cycloalkyl group having a carbon number of 3 to 15, if necessary. Examples thereof include methyl, ethyl, propyl, n-butyl, t-butyl, t-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

The aryl group, alkyl group, cycloalkyl group of R ₂₀₁ to R ₂₀₃ may have an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), and an aryl group (for example, a carbon number of 6). To 14), an alkoxy group (for example, a carbon number of 1 to 15), a halogen atom, a hydroxyl group or a phenylthio group as a substituent. The substituent is preferably a linear or branched alkyl group having a carbon number of 1 to 12, a cycloalkyl group having a carbon number of 3 to 12, or a linear, branched or cyclic group having a carbon number of 1 to 12. The alkoxy group is more preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted on any one of the three members R ₂₀₁ to R ₂₀₃ or may be substituted on all of the three members. In the case where R ₂₀₁ to R ₂₀₃ are aryl groups, the substituent is preferably substituted at the para position of the aryl group.

The formula (ZII') and the formula (ZIII') are described below.

In (ZII') and formula (ZIII'), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl, alkyl and cycloalkyl groups of R ₂₀₄ to R ₂₀₇ are the same as the aryl, alkyl and cycloalkyl groups described for R ₂₀₁ to R ₂₀₃ in the formula (ZI'-1).

The aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent include those which can be substituted with an aryl group, an alkyl group and a cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the formula (ZI'-1).

Z ^- represents a non-nucleophilic anion, and examples thereof are identical to those of the Z ^- non-nucleophilic anion in the formula (ZI').

Other examples of the acid generator (A') which can be used in combination with the acid generator of the present invention include compounds represented by the following formula (ZIV'), formula (ZV') and formula (ZVI').

In the formula (ZIV') to the formula (ZVI'), Ar ₃ and Ar ₄ each independently represent an aryl group.

R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as those of the aryl group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the formula (ZI'-1).

Specific examples of the alkyl group and the cycloalkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as those of the alkyl group and the cycloalkyl group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in (ZI'-1).

The alkylene group of A includes an alkylene group having a carbon number of 1 to 12 (for example, methylene, ethyl, propyl, isopropyl, butyl, isobutyl); The base includes an alkenyl group having 2 to 12 carbon atoms (for example, a vinyl group, a propenyl group, and a butenyl group); and the exoaryl group of A includes an exoaryl group having a carbon number of 6 to 10 (for example, Phenyl, methylphenyl, and naphthyl).

Particularly preferred examples of the acid generator which can be used in combination with the acid generator of the present invention are shown below.

In the case of using the compound (A) and the compound (A') in combination, the amount of the acid generator to be used is usually from 99/1 to 20 in terms of the mass ratio (the compound (A) / the compound (A')). /80, better than 99/1 to 40/60, more preferably 99/1 to 50/50.

[2] Resin (B)

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (B).

The resin (B) is preferably a resin which can be decomposed by the action of an acid to increase the solubility to an alkaline developer (hereinafter, abbreviated as "acid-decomposable resin" in some cases). The acid-decomposable resin has a group which can be decomposed by the action of an acid to produce an alkali-soluble group on one or both of the main chain or the side chain of the resin (hereinafter, sometimes referred to as an abbreviation) It is an "acid-decomposable group").

The resin (B) is preferably insoluble or poorly soluble in an alkaline developing solution.

The acid-decomposable group is preferably a structure having a group which decomposes and desorbs by the action of an acid to protect the alkali-soluble group.

Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamino group, a sulfonimide group, an (alkylsulfonyl) (alkylcarbonyl)methylene group, (alkane) (Alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indolylene, bis(alkylsulfonyl)methylene, bis ( Alkylsulfonyl) fluorenylene, tris(alkylcarbonyl)methylene and tris(alkylsulfonyl)methylene.

Preferred alkali-soluble groups include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

A preferred group as the acid-decomposable group is a group in which a hydrogen atom of the above alkali-soluble group is substituted with a group capable of being detached by the action of an acid.

Examples of the group capable of being detached by the action of an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C(R ₀₁ ). (R ₀₂ ) (OR ₃₉ ).

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like, more preferably It is a tertiary alkyl ester group.

The repeating unit containing the acid-decomposable group which the resin (B) may contain is preferably a repeating unit represented by the following formula (AI):

In the formula (AI), Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by -CH ₂ -R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group. Examples of the monovalent organic group include an alkyl group having a carbon number of 5 or less and an anthracene group having a carbon number of 5 or less. In these examples, an alkyl group having a carbon number of 3 or less is preferred, and a methyl group is more preferred. Xa _{1 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl (monocyclic or polycyclic).

Both of Rx ₁ to Rx ₃ may be combined to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group of T include an alkylene group, a -COO-Rt- group, an -O-Rt- group, and the like. In the formula, Rt represents an alkylene group or a cycloalkyl group.

T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having a carbon number of 1 to 5, more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group or a -(CH ₂ ) ₃ - group.

The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having a carbon number of 1 to 4, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a t-butyl group.

The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polythiol group, a tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group; Cyclocycloalkyl.

The cycloalkyl group formed by combining both of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or such as a thiol group, a tetracyclic fluorenyl group, or a tetracyclic group A polycyclic cycloalkyl group of an alkyl group and an adamantyl group. Among all the above cycloalkyl groups, a monocyclic cycloalkyl group having a carbon number of 5 to 6 is preferred.

An example in which Rx ₁ is a methyl group or an ethyl group and Rx ₂ is bonded to Rx ₃ to form the above cycloalkyl group is preferred.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, and an alkoxy group (having a carbon number of 1) To 4), a carboxyl group and an alkoxycarbonyl group (having a carbon number of 2 to 6). The carbon number is preferably 8 or less.

The content of the repeating unit having an acid-decomposable group is preferably from 20 mol% to 70 mol%, more preferably from 30 mol% to 60 mol%, based on the total of the repeating units constituting the resin.

Preferred specific examples of the repeating unit having an acid-decomposable group are shown below, but the invention is not limited thereto.

In a specific example, Rx and Xa ₁ each represent a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH, and Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when a plurality of Z is present, each Z may be independent of each other Z. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as those of R ₁₀ in the following formula (II-1) and preferred examples.

The resin (B) is more preferably a resin containing a repeating unit represented by the following formula (I) or a repeating unit represented by the following formula (II) as a repeating unit represented by the formula (AI).

In the formulae (I) and (II), R ₁ and R ₃ each independently represent a hydrogen atom, a methyl group which may have a substituent, or a group represented by -CH ₂ -R ₉ . R ₉ represents a monovalent organic group.

R ₂ , R ₄ , R ₅ and R ₆ each independently represent an alkyl group or a cycloalkyl group.

R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.

R ₁ and R _{3 are} each preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Specific examples and preferred examples of the monovalent organic group in R ₉ are the same as those described for R ₉ in the formula (AI).

The alkyl group in R ₂ may be linear or branched and may have a substituent.

The cycloalkyl group in R ₂ may be monocyclic or polycyclic, and may have a substituent.

R _{2 is} preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group and the like.

R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R together with a carbon atom is preferably a monocyclic alicyclic structure, and its carbon number is preferably from 3 to 7, more preferably from 5 or 6.

R _{3 is} preferably a hydrogen atom or a methyl group, more preferably a methyl group.

The alkyl group in R ₄ , R ₅ and R ₆ may be linear or branched and may have a substituent. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl groups.

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic, and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclononyl group, a tetracyclododecyl group, and an adamantyl group.

Examples of the repeating unit represented by the formula (I) include, for example, a repeating unit represented by the following formula (1-a).

In the formula, R ₁ and R ₂ have the same meanings as in the formula (I).

The repeating unit represented by the formula (II) is preferably a repeating unit represented by the following formula (II-1).

In the formula (II-1), R ₃ to R ₅ have the same meanings as in the formula (II).

R ₁₀ represents a substituent having a polar group. In the case where multiple R ₁₀ are present, these R ₁₀ may be the same or different. Examples of the polar group-containing substituent include a hydroxyl group, a cyano group, an amine group, an alkylguanamine group, a sulfonylamino group itself, and a linear or branched alkyl group or a naphthene having at least one of the above groups. base. It is preferably an alkyl group having a hydroxyl group, and more preferably a branched alkyl group having a hydroxyl group. The branched alkyl group is preferably an isopropyl group.

p represents an integer from 0 to 15. p is preferably an integer of 0 to 2, more preferably 0 or 1.

The acid-decomposable resin is preferably a resin containing a repeating unit represented by the formula (I) or a repeating unit represented by the formula (II) as a repeating unit represented by the formula (AI). In another embodiment, the resin is preferably a resin comprising at least two repeating units represented by the formula (I) as a repeating unit represented by the general formula (AI).

As the repeating unit having an acid-decomposable group of the resin (B), one type may be used alone or two or more types may be used in combination. In the case of combined use, preferred examples of the combination are shown below. In the following formula, each R is independent Represents a hydrogen atom or a methyl group.

The resin (B) preferably contains a repeating unit having a lactone structure or a sultone (cyclic sulfonate) structure.

As the lactone group or the sultone group, any one of a lactone group or a sultone group may be used as long as it has a lactone structure or a sultone structure, but the structure is preferably a 5-membered ring to a 7-membered ring. Ester or sultone structure, and the structure is better The other ring structure fuses in the form of a bicyclic or spiro ring structure to a 5-membered ring to a 7-membered ring lactone or sultone structure. More preferably, the resin comprises a repeating unit having a lactone or sultone structure represented by any one of the following formulae (LC1-1) to (LC1-17), (SL1-1), and (SL1-2). The lactone or sultone structure can be directly bonded to the backbone. Preferred lactone or sultone structures are (LC1-1), (LC1-4), (LC1-5) and (LC1-8), with (LC1-4) being more preferred. By using a particular lactone or sultone structure, line width roughness (LWR) and development defects will be improved.

The lactone moiety or the sultone moiety may or may not have a substituent (Rb ₂ ). Preferable examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 2 to 8 carbon atoms. An alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. Among these examples, an alkyl group having a carbon number of 1 to 4, a cyano group, and an acid-decomposable group are more preferable. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, each substituent (Rb ₂ ) may be the same or different from each other substituent (Rb ₂ ), and further, a plurality of substituents (Rb ₂ ) may be bonded to each other to form ring.

The resin (B) preferably contains a repeating unit having a lactone structure or a sultone structure, which is represented by the following formula (III):

In the formula (III), A represents an ester bond (a group represented by -COO-) or a guanamine bond (a group represented by -CONH-).

When a plurality of R ₀ are present, R ₀ represents (each independently represents) an alkylene group, a cycloalkyl group, or a combination thereof.

When a plurality of Z are present, Z represents (each independently represents) an ether bond, an ester bond, a guanamine bond, a urethane bond (by or Representative group), or urea bond (by Representative group) wherein R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.

n is the number of repetitions of the structure represented by -R ₀ -Z- and represents an integer of 0 to 2.

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene and cycloalkyl groups of R ₀ may have a substituent.

Z is preferably an ether bond or an ester bond, more preferably an ester bond.

The alkyl group of R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, still more preferably a methyl group. The alkylene and cycloalkyl groups of R ₀ and the alkyl group of R ₇ may each be substituted, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, and a hydroxyl group. Alkoxy groups such as methoxy, ethoxy, isopropoxy, tert-butoxy and benzyloxy, and oxioxy groups such as acetyloxy group and propyloxy group (acetoxy) Group). R _{7 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The chain alkyl group in R ₀ is preferably a chain alkyl group having a carbon number of 1 to 10, more preferably a chain alkyl group having a carbon number of 1 to 5, and examples thereof include a methylene group and a stretching group. Ethyl and propyl. The cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 20, and examples thereof include a cyclohexylene group, a cyclopentylene group, a pendant decyl group, and an adamantyl group. In order to exhibit the effects of the present invention, a chain alkyl group is more preferable, and a methylene group is more preferable.

The substituent having a lactone or sultone structure represented by R ₈ is not limited as long as it has a lactone or sultone structure. Specific examples thereof include a lactone or a structure represented by the formula (LC1-1) to the formulae (LC1-17), (SL1-1), and (SL1-2), and among these examples, it is preferred to The structure represented by LC1-4). More preferably, the formula (LC1-1) to the formula (LC1-17), (SL1-1), and (SL1-2) has a structure in which n ₂ is 2 or less.

R _{8 is} preferably a monovalent organic group having an unsubstituted lactone or sultone structure, or a monovalent structure having a lactone or sultone structure containing a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. The organic group is more preferably a monovalent organic group having a lactone (cyanolactone) or a sultone (cyanosultone) structure containing a cyano group as a substituent.

Specific examples of the repeating unit including the group having a lactone or sultone structure represented by the formula (III) are shown below, but the invention is not limited thereto.

In a specific example, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a methylol group or an ethoxymethyl group.

In the following formula, Me represents a methyl group.

The repeating unit having a lactone or sultone structure is more preferably a repeating unit represented by the following formula (III-1) or (III-1'):

In the formulae (III-1) and (III-1'), R ₇ , A, R ₀ , Z and n have the same meanings as in the formula (III).

R ₇ ', A', R ₀ ', Z' and n' have the same meanings as R ₇ , A, R ₀ , Z and n in the formula (III), respectively.

When a plurality of R ₉ are present, R ₉ represents (each independently represents) an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, and when a plurality of R ₉ are present, two of the members They can be combined to form a ring.

When a plurality of R ₉ ' are present, R ₉ ' represents (each independently represents) an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, and when a plurality of R ₉ ' are present, Two members can combine to form a loop.

X and X' each independently represent an alkyl group, an oxygen atom or a sulfur atom.

m and m' are each a substituent number and independently represent an integer of 0 to 5. m and m' are each preferably 0 or 1.

The alkyl group of R ₉ and R ₉ ' is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-butoxycarbonyl group, and a third butoxycarbonyl group. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy and butoxy groups. These groups may have a substituent, and the substituent includes a hydroxyl group, an alkoxy group such as a methoxy group and an ethoxy group, a cyano group, and a halogen atom such as a fluorine atom. R ₉ and R ₉ ' are each preferably a methyl group, a cyano group or an alkoxycarbonyl group, more preferably a cyano group.

Examples of the alkylene group of X and X' include a methylene group and an ethyl group. X and X' are each preferably an oxygen atom or a methylene group, more preferably a methylene group.

When m and m' are each 1 or more, at least one of R ₉ and R ₉ ' is preferably substituted at the α-position or the β-position of the carbonyl group of the lactone, and more preferably at the α-position.

Specific examples of the repeating unit having a group having a lactone structure or a sultone structure represented by the formula (III-1) or the formula (III-1') are shown below, but the invention is not limited thereto. In a specific example, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a methylol group or an ethoxymethyl group.

The content of the repeating unit represented by the formula (III) is preferably from 15 mol% to 60 mol%, more preferably in the case of all repeating units in the resin, including a plurality of repeating units as its total repeating unit. 20% to 60% by mole, more preferably 30% by mole and 50% by mole.

In an embodiment, the unit represented by the formula (III) may be a repeating unit represented by the following formula (AII'):

In the formula (AII'), Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferable examples of the substituent which may be substituted with an alkyl group of Rb ₀ include a hydroxyl group and a halogen atom. The halogen atom of Rb ₀ includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb _{0 is} preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.

V represents a group having a structure represented by any one of the formula (LC1-1) to the formula (LC1-17), the formula (SL1-1), and the formula (SL1-2).

The resin (B) may contain a repeating unit other than the repeating unit having a lactone or sultone structure represented by the above formula (III).

Specific examples of the repeating unit having a lactone group or a sultone group include the following, in addition to the specific examples shown above, but the invention is not limited thereto.

(In the formula, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .)

(In the formula, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .)

(In the formula, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .)

In these specific examples, particularly preferred repeating units include the following repeating units. By selecting the preferred lactone group or sultone group, the pattern profile and the iso/dense bias will be improved.

(In the formula, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .)

The repeating unit having a lactone group or a sultone group usually has an optical isomer, but any optical isomer can be used. One optical isomer may be used alone, or a mixture of a plurality of optical isomers may be used. In the case where an optical isomer is mainly used, the optical purity (ee) is preferably 90% or more, more preferably 95% or more.

When the resin as a whole contains a plurality of repeating units, the content of the repeating unit having a lactone or sultone structure other than the repeating unit represented by the formula (III) is preferably 15 mol. The ear% to 60% by mole, more preferably 20% by mole to 50% by mole, still more preferably 30% by mole to 50% by mole.

Further, two or more lactone or sultone repeating units selected from the group consisting of the formula (III) may be used in combination, thereby increasing the efficiency of the present invention. In the case of combined use, it is preferred to use two or more lactone or sultone repeating units selected from the formula (III) in combination in the case where n is 1.

The resin (B) preferably contains a repeating unit having a hydroxyl group or a cyano group other than the formula (AI) and the formula (III). Thanks to this repeating unit, substrate adhesion and developer affinity can be improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group is preferably an adamantyl group, a diadamantyl group or a norbornyl group. The alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group is preferably a partial structure represented by the following formula (VIIa) to formula (VIId):

In the formulae (VIIa) to (VIIc), R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. It is preferred that one or two members selected from R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms. In the formula (VIIa), it is more preferred that two members selected from R ₂ c to R ₄ c are a hydroxyl group and the balance is a hydrogen atom.

The repeating unit having a partial structure represented by the formula (VIIa) to the formula (VIId) includes a repeating unit represented by the following formula (AIIa) to formula (AIId):

In the formula (AIIa) to the formula (AIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c to R ₄ c have the same in formula (Vila) in the (VIIc) to the formula R ₂ c to R ₄ c is meaning.

The content percentage of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 mol% to 40 mol%, more preferably from 5 mol% to 30 mol%, based on all the repeating units in the resin (B). More preferably, it is 10 mol% to 25 mol%.

Specific examples of the repeating unit having a hydroxyl group or a cyano group are shown below, but the invention is not limited thereto.

The resin used in the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may contain a repeating unit having an alkali-soluble group. The alkali-soluble group includes a carboxyl group, a sulfonylamino group, a sulfonimide group, a bissulfonimide group, and an aliphatic alcohol substituted with an electron-withdrawing group at the α-position (for example, hexafluoroisopropanol) And preferably comprises a repeating unit having a carboxyl group. By including a repeating unit having an alkali-soluble group, the resolution in the use of the contact hole will be increased. All of the following repeating units are preferred for use in repeating units having an alkali-soluble group: alkali-soluble radical direct bonding a repeating unit on the main chain of the resin, such as a repeating unit composed of acrylic acid or methacrylic acid; a repeating unit in which an alkali-soluble group is bonded to a main chain of the resin via a linking group; and by polymerization An alkali-soluble group-containing polymerization initiator or chain transfer agent to introduce an alkali-soluble group into a repeating unit at the terminal of the polymer chain. The linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. In particular, a repeating unit composed of acrylic acid or methacrylic acid is preferred.

The content of the repeating unit having an alkali-soluble group is preferably from 0 to 20 mol%, more preferably from 3 mol% to 15 mol%, even more preferably 5 mol, based on all the repeating units in the resin (B). Ear to 10% by mole.

Specific examples of the repeating unit having an alkali-soluble group are shown below, but the invention is not limited thereto.

In specific examples, Rx behalf of H, CH _3, CH ₂ OH or CF _3.

The resin (B) may further contain a repeating unit which does not have an alicyclic hydrocarbon structure of a polar group (for example, the above-mentioned alkali-soluble group, hydroxyl group or cyano group) and which does not exhibit acid decomposition property. Such a repeating unit includes a repeating unit represented by the following formula (IV):

In the above formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.

Ra represents a hydrogen atom, an alkyl group, or a -CH ₂ -O-Ra ₂ group, wherein Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. Ra is preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.

The cyclic structure contained in R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having a carbon number of 3 to 12, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and a cycloalkenyl group having a carbon number of 3 to 12, such as a ring. Hexenyl. The monocyclic hydrocarbon group is preferably a monocyclic hydrocarbon group having a carbon number of 3 to 7, more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a crosslinked cylic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a dicyclohexyl group and a perhydronaphthyl group. Examples of the cross-linked cyclic hydrocarbon ring include, for example, a pinane ring, a bornane ring, a norpinane ring, a norbornane ring, and a bicyclooctane ring (for example, a bicyclo [ 2.2.2] a bicyclic hydrocarbon ring of an octane ring, a bicyclo [3.2.1] octane ring); and a homocyclic ring [4.2.1.0 ^3,7 ]Homobrendane ring, adamantane ring, three Ring [5.2.1.0 ^2,6 ]decane ring and tricyclo[4.3.1.1 ^2,5 ] undecane ring tricyclic hydrocarbon ring; and such as tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] A tetracyclic hydrocarbon ring of dodecane and perhydro-1,4-methano-5,8-methanonaphthalene ring. The crosslinked cyclic hydrocarbon ring also includes a fused cyclic hydrocarbon ring, such as a condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings, such as perhydronaphthalene (decalin) rings. , perhydroanthracene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrofluorene ring, perhydroindene ring and perhydrophenalene ring.

Preferred examples of the crosslinked cyclic hydrocarbon ring include a fluorenyl group, an adamantyl group, a bicyclooctyl group, and a tricyclo[5,2,1,0 ^2,6 ]fluorenyl group. Among these crosslinked cyclic hydrocarbon rings, a decyl group and an adamantyl group are more preferred.

These alicyclic hydrocarbon groups may have a substituent, and preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group in which a hydrogen atom is substituted, and an amine group in which a hydrogen atom is substituted. The halogen atom is preferably a bromine atom, a chlorine atom or a fluorine atom, and the alkyl group is preferably a methyl group, an ethyl group, a butyl group or a tert-butyl group. The alkyl group may have a more substituent, and the substituent which the alkyl group may have further includes a halogen atom, an alkyl group, a hydroxyl group in which a hydrogen atom is substituted, and an amine group in which a hydrogen atom is substituted.

Examples of the group in which the hydrogen atom is replaced include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, a decyl group, an alkoxycarbonyl group, and an aralkoxycarbonyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms; the substituted methyl group is preferably a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a third butoxymethyl group or 2-methoxyethoxymethyl; the substituted ethyl group is preferably 1-ethoxyethyl or 1-methyl-1-methoxyethyl; the fluorenyl group is preferably carbon a number 1 to 6 of an aliphatic thiol group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a valeryl group, and a pivaloyl group; and an alkoxy group The carbonyl group is, for example, an alkoxycarbonyl group having a carbon number of 2 to 4.

The resin (B) used in the present invention may or may not contain a repeating unit having no alicyclic hydrocarbon structure having a polar group and exhibiting no acid decomposition property. However, in the case of including the repeating unit, the content of the above repeating unit is preferably from 1 mol% to 40 mol%, more preferably from 2 mol% to 20 mol% based on all the repeating units in the resin (B). ear%.

Specific examples of the repeating unit which does not have a polar group of an alicyclic hydrocarbon structure and which does not exhibit acid decomposition property are shown below, but the invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

The resin (B) used in the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention has, in addition to the above-mentioned repeating structural unit, in order to control dry etching resistance, standard developer suitability, substrate adhesion, and resist Resist profile and the usual necessary characteristics of the resist (such as resolution, heat resistance and sensitivity) may include various repeating structures unit.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the monomers described below.

Thanks to these repeating units, the necessary properties of the resist used in the composition of the present invention can be finely adjusted, in particular: (1) solubility in a coating solvent, and (2) film forming property (glass transition temperature) ), (3) alkaline developability, (4) film loss (selection of hydrophilicity, hydrophobicity or alkali-soluble group), (5) adhesion of unexposed areas to the substrate, (6) dry etching resistance and the above Similar properties.

Examples of the monomer include one having an addition polymerization property selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. A compound that saturates the bond.

In addition to these, it is also possible to copolymerize an addition polymerizable unsaturated compound which can be copolymerized with a monomer corresponding to each of the above various repeating structural units.

In the resin (B) used in the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention, the dry etching resistance of the individual repeating structural unit including the molar ratio can be appropriately set to control the resist, and the standard developer can be adapted. Properties, substrate adhesion, resist profile, and the usual necessary properties of the resist (such as resolution, heat resistance, inspiration).

In the case where the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is used for ArF exposure, from the viewpoint of transparency to ArF light, The resin (B) used in the composition of the present invention preferably has substantially no aromatic group. More specifically, in all of the repeating units of the resin (B), the proportion of the aromatic group-containing repeating unit is preferably 5 mol% or less, more preferably 5 mol% or less, more preferably 3 mol% or 3 mol% % or less, and desirably 0% by mole, that is, does not contain a repeating unit having an aromatic group. Further, the resin (B) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

Further, the resin (B) preferably does not contain a fluorine atom or a ruthenium atom from the viewpoint of compatibility with a hydrophobic resin of the second resin described later.

The resin (B) used in the composition of the present invention preferably has all of the repeating units being a resin composed of a (meth) acrylate-based repeating unit. In this case, all of the repeating units may be methacrylate-based repeating units, all of the repeating units may be acrylate-based repeating units, or all of the repeating units may be methacrylate-based repeating units and acrylate-based repeating units. The composition, but the content of the acrylate-based repeating unit is preferably 50% by mole or less by 50% by mole based on the total of the repeating units. The copolymerized polymer also preferably contains from 20 mol% to 50 mol% of the acid-decomposable group-containing (meth) acrylate-based repeating unit, and from 20 mol% to 50 mol% of the lactone-containing group ( a methyl (meth) acrylate repeating unit, 5 mol% to 30 mol% of a (meth) acrylate repeating unit having a hydroxy or cyano substituted alicyclic hydrocarbon structure, and 0 to 20 mol% Other (meth) acrylate repeating units.

In the case of irradiating the composition of the present invention with a KrF excimer laser, electron beam, X-ray or a high energy beam of 50 nm or less (for example, EUV), the resin (B) preferably further contains hydroxybenzene. Vinyl repeat yuan. More preferably, it is a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected by an acid-decomposable group, and an acid-decomposable repeating unit such as a tertiary alkyl (meth)acrylate.

Preferable examples of the hydroxystyrene-based repeating unit having an acid-decomposable group include: a third butoxycarbonyloxystyrene, a 1-alkoxyethoxystyrene or a tertiary alkyl (meth)acrylate a repeating unit composed of esters. More preferably, it is a repeating unit consisting of 2-alkyl-2adamantyl (meth)acrylate or dialkyl (1-adamantyl)methyl (meth)acrylate.

The resin (B) of the present invention can be synthesized by a conventional method such as radical polymerization. Examples of the usual synthesis method include: a batch polymerization method which dissolves a monomer substance and an initiator in a solvent and heats the solution to cause polymerization; and a dropping polymerization method, It adds a solution containing a monomer substance and an initiator to the heated solvent dropwise over a period of from 1 hour to 10 hours. A drop-in polymerization method is preferred. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, such as two A guanamine solvent of methylformamide and dimethylacetamide, and a solvent which can dissolve the composition of the present invention, such as propylene glycol monomethyl ether acetate (PGMEA, another Name: 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether (PGME, another name: 1-methoxy-2) -propanol) and cyclohexanone. More preferably, the photosensitive sensitizing or radiation sensitive resin composition of the present invention is used. The same solvent as the solvent used in the polymerization is used for the polymerization. By the use of the same solvent, particle generation during storage can be suppressed.

The polymerization is preferably carried out in an inert gas atmosphere such as nitrogen or argon. The polymerization is started using a commercially available radical initiator (for example, an azo initiator, a peroxide) as a polymerization initiator. The radical initiator is preferably an azo initiator, and is preferably an azo initiator having an ester group, a cyano group or a carboxyl group. Preferable examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis(2-methylpropionate). If necessary, additional or additional initiators are added. After the reaction is completed, the reaction product is charged into a solvent, and the desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is from 5% by mass to 50% by mass, preferably from 10% by mass to 30% by mass; and the reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° °C. (In this specification, the mass ratio is equal to the weight ratio).

The resin (B) used in the present invention preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 2,000 to 20,000, according to gel permeation chromatography (GPC method) using polystyrene. More preferably, it is 3,000 to 15,000, and still more preferably 3,000 to 10,000. When the weight average molecular weight is from 1,000 to 200,000, heat resistance and reduction in dry etching resistance can be avoided, and at the same time, deterioration of film formability due to deterioration of developability or increase in viscosity can be avoided.

The degree of dispersion (molecular weight distribution) is usually from 1.0 to 3.0, preferably from 1.0 to 2.6, more preferably from 1.0 to 2.0, still more preferably from 1.4 to 2.0. The smaller the molecular weight distribution, the more excellent the resolution and the resist profile, and the side walls of the resist pattern. The smoother and the more the roughness is improved.

In the present invention, the mixing of the resin (B) in the overall composition is preferably from 30% by mass to 99% by mass, more preferably from 60% by mass to 95% by mass based on the total solid content.

A plurality of resins may be used one kind or in combination as the resin used in the present invention.

Incidentally, the resins other than the resin (B) used in the present invention may be used in combination as long as they do not detract from the efficiency of the present invention. The resin other than the resin (B) used in the present invention includes an acid-decomposable resin which may include the above-mentioned repeating unit which may be contained in the resin (B), and other known acid-decomposable resins.

[3] Hydrophobic resin

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may contain a hydrophobic resin having a fluorine atom or a ruthenium atom particularly when applied to liquid immersion exposure (hereinafter, sometimes referred to as "hydrophobic resin (HR) for some times). "). The hydrophobic resin (HR) is unevenly distributed on the surface layer of the film, and when the liquid immersion medium is water, the hydrophobic resin (HR) can increase the static/dynamic contact angle of the surface of the resist film to water, and can also be improved. The le-liquidity of the liquid immersion liquid (fo-llowability).

As described above, the hydrophobic resin (HR) is unevenly distributed at the interface, but unlike the surfactant, the hydrophobic resin (HR) does not necessarily need to have a hydrophilic group in the molecule, and is uniformly mixed for the polar/nonpolar substance. Words can be helpless.

The hydrophobic resin typically contains a fluorine atom and/or a germanium atom. Hydrophobic tree The fluorine atom and/or the ruthenium atom in the fat (HR) may be contained in the main chain of the resin or may be contained in the side chain.

In the case where the hydrophobic resin contains a fluorine atom, the resin preferably has a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group or a fluorine atom-containing aryl group as a fluorine atom-containing partial structure.

The fluorine atom-containing alkyl group is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. And may have other substituents other than a fluorine atom.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have other substituents other than a fluorine atom.

The fluorine atom-containing aryl group includes an aryl group such as a phenyl group and a naphthyl group, at least one hydrogen atom is substituted with a fluorine atom, and may further have other substituents other than a fluorine atom.

Preferable examples of the fluorine atom-containing alkyl group, the fluorine atom-containing cycloalkyl group, and the fluorine atom-containing aryl group include a group represented by any one of the following formulas (F2) to (F4), but the present invention does not Limited by it.

In the formulae (F2) to (F4), R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (linear or branched). The restriction is that at least one of R ₅₇ to R ₆₁ , at least one of R ₆₂ to R ₆₄ and at least one of R ₆₅ to R ₆₈ are independently a fluorine atom or an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom. ( Preferably, the carbon number is from 1 to 4).

Preferably, R ₅₇ to R ₆₁ and R ₆₅ to R _{67 are} all fluorine atoms. R ₆₂ , R ₆₃ and R _{68 are} each preferably a fluoroalkyl group (preferably having a carbon number of 1 to 4), more preferably a perfluoroalkyl group having a carbon number of 1 to 4. When R ₆₂ and R ₆₃ are a perfluoroalkyl group, R ₆₄ is preferably a hydrogen atom. R ₆₂ and R ₆₃ may be bonded to each other to form a ring.

Specific examples of the group represented by the formula (F2) include: p-fluorophenyl group, pentafluorophenyl group, and 3,5-bis(trifluoromethyl)phenyl group.

Specific examples of the group represented by the formula (F3) include: trifluoromethyl, pentafluoropropyl, pentafluoroethyl, heptafluorobutyl, hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro (2 -Methyl)isopropyl, nonafluorobutyl, octafluoroisobutyl, nonafluorohexyl, nonafluoro-tert-butyl, perfluoroisopentyl, perfluorooctyl, perfluoro(trimethyl)hexyl 2,2,3,3-tetrafluorocyclobutyl and perfluorocyclohexyl. In these examples, preferred are hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro(2-methyl)isopropyl, octafluoroisobutyl, nonafluoro-tert-butyl and perfluoroisoprene. More preferably, it is hexafluoroisopropyl and heptafluoroisopropyl.

Specific examples of the group represented by the formula (F4) include: -C(CF ₃ ) ₂ OH, -C(C ₂ F ₅ ) ₂ OH, -C(CF ₃ )(CH ₃ )OH, and -CH(CF ₃ ) OH, preferably -C(CF ₃ ) ₂ OH.

The partial structure of the fluorine-containing atom may be directly bonded to the main chain, or may be selected from an alkyl group, a phenyl group, an ether bond, a thioether bond, a carbonyl group, an ester bond, or an anthracene. A group in a group consisting of an amine bond, a urethane bond, and a urea-forming bond, or a group obtained by combining two or more of them, is bonded to the main chain.

The repeating unit having a fluorine atom is preferably a repeating unit shown below.

In the formula, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having a carbon number of 1 to 4 and may have a substituent, and the alkyl group having a substituent particularly includes a fluorinated alkyl group.

W ₃ to W ₆ each independently represent an organic group having at least one or more fluorine atoms. Specific examples thereof include atomic groups of (F2) to (F4).

In addition to these groups, the hydrophobic resin (C) may contain a unit shown below as a repeating unit having a fluorine atom.

In the formula, R ₄ to R ₇ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having a carbon number of 1 to 4 and may have a substituent, and the alkyl group having a substituent particularly includes a fluorinated alkyl group.

However, at least one of R ₄ to R ₇ represents a fluorine atom. A pair of R ₄ and R ₅ or a pair of R ₆ and R ₇ form a ring.

W ₂ represents an organic group containing at least one fluorine atom. Specific examples thereof include atomic groups of (F2) to (F4).

L ₂ represents a single bond or a divalent linking group. The divalent linking group represents a substituted or unsubstituted extended aryl group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted stretched alkyl group, -O-, -SO ₂ -, -CO -, -N(R)- (wherein R represents a hydrogen atom or an alkyl group), -NHSO ₂ -, or a divalent linking group formed by combining a plurality of these groups.

Q represents an alicyclic structure. The alicyclic structure may have a substituent and may be a monocyclic or polycyclic ring, and in the case of a polycyclic ring, the structure may be a crosslinked one. The monocyclic structure is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic structure include a bicyclic, tricyclic or tetracyclic structure having a carbon number of 5 or more. A cycloalkyl group having a carbon number of 6 to 20 is preferable, and examples thereof include an adamantyl group, a norbornyl group, a dicyclopentyl group, a tricyclodecyl group, and a tetracyclododecyl group. At least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom. In particular, Q is preferably, for example, a thiol group, a tricyclodecanyl group or a tetracyclododecyl group.

The hydrophobic resin may contain a ruthenium atom. Preferably, it has an alkyl fluorenyl structure (preferably a trialkyl decyl group) or a cyclic decane structure as a ruthenium containing Part of the structure of the resin.

Specific examples of the alkyl fluorenyl structure and the cyclic siloxane structure include groups represented by the following formula (CS-1) to formula (CS-3):

In the formulae (CS-1) to (CS-3), R ₁₂ to R ₂₆ each independently represent a linear or branched alkyl group (preferably having a carbon number of 1 to 20) or a cycloalkyl group (preferably carbon). The number is 3 to 20).

L ₃ to L ₅ each represent a single bond or a divalent linking group. The divalent linking group includes a single one selected from the group consisting of alkylene, phenyl, ether, thioether, carbonyl, ester, amide, urethane, or urea linkages. A group or a combination of two or more groups.

n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

The repeating unit having a fluorine atom or a ruthenium atom is preferably a (meth) acrylate-based repeating unit.

Specific examples of the repeating unit having a fluorine atom or a halogen atom are shown below, but the invention is not limited thereto. In a specific example, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ , and X ₂ represents -F or -CF ₃ .

The hydrophobic resin preferably comprises a repeating unit (b) having at least one group selected from the group consisting of (x) to (z): an alkali-soluble group (x); a group (y) capable of borrowing Decomposed by the action of an alkaline developing solution to increase the solubility to an alkaline developing solution (hereinafter, sometimes referred to simply as a polar converting group); and the group (z), which can be decomposed by the action of an acid to increase the alkalinity The solubility of the developer.

The repeating unit (b) includes the following types: a repeating unit (b') having a fluorine atom or a halogen atom on one side chain and at least one group selected from the group consisting of (x) to (z); (b*) having at least one group selected from the group consisting of (x) to (z) above, without a fluorine atom or a ruthenium atom; and a repeating unit (b") having a side chain At least one of the groups consisting of the above (x) to (z) is selected, and at the same time, at least any one of a fluorine atom or a ruthenium atom in the side chain different from the above side chain in the same repeating unit.

More preferably, the hydrophobic resin contains a repeating unit (b') as a repeating unit (b). In other words, it is more preferred that the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has a fluorine atom or a halogen atom.

In the case where the hydrophobic resin contains the repeating unit (b*), the resin is preferably a repeating unit having a fluorine atom or a ruthenium atom (with the above repeating unit) a copolymer of (b') and a repeating unit (b") different repeating unit). Further, in the repeating unit (b"), having at least one group selected from the group consisting of (x) to (z) The side chain of the group and the side chain having a fluorine atom or a ruthenium atom are preferably bonded to the same carbon atom in the main chain, that is, have a positional relationship in the following formula (K1).

In the formula, B1 represents a partial structure having at least one group selected from the group consisting of (x) to (z), and B2 represents a partial structure having a fluorine atom or a ruthenium atom.

The group selected from the group consisting of (x) to (z) is preferably an alkali-soluble group (x) or a polar group (y), more preferably a polar group (y).

Examples of the alkali-soluble group (x) include: a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamino group, a sulfonimide group, an (alkylsulfonyl group) (alkylcarbonyl group) Methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indenylene, bis(alkylsulfonyl) Methylene, bis(alkylsulfonyl) fluorenylene, tris(alkylcarbonyl)methylene, and tris(alkylsulfonyl)methylene.

Preferred alkali-soluble groups include a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, and a bis(carbonyl)methylene group.

The repeating unit (bx) having an alkali-soluble group (x) includes a repeating unit in which an alkali-soluble group is directly bonded to a main chain of the resin, such as derived from a repeating unit of acrylic acid or methacrylic acid; and a repeating unit in which an alkali-soluble group is bonded to a main chain of the resin via a linking group. Further, an alkali-soluble group may be introduced to the terminal of the polymer chain by polymerization using a polymerization initiator or a chain transfer agent containing an alkali-soluble group. These cases are all better.

In the case where the repeating unit (bx) is a repeating unit having a fluorine atom or a halogen atom (that is, a case corresponding to the repeating unit (b') or the repeating unit (b")), the content in the repeating unit (bx) Examples of the partial structure of the fluorine atom are the same as those of the above repeating unit having a fluorine atom or a halogen atom, and are preferably a group represented by the formula (F2) to the formula (F4). Further, in the repeating unit (bx) Examples of the moiety containing a halogen atom are the same as those of the above repeating unit having a fluorine atom or a halogen atom, and are preferably a group represented by the formula (CS-1) to the formula (CS-3).

The content of the repeating unit (bx) having an alkali-soluble group (x) is preferably from 1 mol% to 50 mol%, more preferably from 3 mol% to 35 mol%, based on all the repeating units in the hydrophobic resin. Ear %, more preferably 5 mole % to 20 mole %.

Specific examples of the repeating unit (bx) having an alkali-soluble group (x) are shown below, but the invention is not limited thereto. In a specific example, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ .

In the formula, Rx represents H, CH ₃ , CF ₃ or CH ₂ OH.

Examples of the polar conversion group (y) include a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C(O)OC(O)-), an acid sulfonimide group (-NHCONH-), Carboxylic acid ester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO ₂ O-), and sulfonate group (-SO ₂ O-), lactone The base is preferred.

The polar conversion group (y) is preferably one of the following: a group is, for example, included in a repeating unit derived from an acrylate or a methacrylate, and thus introduced into a side chain of the resin; and a group An example of introduction to the end of the polymer chain using a polymerization initiator or a chain transfer agent having a polar conversion group (y).

Specific examples of the repeating unit (by) having a polar conversion group (y) include repeating units having a lactone structure represented by the following formula (KA-1-1) to formula (KA-1-17).

The repeating unit (by) having a polar shift group (y) is preferably a repeating unit having a fluorine atom or a ruthenium atom (that is, a repeating unit corresponding to the repeating unit (b'), the repeating unit (b"). The resin of the repeating unit (by) is hydrophobic, but it is particularly preferable to repeat the unit for the purpose of reducing development defects.

The repeating unit (by) includes, for example, a repeating unit represented by the formula (K0):

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polar group.

R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group having a polar translating group.

However, at least one of R _k1 and R _k2 represents a group containing a polar transrading group.

As described above, the polar conversion group is a group which can be decomposed by the action of an alkaline developer to increase the solubility to the alkaline developer. The polar conversion group is preferably a group X in a partial structure represented by the formula (KA-1) or the formula (KB-1):

In formula (KA-1) or formula (KB-1), X represents a carboxylate group: -COO-, an acid anhydride group: -C(O)OC(O)-, a phosphonium imine group: -NHCONH- Carboxylic acid ester group: -COS-, carbonate group: -OC(O)O-, sulfate group: -OSO ₂ O-, or sulfonate group: -SO ₂ O-.

Y ¹ and Y ² each (may be the same or different) represent a pull electron group.

Incidentally, the repeating unit (by) has a preferred group capable of increasing the solubility to an alkaline developer by including a group having a partial structure represented by the formula (KA-1) or the formula (KB-1). a group, but in the case of a partial structure represented by the formula (KA-1) or a partial structure represented by the formula (KB-1) when Y ¹ and Y ² are monovalent, when the partial structure does not have a joint In the case of a bond, a group having a partial structure is a group having a group which is monovalent or higher by removing at least one of any hydrogen atom in a part of the structure.

A partial structure represented by the formula (KA-1) or the formula (KB-1) is bonded to an arbitrary position on the main chain of the hydrophobic resin via a substituent.

The partial structure represented by the formula (KA-1) is a structure which forms a ring structure together with a group which is X.

In the formula (KA-1), X is preferably a carboxylate group (that is, a case where a lactone ring structure is formed as KA-1), an acid anhydride group or a carbonate group, and more preferably a carboxylate group.

The ring structure represented by the formula (KA-1) may have a substituent and may have, for example, nka substituents Z _ka1 .

When a plurality of Z _ka1 are present, Z _ka1 represents (each independently represents) a halogen atom, an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, a decylamino group, an aryl group, a lactone ring group or a pendant electron group.

A plurality of Z _ka1 may be combined with each other to form a ring. Examples of the ring which can be formed by bonding Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (for example, a cyclic ether ring, a lactone ring).

Nka represents an integer of 0 to 10 and is preferably an integer of 0 to 8, more preferably an integer of 0 to 5, still more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

The electron withdrawing group of Z _ka1 has the same meaning as the electron withdrawing group of Y ¹ and Y ² described later. The above electron withdrawing group may be substituted by another electron withdrawing group.

Z _{ka1 is} preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group or an electron-withdrawing group, more preferably an alkyl group, a cycloalkyl group or an electron-withdrawing group. The ether group is preferably a group substituted with, for example, an alkyl group or a cycloalkyl group, that is, an alkyl ether group. The pull electron group has the same meaning as described above.

_Examples of the halogen atom of Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

The alkyl group as Z _ka1 may have a substituent and may be any of a linear type or a branched type. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include methyl group, ethyl group, n-propyl group, n-butyl group, second butyl group and t-butyl group. , n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl and n-decyl. The branched alkyl group preferably has a carbon number of from 3 to 30, more preferably from 3 to 20, and examples thereof include: isopropyl, isobutyl, tert-butyl, isopentyl, third pentyl, isohexyl And a third hexyl group, an isoheptyl group, a third heptyl group, an isooctyl group, a third octyl group, an isodecyl group and a third fluorenyl group. The alkyl group preferably has a carbon number of from 1 to 4, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.

The cycloalkyl group as Z _ka1 may have a substituent and may be a single ring or a polycyclic ring. In the case of multiple rings, the cycloalkyl group can be crosslinked. That is, in this case, the cycloalkyl group may have a bridged structure.

The monocyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group.

Examples of the polycyclic cycloalkyl group include a bicyclic, tricyclic or tetracyclic structure and A group having a carbon number of 5 or more. Preferred is a cycloalkyl group having a carbon number of 6 to 20, and examples thereof include: adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-decenyl group (α-pinenyl), tricyclodecyl, tetracyclododecyl and androstanyl.

The structure of the following example is also preferred as a cycloalkyl group. Incidentally, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The alicyclic moiety is preferably adamantyl, noradamantyl, decahydronaphthyl, Tricyclic fluorenyl, tetracyclododecyl, norbornyl, cedrol group, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl, more preferably adamantane Base, decahydronaphthyl, norbornyl, cedar, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl or tricyclodecyl.

The substituent of the alicyclic structure includes an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably an alkyl group having a smaller carbon number such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. The alkoxy group is preferably an alkoxy group having a carbon number of 1 to 4, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the substituent which the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (the number of carbon atoms is preferably from 1 to 4).

The above group may have a more substituent, and the substituent further includes: a hydroxyl group; a halogen atom (e.g., fluorine, chlorine, bromine, iodine); a nitro group; a cyano group; the above alkyl group; such as a methoxy group, an ethoxy group, a hydroxyl group Alkoxy groups of ethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, second butoxy and tert-butoxy; such as methoxycarbonyl and ethoxycarbonyl Alkoxycarbonyl; aralkyl such as benzyl, phenethyl and cumene; aralkyloxy; such as formazan, ethyl hydrazino, butyl fluorenyl, benzhydryl, cianamyl group And a fluorenyl group of a pentyl group; a decyloxy group such as a butenyloxy group; an alkenyl group such as a vinyl group, a propenyl group and an allyl group; such as a vinyloxy group, a propyleneoxy group, an allyloxy group and a butenyloxy group Alkenyloxy; aryl such as phenyl and naphthyl; aryloxy such as phenoxy; and aryloxycarbonyl such as benzhydryloxy.

Preferably, X in the formula (KA-1) is a carboxylate group, and a partial structure represented by the formula (KA-1) is a lactone ring, and the lactone ring is preferably from 5 to 7 members. a cyclic lactone ring.

In this regard, as shown in the following (KA-1-1) to (KA-1-17), the other ring structure is preferably 5 to 7 members of the partial structure represented by the formula (KA-1) The cyclic lactone is fused in the form of a bicyclic structure or a spiro ring structure.

Examples of the peripheral ring structure which can be bonded to the ring structure represented by the formula (KA-1) include those shown in the following (KA-1-1) to (KA-1-17) and derived based on these structures. structure.

The structure including the lactone ring structure represented by the formula (KA-1) is more preferably a structure represented by any one of the following examples (KA-1-1) to (KA-1-17). The lactone structure can be directly bonded to the backbone. Preferred structures are (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14) and (KA-1-17).

The structure containing the above lactone ring structure may or may not have a substituent. Preferred examples of the substituent are the same as the substituent Z _ka1 which the ring structure represented by the formula (KA-1) may have.

In the formula (KB-1), X is preferably a carboxylate group (-COO-).

In the formula (KB-1), Y ¹ and Y ² each independently represent a pull electron group.

The electron withdrawing group is a partial structure represented by the following formula (EW). In the formula (EW), * represents a bonding bond directly bonded to (KA-1) or a bonding bond directly bonded to X in (KB-1).

In the formula (EW), R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

n _{ew is} an integer of a repeating group represented by -C(R _ew1 )(R _ew2 )- and represents an integer of 0 or 1. In the case where n _ew is 0, it means that the bonding key is a single bond and Y _ew1 is a direct bond.

Y _ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halogenated (cyclo)alkyl group represented by a -C(R _f1 )(R _f2 )-R _f3 described later, or a halogenated aryl group, an oxy group, A carbonyl group, a sulfonyl group, a sulfinyl group, or a combination of the above groups. The electron withdrawing group can be, for example, the following structure. The term "halo(cyclo)alkyl" denotes an at least partially halogenated alkyl or cycloalkyl group, and "haloaryl" means an at least partially halogenated aryl group. In the following structural formula, R _ew3 and R _ew4 each independently represent an arbitrary structure. Regardless of the structure of R _ew3 or R _ew4 , the partial structures represented by the formula (EW) have a pull electron group. Further, R _ew3 and R _ew4 may each be bonded to the main chain of the resin, for example, preferably an alkyl group, a cycloalkyl group or a fluorinated alkyl group.

In the case where Y _ew1 is a divalent or higher group, the remaining bond forms a bond to any atom or substituent. At least one of Y _ew1 , R _ew1 and R _ew2 may be bonded to the main chain of the hydrophobic resin via a further substituent.

Y _{ew1 is} preferably a halogen atom or a halogenated (cyclo)alkyl group or a halogenated aryl group represented by -C(R _f1 )(R _f2 )-R _f3 .

At least two members selected from R _ew1 , R _{ew2 ,} and Y _ew1 may be combined with each other to form a ring.

R _f1 represents a halogen atom, a perhaloalkyl group, a perhalogenated cycloalkyl group or a perhalogenated aryl group, and is preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoro group. methyl.

R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be bonded to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. R _{f2 is} preferably the same group as R _f1 or combined with R _f3 to form a ring.

R _f1 to R _f3 may be bonded to form a ring, and examples of the ring formed include a (halogenated) cycloalkyl ring and a (halogenated) aryl ring.

Examples of the (halogenated)alkyl group in R _f1 to R _f3 include the above alkyl group in Z _ka1 and a halogenated structure thereof.

Examples of the ( _per )halocycloalkyl group and the ( _per )haloaryl group in the ring formed by the combination of R _f1 to R _f3 or R _f2 and R _f3 include the halogenated structure of the cycloalkyl group in the above Z _ka1 Preferred is a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H and a perfluoroaryl group represented by -C _(n) F _(n-1) , wherein the carbon number n It is not particularly limited, but it is preferably 5 to 13, more preferably 6.

The ring which can be formed by bonding at least two members of R _ew1 , R _ew2 and Y _ew1 to each other is preferably a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include a structure represented by the formula (KA-1-1) to the formula (KA-1-17).

Incidentally, the repeating unit (by) may have a plurality of partial structures represented by the formula (KA-1), a plurality of partial structures represented by the formula (KB-1), or a formula (KA-1). The partial structure represented and the partial structure represented by the formula (KB-1).

In this regard, the partial structure of the formula (KA-1) may partially or wholly also serve as the electron withdrawing group of Y ¹ or Y ² in the formula (KB-1). For example, in the case where X of the formula (KA-1) is a carboxylate group, the carboxylate group can also function as a pull electron group of Y ¹ or Y ² in the formula (KB-1).

Further, in the case where the repeating unit (by) conforms to the repeating unit (b*) or the repeating unit (b") and has a partial structure represented by the formula (KA-1), represented by the formula (KA-1) The partial structure is more preferably a partial structure in which the polar conversion group is -COO- in the structure represented by the formula (KA-1).

The repeating unit (by) may be a repeating unit having a partial structure represented by the formula (KY-0):

In the formula (KY-0), R ₂ represents a chain or cyclic alkyl group, and when a plurality of R ₂ are present, these R ₂ may be the same or different.

R ₃ represents a linear, branched or cyclic hydrocarbon group in which a part or the whole of a hydrogen atom on the carbon component is substituted with a fluorine atom.

R ₄ represents a halogen atom, a cyano group, a hydroxyl group, a decylamino group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, a decyl group, an alkoxycarbonyl group, or RC(=O)- or RC(=O) a group represented by O- (wherein R represents an alkyl group or a cycloalkyl group). When a plurality of R ₄ are present, these R ₄ may be the same or different, and two or more R ₄ may be combined to form a ring.

X represents an alkyl group, an oxygen atom or a sulfur atom.

Z and Za each represent a single bond, an ether bond, an ester bond, a guanamine bond, a urethane bond or a urea bond, and when a plurality of Z or Za are present, each Z or Za may be the same or different from each Other Z or Za.

* represents a bonding bond on the main chain or side chain of the resin.

o is a substituent number and represents an integer from 1 to 7.

m is the number of substituents and represents an integer from 0 to 7.

n represents a repeating number and represents an integer from 0 to 5.

The structure of -R ₂ -Z- is preferably a structure represented by -(CH ₂ ) _l -COO- (wherein represents an integer of 1 to 5).

The preferred carbon number range and specific examples of the chain or cyclic alkyl group as R ₂ are the same as those described for the chain alkyl group and the cyclic alkyl group in Z ₂ of the above formula (bb).

The carbon number of the linear, branched or cyclic hydrocarbon group as R ₃ is preferably from 1 to 30, more preferably from 1 to 20, in the case of the linear hydrocarbon group; in the case of the branched hydrocarbon group, it is preferably It is 3 to 30, more preferably 3 to 20; and in the case of a cyclic hydrocarbon group, 6 to 20. Specific examples of R ₃ include specific examples of the alkyl group and the cycloalkyl group as the above Z _ka1 .

Preferred carbon numbers and specific examples of the alkyl group and the cycloalkyl group of R ₄ and R are the same as those described above for the alkyl group and the cycloalkyl group of Z _ka1 .

The fluorenyl group as R ₄ is preferably a fluorenyl group having a carbon number of 1 to 6, and examples thereof include a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a amyl group, and a pentamidine group.

The alkyl moiety in the alkoxy group and the alkoxycarbonyl group of R ₄ includes a linear, branched or cyclic alkyl moiety, and a preferred carbon number of the alkyl moiety and specific examples are the same for the above Z _ka1 The alkyl and cycloalkyl groups are described.

The alkylene group as X includes a chain or cyclic alkyl group, and its preferred carbon number and specific examples are the same as those described for the chain alkyl group and the cyclic alkyl group for R ₂ .

As a specific structure for the repeating unit (by), the repeating unit also includes a repeating unit having a partial structure shown below.

In the formula (rf-1) and the formula (rf-2), X' represents a pull-electron substituent, and preferably a carbonyloxy group, an oxycarbonyl group, an alkyl group substituted by a fluorine atom or a fluorine atom-substituted extension. Cycloalkyl.

A represents a single bond or a divalent linking group represented by -C(Rx)(Ry)-, wherein Rx and Ry each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (preferably having a carbon number of 1 to 6, Substituted by a fluorine atom or the like, or a cycloalkyl group (preferably having a carbon number of 5 to 12, which may be substituted by a fluorine atom or the like). Rx and Ry are each preferably a hydrogen atom, an alkyl group or an alkyl group substituted with a fluorine atom.

X represents a pull electron group and specific examples thereof include a pull electron group as the above Y ¹ and Y ² . In these examples, preferred are fluorinated alkyl groups, fluorinated cycloalkyl groups, aryl groups substituted by fluorine or fluorinated alkyl groups, aralkyl groups substituted with fluorine or fluorinated alkyl groups, cyano groups and nitro groups.

* represents a bonding bond on the main chain or side chain of the resin. That is, it represents a bond which is bonded to the resin main chain via a single bond or a linking group.

Incidentally, when X' is a carbonyloxy group or an oxycarbonyl group, A is not a single bond.

The polarity conversion group is decomposed by the action of the alkaline developing solution to generate a polarity change, whereby the receding contact angle of the resist film and the water after the alkali development can be reduced. From the viewpoint of suppressing development defects, it is preferred that the receding contact angle of the film and water after alkali development is lowered.

When the temperature is 23±3° C. and the humidity is 45±5%, the receding contact angle of the resist film after alkali development with water is preferably 50° or less, more preferably 40° or 40° or less, more preferably 35° or less, and most preferably 30° or less.

The receding contact angle refers to the contact angle measured when the contact line of the droplet-substrate interface retreats, and it is well known that this is useful for simulating the mobility of droplets in a dynamic state. For the sake of simplicity, the receding contact angle can be defined as the contact angle when the droplets ejected from the tip end of the needle are dropped onto the substrate, and the droplets are retracted into the needle when the interface of the droplet retreats. In general, the receding contact angle can be measured by a measurement method of a contact angle generally called an expansion/contraction method.

The hydrolysis rate of the hydrophobic resin to the alkaline developer is preferably 0.001 nm/sec or faster, more preferably 0.01 nm/sec or faster, still more preferably 0.1 nm/sec or faster, and most Good for 1 nm / sec or faster.

When the rate of hydrolysis of the alkaline developer in the hydrophobic developer is treated with TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%) at 23 ° C, the film thickness is reduced when the resin film is formed only from the hydrophobic resin. rate.

The repeating unit (by) is more preferably a repeating unit having at least two or more polar transforming groups.

In the case where the repeating unit (by) has at least two polar transforming groups, the repeating unit preferably contains a group having a partial structure of two polar converting groups represented by the following formula (KY-1). Incidentally, when the structure represented by the formula (KY-1) does not have a bonding bond, it is a group containing a monovalent or higher valence group by removing at least one of any hydrogen atom in the structure.

In formula (KY-1) in a, R _{ky1, R} ky4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyl group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, acyl group Or aryl. Further, R _ky1 and _R ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and _R ky4 may form part of a carbonyl group (= O) bonded to the same oxygen atom.

R _ky2 and _R ky3 each independently represent an electron withdrawing group, or when R _ky1 and R _ky2 bonded form a lactone ring, _R ky3 is an electron withdrawing group. The lactone ring formed is preferably a structure of (KA-1-1) to (KA-1-17). Examples of the electron withdrawing group are the same as Y ¹ and Y ² in the formula (KB-1), and are preferably a halogen atom, and the above halogen represented by -C(R _f1 )(R _f2 )-R _f3 ( Cyclo)alkyl or haloaryl. Preferably, _say, R ky3 is a halogen atom or a halo (cyclo) a _{-C (R f1) (R f2} ) -R f3 represents an alkyl group or a halogenated aryl group, and R _ky2 coupling is formed with R _ky1 a lactone ring or a pull electron group that does not contain a halogen atom.

R _ky1, R _ky2, and _R ky4 may be bonded to each other to form a monocyclic or polycyclic structure.

Specific examples of R _ky1 and _R ky4 include the formula (KA-1) in the same _ka1 Z group.

Preferred R _ky1 lactone ring and R _ky2 formed is connected to (KA-1-1) to (KA-1-17) structure. Examples of the electron withdrawing group are the same as Y ¹ and Y ² in the formula (KB-1).

The structure represented by the formula (KY-1) is preferably a structure represented by the following formula (KY-2). Here, the structure represented by the formula (KY-2) has Any hydrogen atom in the structure removes at least one group of a monovalent or higher valent group.

In the formula (KY-2), R _ky6 to R _ky10 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group or a decylamino group. Or aryl.

Two or more members of R _ky6 to R _ky10 may be bonded to each other to form a monocyclic or polycyclic structure.

R _ky5 represents the electron-based base. The electron withdrawing group is the same as those described for Y ¹ and Y ² , and is preferably a halogen atom and a halogenated (cyclo)alkyl group or a halogenated aromatic group represented by -C(R _f1 )(R _f2 )-R _f3 . base.

Specific examples of R _ky5 to R _ky10 include the same groups as Z _ka1 in the formula (KA-1).

The structure represented by the formula (KY-2) is preferably a partial structure represented by the following formula (KY-3):

In the formula (KY-3), Z _ka1 and nka have the same meanings as in the formula (KA-1). R _ky5 has the same meaning as in the formula (KY-2).

L _ky represents an alkyl group, an oxygen atom or a sulfur atom. Examples of the alkylene group of L _ky include a methylene group and an ethyl group. L _{ky is} preferably an oxygen atom or a methylene group, more preferably a methylene group.

The repeating unit (b) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, and addition condensation, but the repeating unit is preferably added by a carbon-carbon double bond. The resulting repeating unit is polymerized. And examples thereof include: an acrylate-based repeating unit (including a system having a substituent at the α-position and the β-position), a styrene-based repeating unit (including a system having a substituent at the α-position and the β-position), and a vinyl ether-based repeating unit. a repeating unit of a norbornene-based repeating unit, and a maleic acid derivative such as maleic anhydride, a derivative thereof, and maleimide. Preferred are an acrylate-based repeating unit, a styrene-based repeating unit, a vinyl ether-based repeating unit, and a norbornene-based repeating unit; more preferably an acrylate-based repeating unit, a vinyl ether-based repeating unit, and a norbornene-based repeating unit; And preferably an acrylate-based repeating unit.

In the repeating unit (by) is a repeating unit having a fluorine atom or a helium atom (that is, corresponding to a repeating unit (b') or a repeating unit (b") In the case of the unit), examples of the partial structure of the fluorine-containing atom in the repeating unit (by) are the same as those described above for the repeating unit having a fluorine atom or a halogen atom, and are preferably from the above formula (F2) to (F4) The group represented. Further, examples of the partial structure of the halogen-containing atom in the repeating unit (by) are the same as those described above for the repeating unit having a fluorine atom or a halogen atom, preferably from the above formula (CS-1) to the formula (CS-). 3) The group represented.

The content of the repeating unit (by) in the hydrophobic resin is preferably from 10 mol% to 100 mol%, more preferably from 20 mol% to 99 mol%, based on all the repeating units in the hydrophobic resin. More preferably, it is 30% by mole to 97% by mole, and most preferably 40% by mole to 95% by mole.

Specific examples of the repeating unit (by) having a group capable of increasing the solubility to the alkaline developing solution are shown below, but the invention is not limited thereto. Specific examples of the repeating unit (by) also include those described as specific examples of the repeating unit (a3) of the resin (B).

In a specific example, Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

As a synthesis method of a monomer corresponding to a repeating unit (by) having a polar conversion group (y), a monomer can be synthesized by, for example, the method described in International Publication No. 2010/067905 and International Publication No. 2010/067905 .

An example of the repeating unit (bz) having a group (z) which can be decomposed by the action of an acid in the hydrophobic resin is the same as an example of a repeating unit having an acid-decomposable group in the resin (B).

In the case where the repeating unit (bz) is a repeating unit having a fluorine atom or a halogen atom (that is, a repeating unit corresponding to the repeating unit (b') or the repeating unit (b"), the fluorine in the repeating unit (bz) The partial structure of the atom is the same as that described above for the repeating unit of the fluorine atom or the halogen atom, and is preferably a group represented by the formula (F2) to the formula (F4). Further, the content in the repeating unit (by) The partial structure of the ruthenium atom is the same as that described above for the repeating unit having a fluorine atom or a ruthenium atom, and is preferably a group represented by the formula (CS-1) to the formula (CS-3).

The content of the repeating unit (bz) having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin is preferably from 1 mol% to 80 mol% based on all the repeating units in the hydrophobic resin. The ear %, more preferably 10 mol% to 80 mol%, still more preferably 20 mol% to 60 mol%.

The above describes a repeating unit (b) having at least one group selected from the group consisting of (x) to (z), which is a repeating unit in a hydrophobic resin based on all repeating units in the hydrophobic resin ( The content of b) is preferably from 1 mol% to 98 mol%, more preferably from 3 mol% to 98 mol%, still more preferably from 5 mol% to 97 mol%, and most preferably 10 mol% Ears to 95% ear%.

The content of the repeating unit (b') is preferably from 1 mol% to 100 mol%, more preferably from 3 mol% to 99 mol%, and particularly preferably 5, based on all the repeating units in the hydrophobic resin. Molar% to 97% by mole, and most preferably from 10 mole% to 95% by mole.

The content of the repeating unit (b*) is preferably from 1 mol% to 90 mol%, more preferably from 3 mol% to 80 mol%, more preferably from all repeating units in the hydrophobic resin. 5 moles to 70 mole%, and most preferably 10 mole% to 60 mole%. The content of the repeating unit having a fluorine atom or a ruthenium atom used together with the repeating unit (b*) is preferably from 10 mol% to 99 mol%, more preferably 20, based on all the repeating units in the hydrophobic resin. Molar% to 97% by mole, particularly preferably 30% by mole to 95% by mole, and most preferably 40% by mole to 90% by mole.

The content of the repeating unit (b") is preferably from 1 mol% to 100 mol%, more preferably from 3 mol% to 99 mol%, more preferably from all repeating units in the hydrophobic resin. 5 moles % to 97 mole %, and most preferably 10 mole % to 95 mole %.

The hydrophobic resin may further comprise a repeating unit represented by the following formula (CIII):

In the formula (CIII), R _c31 represents a hydrogen atom, an alkyl group (which may be substituted by a fluorine atom and the like), a cyano group or a -CH ₂ -OR _ac2 group, wherein R _ac2 represents a hydrogen atom, an alkyl group or a fluorenyl group. . R _{c31 is} preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. Each of these groups may be substituted with a fluorine atom or a halogen atom-containing group and the like.

L _c3 represents a single bond or a divalent linking group.

In the formula (CIII), the alkyl group of R _c32 is preferably a linear or branched alkyl group having a carbon number of 3 to 20.

The cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 20.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

The aryl group is preferably an aryl group having a carbon number of 6 to 20, more preferably a phenyl group or a naphthyl group, and each of these groups may have a substituent.

R _{c32 is} preferably an unsubstituted alkyl group or an alkyl group substituted by a fluorine atom.

The divalent linking group of L _c3 is preferably an alkylene group (preferably having a carbon number of 1 to 5), an oxy group, a phenyl group or an ester bond (a group represented by -COO-).

It is also preferred that the hydrophobic resin further comprises a repeating unit represented by the following formula (BII-AB):

In the formula (BII-AB), R _c11 'and R _c12 ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Zc' represents an atomic group for forming an alicyclic structure containing two carbon atoms (C-C) bonded to Zc'.

In the case where each group in the repeating unit represented by the formula (III) and the formula (BII-AB) is substituted with a fluorine atom-containing or a halogen atom-containing group, the repeating unit also corresponds to the above-mentioned fluorine atom or A repeating unit of a ruthenium atom.

Specific examples of the repeating unit represented by the formula (III) and the formula (BII-AB) are shown below, but the invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN. Incidentally, the repeating unit in which Ra is CF ₃ also corresponds to the above repeating unit having a fluorine atom or a ruthenium atom.

Similarly to the above-mentioned resin (B), in the hydrophobic resin, it is of course preferable that the content of impurities such as a metal is small, and the residual monomer or oligomer component is preferably from 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, and more preferably 0% by mass to 1% by mass. When these conditions are satisfied, a resist composition which does not have a foreign matter in the liquid or a sensitivity or the like which changes with time can be obtained. Further, the molecular weight distribution (Mw/Mn, also referred to as dispersion) is preferably from 1 to 3, more preferably in terms of resolution, resist profile, sidewall of the resist pattern, roughness, and the like. It is from 1 to 2, more preferably from 1 to 1.8, most preferably from 1 to 1.5.

Various commercially available products can be used as the hydrophobic resin, or the resin can be synthesized by a conventional method such as radical polymerization. Examples of general synthetic methods include: a batch polymerization method in which a monomer substance and an initiator are dissolved in a solvent, and the solution is heated to cause polymerization; and a dropping polymerization method which is carried out within 1 hour to 10 hours. A solution containing a monomer substance and a starter is added dropwise to the heated solvent. A drop-in polymerization method is preferred.

Reaction solvent, polymerization initiator, reaction conditions (eg temperature, concentration), And the purification method after the reaction is the same as that described for the resin (B).

Specific examples of the hydrophobic resin (HR) are shown below. Further, Table 1 below shows the molar ratio of the repeating unit in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains a fluorine- or atom-containing hydrophobic resin, and the hydrophobic resin is unevenly distributed on a film formed of a sensitized ray-sensitive or radiation-sensitive resin composition. The surface layer, therefore, when the liquid immersion medium is water, the receding contact angle of the film surface after baking and before exposure can be improved, and the followability of the liquid immersion liquid can also be improved.

When the temperature at the time of exposure (usually room temperature 23±3° C.) and the humidity of 45±5%, the coating film of the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention is baked and the receding contact angle before exposure Preferably 60° to 90°, more preferably 65° or more, more preferably 70° or more, and still more preferably 75° or more.

As described above, the hydrophobic resin is not uniformly distributed at the interface, but unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule, and it may not contribute to uniform mixing of the polar/nonpolar substance.

In the immersion exposure step, the liquid immersion liquid must follow the movement of the exposure head that scans on the wafer at a high speed to form an exposure pattern to move on the wafer. Therefore, the contact angle of the liquid immersion liquid with the resist film in the dynamic state is important, and the resist needs to have a property of allowing the liquid droplets to follow the high-speed scanning of the exposure head without leaving liquid droplets.

The hydrophobic resin is hydrophobic, and thus the development residue (scum) and BLOB defects are easily deteriorated after alkaline development, but the alkali dissolution rate is improved by having three or more polymer chains in at least one branch portion. (Compared to linear resin), and thus improved development residue (scum), BLOB defect performance.

In the case where the hydrophobic resin contains a fluorine atom, the fluorine atom content is preferably from 5% by mass to 80% by mass, and more preferably from 10% by mass to 80% by mass based on the molecular weight of the hydrophobic resin. Further, the repeating unit of the fluorine atom is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%, based on all the repeating units in the hydrophobic resin.

In the case where the hydrophobic resin contains a ruthenium atom, the ruthenium atom content is preferably from 2% by mass to 50% by mass, and more preferably from 2% by mass to 30% by mass based on the molecular weight of the hydrophobic resin. Further, the repeating unit containing a halogen atom is preferably from 10 mol% to 90% based on all the repeating units in the hydrophobic resin. More than 20% by mole, more preferably 20% by mole to 80% by mole.

The weight average molecular weight of the hydrophobic resin is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000, still more preferably from 3,000 to 35,000. Here, the weight average molecular weight of the resin represents a polystyrene-converted molecular weight measured by GPC (carrier: tetrahydrofuran (THF)).

The hydrophobic resin can be used by appropriately adjusting its content in the photosensitive ray-sensitive or radiation-sensitive resin composition so that the photosensitive ray-sensitive or radiation-sensitive resin film has a receding contact angle in the above range. The content of the hydrophobic resin is preferably from 0.01% by mass to 20% by mass, more preferably from 0.1% by mass to 15% by mass, even more preferably 0.1%, based on the total solid content of the photosensitive ray-sensitive or radiation-sensitive resin composition. The mass% to 10% by mass, and more preferably 0.5% by mass to 8% by mass.

The hydrophobic resin may be used alone or in combination of two or more.

[4] Basic compounds

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound, thereby reducing the change in performance over time from exposure to heating.

Preferred basic compounds include compounds having a structure represented by the following formula (A) to formula (E):

In the formulae (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may each be the same or different and represent a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), or a cycloalkyl group ( A preferred carbon number is 3 to 20) or an aryl group (carbon number is 6 to 20), and R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may each be the same or different and represent an alkyl group having 1 to 20 carbon atoms.

As the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.

The alkyl group in the formula (A) and the formula (E) is more preferably unsubstituted.

Examples of preferred compounds include: guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, amino morpholine, amine Aminoalkylmorpholine and piperidine. Examples of more preferable compounds include: a compound having an imidazole structure, a diazabicyclo structure, a ruthenium hydroxide structure, a ruthenium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure; having a hydroxyl group and/or an ether; An alkylamine derivative of a bond; and an aniline derivative having a hydroxyl group and/or an ether bond.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the compound having a diazabicyclo structure include: 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]fluorene- 5-ene and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of the compound having a ruthenium hydroxide structure include: tetrabutyl hydrogen Ammonium oxide, triarylphosphonium hydroxide, phenacyl sulfonium hydroxide and barium hydroxide having a 2-sided oxyalkyl group, specifically triphenylphosphonium hydroxide, three (third Butylphenyl)phosphonium hydroxide, bis(t-butylphenyl)phosphonium hydroxide, benzamidine methylthiophene hydroxide and 2-oxopropylthiophene hydroxide. The compound having a ruthenium carboxylate structure is a compound having an anion portion of a compound having a ruthenium hydroxide structure as a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylic acid. salt. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the aniline compound include: 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Other preferred basic compounds include a phenoxy-containing amine compound, a phenoxy-containing ammonium salt compound, a sulfonate group-containing amine compound, and a sulfonate group-containing ammonium salt compound.

The amine compound may be a primary, secondary or tertiary amine compound, and is preferably an amine compound in which at least one alkyl group is bonded to a nitrogen atom. The amine compound is more preferably a tertiary amine compound. In the amine compound, as long as at least one alkyl group (preferably having a carbon number of 1 to 20) is bonded to the nitrogen atom, a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group in addition to the alkyl group. (preferably having a carbon number of 6 to 12) may also be bonded to a nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain to form an oxygen alkyl group. The number of oxygen alkyl groups in the molecule is one or more, preferably from 3 to 9, more preferably from 4 to 6. In the oxygen alkyl group, an oxygen extended ethyl group (-CH ₂ CH ₂ O-) or an oxygen extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. More preferably, it is an oxygen-extended ethyl group.

The ammonium salt compound may be a primary, secondary, tertiary or tertiary ammonium salt compound, preferably an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom. In the ammonium salt compound, as long as at least one alkyl group (preferably having a carbon number of 1 to 20) is bonded to the nitrogen atom, a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aromatic group in addition to the alkyl group. The base (preferably having a carbon number of 6 to 12) may also be bonded to the nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain to form an oxygen alkyl group. The number of oxygen alkyl groups in the molecule is one or more, preferably from 3 to 9, more preferably from 4 to 6. In the oxygen alkyl group, an oxygen extended ethyl group (-CH ₂ CH ₂ O-) or an oxygen extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. More preferably, it is an oxygen-extended ethyl group.

Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate, and a halogen atom and a sulfonate are preferred. The halogen atom is preferably a chloride, a bromide or an iodide, and the sulfonate is preferably an organic sulfonate having a carbon number of 1 to 20. Examples of the organic sulfonate include an alkylsulfonate having a carbon number of 1 to 20, and an arylsulfonate. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy, decyl and aryl. Specific examples of the alkyl sulfonate include: methanesulfonate, ethanesulfonate, butanesulfonate, hexanosulfonate, octanesulfonate, benzylsulfonate, trifluoromethanesulfonate, pentafluoro Ethane sulfonate and nonafluorobutane sulfonate. The aryl group of the aryl sulfonate includes a benzene ring, a naphthalene ring and an anthracene ring. Benzene ring, naphthalene ring and anthracene ring The substituent has a substituent, and the substituent is preferably a linear or branched alkyl group having a carbon number of 1 to 6, and a cycloalkyl group having a carbon number of 3 to 6. Specific examples of the linear or branched alkyl group and the cycloalkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group and cyclohexyl group. Other examples of the substituent include an alkoxy group having a carbon number of 1 to 6, a halogen atom, a cyano group, a nitro group, a decyl group, and a decyloxy group.

The phenoxy-containing amine compound and the phenoxy-containing ammonium salt compound are amine compounds or ammonium salt compounds having a phenoxy group at the terminal end of the alkyl group opposite to the nitrogen atom. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, a decyloxy group and an aromatic group. Oxygen. The substitution position of the substituent may be any of the 2 to 6 positions, and the number of the substituents may be any of the range of 1 to 5.

The compound preferably has at least one oxygen alkyl group between the phenoxy group and the nitrogen atom. The number of oxygen alkyl groups in the molecule is one or more, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen extended ethyl group (-CH ₂ CH ₂ O-) and an oxygen extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) are preferred. More preferably, it is an oxygen-extended ethyl group.

The sulfonate group in the ammonium salt compound having a sulfonate group and the ammonium salt compound having a sulfonate group may be any one of an alkylsulfonate, a cycloalkylsulfonate, and an arylsulfonate. By. In the case of the alkyl sulfonate, an alkyl group having a carbon number of 1 to 20 is preferred; in the case of the cycloalkyl sulfonate, a cycloalkyl group having a carbon number of 3 to 20 is preferred; In the case of the aryl sulfonate, an aryl group having 6 to 12 carbon atoms is preferred. Alkyl sulfonate, cycloalkyl sulfonate and aromatic The sulfonate may have a substituent, and the substituent is preferably a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group or a sulfonate group.

The compound preferably has at least one oxygen alkyl group between the sulfonate group and the nitrogen atom. The number of oxygen alkyl groups in the molecule is one or more, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen extended ethyl group (-CH ₂ CH ₂ O-) and an oxygen extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) are preferred. More preferably, it is an oxygen-extended ethyl group.

The compounds shown below are also preferred as basic compounds.

The basic compounds may be used alone or in combination of two or more.

The composition of the present invention may or may not contain a basic compound, but in the case of containing a basic compound, the amount of the basic compound is usually 0.001 by mass based on the solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition. From 0.01% by mass to 5% by mass, preferably from 0.01% by mass to 5% by mass.

The acid generator (including the acid generator (A')) and the basic compound are preferably used in the composition in an acid generator/basic compound (mole ratio) = 2.5 to 300. That is, from the viewpoint of sensitivity and resolution, the molar is preferably 2.5 or more; from the inhibition to the heat treatment From the viewpoint of a decrease in the resolution caused by the thickening of the front resist pattern over time, the molar ratio is preferably 300 or less. The acid generator/basic compound (mole ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.

In the case of the low molecular compound (D) described in the item [5] described later, the use condition of the basic resin is preferably from the low molecular compound (D) / basic compound = 100 / 0 to 100 / 90, more preferably 100/0 to 30/70, and even better at 100/0 to 50/50.

Incidentally, the basic compound used herein does not include a low molecular compound (D) which is also a basic compound containing a nitrogen atom and having a group capable of being detached by the action of an acid.

[5] Low molecular compound containing a nitrogen atom and having a group capable of being detached by the action of an acid

The composition of the present invention may include a low molecular compound having a nitrogen atom and having a group capable of being detached by the action of an acid (hereinafter, sometimes referred to as "low molecular compound (D)" or "component (D) in some cases). ").

The group which can be detached by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group or a semi-amine amine group ( Hemiaminal ether group), more preferably a carbamate or a hemiamine ether group.

The molecular weight of the low molecular compound (D) having a group capable of being detached by the action of an acid is preferably from 100 to 1,000, more preferably from 100 to 700, still more preferably from 100 to 500.

The compound (D) preferably has an acid capable of being on its nitrogen atom An amine derivative of a group which acts as a detachment.

The compound (D) may have a protecting group-containing carbamate group on its nitrogen atom. The protecting group constituting the carbamate group can be represented by the following formula (d-1):

In the formula (d-1), each Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkoxyalkyl group. Each Rb may be bonded to each other to form a ring.

The alkyl group, the cycloalkyl group, the aryl group and the aralkyl group represented by Rb may each pass through a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group and a pendant oxy group, and an alkane. Substituted by an oxy group or a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

Examples of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group of Rb (each of which may be substituted by the above functional group, alkoxy group or halogen atom) include: a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, decane, decane, undecane and dodecane, Or a group substituted with an alkane-substituted group with one or more or more groups such as cyclobutyl, cyclopentyl and cyclohexyl cycloalkyl; derived from, for example, cyclobutane, cyclopentane, ring a group of cyclohexanes of cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, and adamantane, or a group derived from a cycloalkane in a linear form such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl and t-butyl or a group substituted with one or more groups of a branched alkyl group; a group derived from an aromatic compound such as benzene, naphthalene, and anthracene, or a group derived from an aromatic compound such as a methyl group, a One or more or more groups of a linear or branched alkyl group of a group, n-propyl group, isopropyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group and tert-butyl group Substituted group; derived from impurities such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, hydrazine, porphyrin, quinoline, perhydroquinoline, indazole, and benzimidazole a group of a ring compound, or a group substituted with a group derived from a heterocyclic compound, substituted with one or more groups derived from a linear or branched alkyl group or a group derived from an aromatic compound; a group derived from a linear or branched type alkane/a group derived from a cycloalkane derived from a group such as a phenyl group, a naphthyl group and a fluorenyl group a group substituted with one or more groups of a group of a fragrance compound; and the above substituents are via, for example, a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, and a pendant oxy group. A functional group substituted group.

Rb is preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group. More preferably, it is a linear or branched alkyl or cycloalkyl group.

Examples of the ring formed by bonding two Rbs to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, and a derivative thereof.

The specific structure of the group represented by the formula (d-1) is shown below.

The compound (D) can also be constituted by arbitrarily combining the above basic compound with the structure represented by the formula (d-1).

The compound (D) is more preferably a compound having a structure represented by the following formula (A).

Incidentally, the compound (D) may be a compound corresponding to the above basic compound as long as it is a low molecular compound having a group which can be detached by the action of an acid.

In the formula (A), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Further, when n = 2, the two Ra may be the same or different, and the two Ra may be bonded to each other to form a divalent heterocycloalkyl group (preferably having a carbon number of 20 or less) or a derivative thereof.

Rb has the same meaning as Rb in the above formula (d-1), and preferred examples are also the same, with the constraint that when one or more Rb in -C(Rb)(Rb)(Rb) is In the case of a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.

n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n+m=3.

In the formula (A), the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group represented by Ra may be substituted by a group which is the same as the alkyl group, cycloalkyl group, and aromatic group represented by Rb. Substitutable groups on the aryl and alkyl groups.

Specific examples of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group of Ra (each of which may be substituted by the above groups) include the same as the above specific examples of Rb. Group.

Examples of the divalent heterocyclic hydrocarbon group (preferably having a carbon number of 1 to 20) or a derivative thereof formed by Ra bonding to each other include a group derived from a heterocyclic compound such as pyrrolidine or piperidine. Porphyrin, 1,4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, Homopiperazine, 4-azabenzo Imidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, Carbazole, benzimidazole, imidazo[1,2-a]pyridine, (1S,4S)-(+)-2,5-diazabicyclo[2.2 .1] heptane, 1,5,7-triazabicyclo[4.4.0]non-5-ene, anthracene, porphyrin, 1,2,3,4-tetrahydroquinoxaline (1 , 2,3,4-tetrahydroquino xaline), perhydroquinoline and 1,5,9-triazacyclododecane; and a group derived from a heterocyclic compound derived from a linear or branched alkane a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, and a group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholine. a group substituted with one or more than one group of the functional groups of the pendant oxy group.

Particularly preferred examples of the compound (D) in the present invention are shown below, but the invention is not limited thereto.

The compound represented by the formula (A) can be synthesized based on, for example, JP-A-2007-298569 and JP-A-2009-199021.

In the present invention, the low molecular compound (D) having a nitrogen atom and having a group capable of being detached by the action of an acid may be used singly or in combination of two or more kinds.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may or may not include a low molecular compound (D) containing a nitrogen atom and having a group capable of being detached by the action of an acid, but containing a low molecular compound ( In the case of D), the content of the low molecular compound (D) is usually 0.001% by mass to 20% by mass, preferably 0.001% by mass to 10% by mass based on the total solid compound of the composition combined with the above basic compound. More preferably, it is 0.01% by mass to 5% by mass.

[6] surfactants

The composition of the present invention may further comprise a surfactant, but in the case of including a surfactant, the surfactant is preferably a fluorine-containing and/or cerium-containing surfactant.

Examples of the surfactants satisfying the above include: Megafac F176 and Megafac R08 (manufactured by Dainippon Ink Chemical Industry (DIC Corporation); PF656 and PF6320 (manufactured by OMNOVA); Troysol S-366 (by Troy Chemical) Manufactured; Fluorad FC430 (manufactured by Sumitomo 3M); and polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Surfactants other than fluorine-containing and/or barium-containing surfactants may also be used. Specifically, it includes polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

Further, a known surfactant can be suitably used. Examples of surfactants that can be used include the surfactants described in paragraph [0273] of U.S. Patent Publication No. 2008/0248425 A1.

The surfactants may be used alone or in combination of two or more.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant, but in the case of including a surfactant, the surfactant is preferably used in terms of the total solid content of the composition. It is 0 to 2% by mass, more preferably 0.0001% by mass to 2% by mass, still more preferably 0.0005% by mass to 1% by mass.

On the other hand, it is also preferred to add the surfactant to the amount of 10 ppm or less, or no surfactant. Thanks to this configuration, the hydrophobic resin is more unevenly distributed on the surface, so that the surface of the resist film is more hydrophobic and the water followability at the time of immersion exposure can be improved.

[7] Solvent

The solvent which can be used in the preparation of the composition is not particularly limited as long as it dissolves the respective components, but examples thereof include: an alkylene glycol monoalkyl ether carboxylate (for example, propylene glycol monomethyl ether acetate), An alkylene glycol monoalkyl ether (such as propylene glycol monomethyl ether), an alkyl lactate (such as ethyl lactate, methyl lactate), a cyclic lactone (such as γ-butyrolactone, preferably having a carbon number of 4) To 10), a chain or cyclic ketone (for example, 2-heptanone, cyclohexanone, preferably having a carbon number of 4 to 10), an alkyl carbonate (preferably an alkyl acetate such as butyl acetate), And an alkyl alkoxyacetate (ethyl ethoxypropionate). Other solvents that can be used include, for example, the solvents described below in paragraph [0244] of U.S. Patent Application Publication No. 2008/0248425 A1.

Among the above solvents, an alkylene glycol monoalkyl ether carboxylate and an alkylene glycol monoalkyl ether are preferred.

The solvent may be used singly or in combination of two or more. In the case of mixing two or more solvents, a solvent having a hydroxyl group is preferably mixed with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40.

The solvent having a hydroxyl group is preferably an alkylene glycol monoalkyl ether, and the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate.

[8] Other components

In addition to the above components, the composition of the present invention may suitably contain a cerium carboxylate salt, for example, in Proceeding of Society of Photo-optical Instrumentation Engineers, Proceeding of SPIE, No. 2724, 355 (1996). The dissolution preventing compounds, dyes, plasticizers, photosensitizers, light absorbers, and the like having a molecular weight of 3,000 or less are described.

[9] Pattern forming method

The pattern forming method of the present invention includes the step of exposing and developing a resist film.

The resist film is formed of the above-described sensitized ray-sensitive or radiation-sensitive resin composition of the present invention, and more specifically, is preferably formed on a substrate. In the pattern forming method of the present invention, the step of forming a film on a substrate by a resist composition, the step of exposing the film, and the developing step can be performed by a known method.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used in a thickness of 30 nm to 250 from the standpoint of improving the resolution. The film of nano is preferably used in a film having a thickness of 30 nm to 200 nm. The film thickness can be obtained by setting the solid content concentration in the photosensitive ray-sensitive or radiation-sensitive resin composition to an appropriate range, thereby imparting an appropriate viscosity to the film and improving coatability and film formability.

The total solid content concentration in the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is usually from 1% by mass to 10% by mass, preferably from 1% by mass to 8.0% by mass, more preferably from 1.0% by mass to 6.0% by mass. %.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is used by dissolving the above components in a solvent and filtering them through a filter, and applying them to a support. The filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon having a pore diameter of 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or 0.03 μm. the following. A variety of filters can be used in series or in parallel. Also, the composition can be filtered multiple times. Further, the composition may be degassed or treated similarly before/after filtration of the composition through the filter.

The composition is applied to a substrate (for example, a substrate coated with tantalum/cerium oxide) for use in manufacturing integrated circuit components by a suitable coating method such as a spin coater. Then, the coating material is dried to form a photosensitive resist film.

The film is irradiated with actinic rays or radiation passing through a predetermined mask, and the film is preferably baked (heated), followed by development and rinsing, whereby a good pattern can be obtained. Incidentally, in the case of irradiation with an electron beam, a maskless lithography (direct lithography) is usually performed.

The pattern forming method preferably includes a pre-filming method and before the exposing step Heating step (pre-bake, PB).

Further, after the exposure step and before the development step, the pattern forming method preferably further includes a Post Exposure Bake (PEB).

Regarding the heating temperature, both PB and PEB are preferably from 70 ° C to 120 ° C, more preferably from 80 ° C to 110 ° C.

The heating time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, still more preferably from 30 seconds to 90 seconds.

Heating may be performed using an element attached to a conventional exposure/developer, or a heating plate or the like may be used for heating.

Thanks to baking, the reaction in the exposed area is accelerated and the sensitivity and pattern profile are improved.

The actinic ray or radiation is not particularly limited, but it is, for example, a KrF excimer laser, an ArF excimer laser, an EUV light or an electron beam, preferably an ArF excimer laser, an EUV light or an electron beam.

The alkaline developing solution used in the developing step usually uses a quaternary ammonium salt represented by tetramethylammonium hydroxide, but in addition to the compound, an inorganic base, a primary to tertiary amine, an alcoholamine, a cyclic amine can also be used. Or an alkaline aqueous solution of its analog.

Further, after adding an appropriate amount of an alcohol and a surfactant to the alkaline developing solution, the alkaline developing solution may be used.

The alkali concentration of the alkaline developer is usually from 0.1% by mass to 20% by mass.

The pH of the alkaline developer is usually from 10.0 to 15.0.

Pure water may also be used for the rinsing solution, and an appropriate amount of surfactant may be added to the rinsing solution before use.

The developing method to be applied is, for example, a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dipping method); by the effect of surface tension, a developing solution is piled up on the surface of the substrate, and it is allowed to stand for a certain period of time. a method of developing (puddle method); a method of spraying a developer on a surface of a substrate (spraying method); and scanning a developer jet nozzle at a constant rate when the substrate is rotated at a constant speed, continuously ejecting on the substrate A method of developing a solution (dynamic dispense method).

After the developing step or the rinsing step, a treatment of removing the developing solution or the rinsing solution attached to the pattern by a supercritical fluid may be performed.

The antireflection film may be provided in advance by coating on the substrate before forming the photosensitive film (resist film).

The antireflection film which can be used may be an inorganic film type such as titanium, titanium oxide, titanium nitride, chromium oxide, carbon, and amorphous germanium or an organic film type composed of a light absorbing agent and a polymer material. As the organic antireflection film, a commercially available organic antireflection film such as DUV30 series and DUV-40 series manufactured by Brewer Science Co., Ltd., and AR-2, AR-3, and AR-5 manufactured by Shipley Corporation can also be used.

When irradiated with actinic rays or radiation, exposure (liquid immersion exposure) can be performed by filling a liquid (liquid immersion medium) having a refractive index higher than air between the film and the lens. By this exposure, the resolution can be improved. The liquid immersion medium used is preferably water. Water is also preferable from the viewpoint of a small refractive index temperature coefficient, ease of acquisition, and ease of handling.

Furthermore, in terms of the position at which the refractive index can be increased, refraction can also be used. A medium with a ratio of 1.5 or more. The medium can be an aqueous solution or an organic solvent.

In the case of using water as the liquid immersion liquid, an additive for the purpose of increasing the refractive index or the like may be added in a small ratio. Examples of the additive are described in detail in Chapter 12 of the Ekishin Lithography no Process to Zairyo (Process and Material of Immersion Lithography) by CMC Press (CMC Shuppan). On the other hand, the presence of an opaque substance of 193 nm or an impurity having a refractive index different from that of water causes distortion of an optical image projected onto the film. Therefore, the water used is preferably distilled water. Pure water further purified via an ion exchange filter or similar equipment can also be used. The resistance of pure water is preferably 18.3 mega-cm (MQcm) or 18.3 mega-cm cm or more, and the total organic carbon (TOC) is preferably 20 parts per billion or 20 parts per billion. The following. Further, it is preferred to subject the water to a degassing treatment.

In order to prevent the resist film from directly contacting the liquid immersion liquid, a liquid immersion liquid poorly soluble film (hereinafter, sometimes referred to simply as "top coat layer") may be provided between the formed resist film and the liquid immersion liquid. The functions necessary for the top coat are: suitability for coating as a resist cover layer; transparency for radiation (especially radiation of 193 nm wavelength); and poor solubility of liquid immersion liquid. The top coat layer preferably does not mix with the resist film and can uniformly coat the cover layer as a resist.

From the viewpoint of transparency of 193 nm light, the top coat layer is preferably an aromatic-free polymer, and examples of such a polymer include: a hydrocarbon polymer, an acrylate polymer, a polymethacrylic acid, a poly Acrylic acid, polyvinyl ether, A ruthenium containing polymer and a fluoropolymer. The above hydrophobic resin is suitable as a top coat. If impurities are eluted from the top coat into the liquid immersion liquid, the optical lens is contaminated. Therefore, the amount of the residual monomer component of the polymer contained in the top coat layer is preferably as small as possible.

When the top coat is peeled off, a developer may be used, or a releasing agent may be additionally used. The release agent is preferably a solvent which is less permeable to the resist. Insofar as the stripping step can be performed simultaneously with the development step of the resist, the top coat layer is preferably peeled off with an alkaline developer; and from the viewpoint of peeling off with an alkaline developer, the top coat layer It is preferably acidic; however, the top coat layer may be neutral or alkaline from the viewpoint of non-mixability with the resist.

The difference in refractive index between the top coat and the liquid immersion liquid is preferably zero or small. In this case, the resolution can be improved. In the case where the exposure light source is an ArF excimer laser (wavelength: 193 nm), water is preferably used as the liquid immersion liquid, and thus the refractive index of the top coat for ArF immersion exposure is preferably close to water. Refractive index (1.44).

Further, the top coat layer is preferably a film from the viewpoint of transparency and refractive index. The top coat layer is preferably not mixed with the resist film and, in turn, is not mixed with the liquid immersion liquid. From this standpoint, when the liquid immersion liquid is water, the solvent for the top coat layer is preferably poorly soluble in the solvent used in the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention, and is insoluble in water. . Further, when the liquid immersion liquid is an organic solvent, the top coat layer may be water-soluble or water-insoluble.

The present invention also relates to a method of manufacturing an electronic component, including the pattern forming method of the present invention, and an electronic component manufactured by the manufacturing method.

The electronic component of the present invention is adapted to be loaded on an electronic device (such as household electricity) Sub-components, OA ̇media-related devices, optical components, and communication components.

Instance

The invention is explained in more detail below by reference to examples, but the invention is not limited thereto.

[Synthesis Example 1: Synthesis of Compound A-6] 9-ethylcarbazole-2,7-ditetrahydrothiophene quinodifluorosulfonate

Ethyl oxazole (5 g) and 11.7 g of tetramethylene sulfonium were dissolved in 80 g of chloroform, and the solution was cooled to -50 °C. Next, 23.7 g of trifluoroacetic anhydride and 16.9 g of trifluoromethanesulfonic acid were slowly added dropwise, and the temperature was heated to -20 °C. After stirring for 2 hours, the temperature was raised to room temperature, and a solution of 25 g of potassium nonafluorobutanesulfonate and 50 g of acetonitrile were dissolved in 150 g of water. After stirring for 30 minutes, the chloroform layer was washed three times with pure water, and then the solvent was removed with distilled water under reduced pressure. The residue was slurried with cyclopentyl methyl ether slurry to obtain 23.6 g of the compound A-6 shown below.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 9.0 (s. 2H), δ 7.9 (d. 2H), δ 7.65 (d. 2H), δ 4.3 (q. 2H), δ 4. 1 (m. 4H), δ 3.9 (m. 4H), δ 2.8 (m. 4H), δ 2.4 (m, 4H), δ 1.4 (t. 3H).

Other photoacid generators shown in Table 2 below were synthesized by the same method as in Synthesis Example 1.

[Synthesis Example 2: Synthesis of Resin C]

11.5 g of cyclohexanone was charged into a three-necked flask under a nitrogen stream and heated to 85 °C. Next, by dissolving the following compounds (monomers) (the amount of the compound is 1.98 g, 3.05 g, 0.98 g, 2.19 g, and 2.76 g from the left), and the polymerization initiator V-610 (from Wako Pure Chemical Industries, Ltd.) (Wako Pure Chemical Industries, Ltd.), 0.599 g) A solution obtained from 21.0 g of cyclohexanone was added dropwise to the above-mentioned three-necked flask over 6 hours. After completion of dropwise addition, the reaction was allowed to proceed for 2 hours at 85 °C. After the reaction solution was allowed to cool, the reaction solution was added dropwise to a mixed solution of 420 g of hexane/180 g of ethyl acetate over a period of 20 minutes, and the precipitated powder was collected by a filter and dried to obtain 9.1 g of resin c were obtained. The polymer composition ratio (Mohr ratio) determined by NMR was 20/25/10/30/15. The resin c obtained by standard polystyrene had a weight average molecular weight of 9,200 and a polydispersity (Mw/Mn) of 1.55.

Resin a, resin b, and resin d to resin f were synthesized by the same method as in Synthesis Example 2.

<Preparation of sensitized ray-sensitive or radiation-sensitive resin composition>

The components shown in the following Table 2 were dissolved in a solvent to prepare a solution having a solid content concentration of 4% by mass, and the solution was filtered through a polyethylene filter having a pore size of 0.05 μm to prepare sensitized ray or radiation. Resin composition. The sensitized ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in Table 2.

The ratio of each component in the table in the case of using multiple types is the mass ratio.

Incidentally, in Table 2, when the photosensitive ray-sensitive or radiation-sensitive resin composition contains a hydrophobic resin (HR), its use form is referred to as "addition". When the photosensitive ray-sensitive or radiation-sensitive resin composition does not contain a hydrophobic resin (HR), and after the film is formed, a top coat protective film containing a hydrophobic resin (HR) is formed as a cover layer of the film, Its usage pattern is marked as "TC".

<Evaluation of Resist> (Exposure Condition 1: ArF immersion exposure) (Examples 1 to 10 and Examples 13 to 23, Comparative Example 1 and Comparative Example 2)

An organic anti-reflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was coated on a 12-inch wafer and baked at 205 ° C for 60 seconds to form an anti-reflection having a thickness of 98 nm. A film, and the above-prepared photosensitive ray-sensitive or radiation-sensitive resin composition was applied onto the above 12-inch wafer and baked at 130 ° C for 60 seconds to form a resist film having a thickness of 120 nm. In the case of using a top coat, A 3% by mass solution was applied to the film obtained above (this solution was dissolved in decane/octanol by mass ratio of hydrophobic resin (HR) as a top coat resin shown in Table 2 below) : Prepared in 9/1), and then baked at 85 ° C for 60 seconds to form a top coat having a thickness of 50 nm. The resulting wafer was passed via an immersion scanner (XT1700i, manufactured by ASML, NA: 1.20, C-Quad, external σ: 0.981, internal σ: 0.895, XY deflection) using an ArF excimer laser immersion scanner (XT1700i) A halftone mask exposure with a line width of 48 nm and a space ratio of 1:1. Ultrapure water was used as the liquid immersion liquid. Thereafter, the wafer was heated at 100 ° C for 60 seconds, immersed in a tetramethylammonium hydroxide aqueous solution (2.38 mass %) for development for 30 seconds, and then immersed in pure water for washing, and then rotated. Dry to form a pattern.

(Exposure Condition 2: ArF Dry Exposure) (Example 11 and Example 12)

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was coated on a 12-inch wafer and baked at 205 ° C for 60 seconds to form an anti-reflection having a thickness of 78 nm. A film was prepared, and the prepared positive resist composition was applied onto the above 12-inch wafer and baked at 130 ° C for 60 seconds to form a resist film having a thickness of 120 nm. The obtained wafer was passed through a line having a line width of 75 nm by using an ArF excimer laser scanner (PAS5500/1100, manufactured by ASML, NA: 0.75, even polarity, σo/σi = 0.89/0.65). Exposure to a halftone mask with a spatial ratio of 1:1, followed by heating at 100 ° C for 60 seconds, immersing the wafer in tetramethylammonium hydroxide aqueous solution (2.38 mass%) for 30 seconds, and then Wash in pure water, then spin dry to obtain a resist pattern case.

(Evaluation of exposure sensitivity)

The exposure dose for the line and space mask pattern having a line width of 48 nm in line exposure condition 1 and a line width of 75 nm in exposure condition 2 as the preferred exposure dose And use it as exposure sensitivity. Smaller values indicate higher performance.

(Evaluation of development defects)

A defect detector KLA 2360 (trade name) manufactured by KLA Tencor Ltd. was used, and the pixel size of the defect detector was set to 0.16 μm, and the threshold was set to 20 to perform the amount of the random mode. Measurement. The development defect extracted from the difference made by the reference image plus the pixel unit is detected, and the number of development defects per unit area (1 square centimeter) is calculated electronically. The smaller the value of the table, the higher the performance.

The abbreviations in the table represent those shown above or in the specific examples below.

[Compound (A)]

[Other acid generators]

[Resin (B)]

In the following resin a to resin f, the composition ratio of the repeating unit is a molar ratio.

[alkaline compound]

DIA: 2,6-diisopropylaniline

TEA: Triethanolamine

DBA: N,N-dibutylaniline

PBI: 2-phenylbenzimidazole

PEA: N-phenyldiethanolamine

[Low Molecular Compound (D) (Compound (D)) having a group capable of being detached by the action of an acid]

[Surfactant]

W-1: Megafac F176 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) (fluorine-containing)

W-2: Megafac R08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) (fluorine-containing and antimony containing)

W-3: PF6320 (manufactured by OMNOVA) (fluorine-containing)

W-4: Troysol S-366 (manufactured by Troy Chemical)

[solvent]

A1: Propylene glycol monomethyl ether acetate (PGMEA)

A2: cyclohexanone

A3: γ-butyrolactone

B1: Propylene glycol monomethyl ether (PGME)

B2: ethyl lactate

As is apparent from the results in Table 2, exposure sensitivity was used in Comparative Example 1 using an acid generator having one fluorene structure, and Comparative Example 2 having two fluorene structures but not satisfying Formula (I) It is low (preferably the exposure dose is large), and the number of development defects is large.

On the other hand, in Examples 1 to 23 using the compound (A) represented by the formula (I) as the acid generator, the exposure sensitivity is high (preferably, the exposure amount is small) and the number of development defects is small. .

Industrial applicability

According to the sensitizing ray-sensitive or radiation-sensitive resin composition and the resist film and pattern forming method using the composition, excellent excellent exposure sensitivity and low development defects are ensured. The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention can be suitably used in, for example, an ArF immersion exposure process.

Moreover, the pattern forming method of the present invention can provide a method of manufacturing an electronic component and an electronic component manufactured by the manufacturing method.

The present application is based on Japanese Patent Application No. JP 2011-153233, filed on Jul. 2011, the entire content of which is hereby incorporated by reference.

Claims (12)

A photosensitive ray-sensitive or radiation-sensitive resin composition comprising: a compound (A) represented by the following formula (I); and a resin (B): Wherein X represents an oxygen atom, a sulfur atom or -N(Rx)-; R ₁ to R ₈ and R _X each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group or an alkane group. a carbonyloxy group, an aryl group, an aryloxy group, an aryloxycarbonyl group or an arylcarbonyloxy group; and R ₁ to R ₈ may be bonded to each other to form a ring; the limitation is that at least two are from R ₁ to R ₈ The selected members represent the structure represented by the following formula (II): Wherein when X is an oxygen atom or a sulfur atom, R ₉ and R ₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group; when X is -N(Rx)-, R ₉ and R ₁₀ each independently represent an alkyl group. Or a cycloalkyl group; and each R ₉ and each R ₁₀ may be the same or different from each other R ₉ and each other R ₁₀ ; R ₉ and R ₁₀ may be bonded to each other to form a ring; and Z ^- represents non-nucleophilic anion, each of Z ^- may be the same or different from every other Z ^-, and a plurality of Z ^- can be combined to form a multi-valent non-nucleophilic anion. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein Z ^- in the formula (II) is a sulfonate anion. The sensitizing ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein Z ^- in the formula (II) is an anion represented by the following formula (III): Wherein each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom; and R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom, and when a plurality of R _{When 11} and a plurality of R ₁₂ are present, each R ₁₁ and each R ₁₂ may be the same as or different from each of the other R ₁₁ and each of the other R ₁₂ ; L represents a divalent linking group, and when a plurality of L exist Each L may be the same as or different from each other L; A represents a cyclic organic group; and x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein R ₉ and R ₁₀ in the formula (II) are each independently an alkyl group or a cycloalkyl group, and R ₉ and R are the same. ₁₀ may be combined with each other to form a loop. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein R ₉ and R ₁₀ in the formula (II) are combined to form a ring. The photosensitive ray-sensitive or radiation-sensitive resin composition as described in claim 1, wherein X represents -N(Rx)-, and Rx in the formula (I) each has a structure represented by the formula (II) The alkyl group, the cycloalkyl group or the aryl group as a substituent, and at least one member selected from R ₁ to R ₈ is a structure represented by the formula (II). The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (B) is decomposable by an action of an acid to increase the alkali development of the resin (B). A soluble resin in the liquid. A resist film formed by using a photosensitive ray-sensitive or radiation-sensitive resin composition as described in any one of claims 1 to 7. A pattern forming method comprising: exposing a resist film as described in claim 8 of the patent application a step of forming an exposed resist film; and a step of developing the exposed resist film. The pattern forming method according to claim 9, wherein the exposure method is liquid immersion exposure. A method of manufacturing an electronic component, comprising: the pattern forming method according to claim 9 of the patent application. An electronic component manufactured by the method of manufacturing an electronic component according to claim 11 of the patent application.