TW201610569A - Actinic ray-sensitive or radiation-sensitive resin composition, pattern-forming method, electronic device production method, and electronic device - Google Patents

Abstract

An objective of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition and a pattern-forming method using the same, the resin composition being highly sensitive and having a large depth of focus, especially in the formation of ultra fine (e.g. a linewidth of at most 50nm) patterns. Another objective is to provide an electronic device production method comprising said pattern-forming method, and an electronic device produced by said production method. The actinic ray-sensitive or radiation-sensitive resin composition comprises a compound (A) that generates a sulfonic acid represented by general formula (I) when irradiated with actinic rays or radiation.

Description

Photosensitive ray- or radiation-sensitive resin composition, pattern forming method, electronic component manufacturing method, and electronic component

The present invention relates to a sensitized ray- or radiation-sensitive resin composition and a pattern forming method. More specifically, the present invention relates to a semiconductor manufacturing process for an integrated circuit (IC) or the like, a circuit substrate of a liquid crystal, a thermal head, or the like, and other photo-etching processes (photofabrication). a step, a lithographic printing plate, a sensitizing ray-sensitive or radiation-sensitive resin composition and a pattern forming method of an acid-curable composition. Further, the present invention relates to a method of manufacturing an electronic component including the pattern forming method, and an electronic component manufactured by the method.

The chemically amplified resist composition is a pattern forming material in which an acid is formed in an exposed portion by irradiation with actinic rays such as ArF or radiation, and photochemical reaction is carried out by reacting the acid as a catalyst. The solubility of the irradiated portion and the non-irradiated portion of the radiation or the radiation to the developer changes to form a pattern on the substrate.

Various compounds have been developed as a photoacid generator which is a main constituent component of a chemically amplified resist composition (for example, Patent Document 1 to Patent Document 2). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-2252 [Patent Document 2] International Publication No. 2009/051088

[Problems to be solved by the invention]

However, the inventors of the present invention have studied the composition containing the photoacid generator described in Patent Documents 1 to 2, and as a result, it has been found that particularly in the formation of extremely fine (for example, a line width of 50 nm or less). , the desired focus tolerance (DOF: Depth Of Focus) and sensitivity are further improved.

In view of the above circumstances, an object of the present invention is to provide a sensitized ray-sensitive or radiation-sensitive resin composition which has a large focal latitude and high sensitivity, particularly in pattern formation which is extremely fine (for example, a line width of 50 nm or less). And a pattern forming method using the same. Further, an object of the present invention is to provide a method of manufacturing an electronic component including the pattern forming method, and an electronic component manufactured by the manufacturing method. [Means for solving the problem]

That is, the present invention is as follows.

[1] A photosensitive ray-sensitive or radiation-sensitive resin composition containing the compound (A), and the compound (A) represented by the following formula (I) is irradiated by actinic rays or radiation. A sulfonic acid is produced. [Chemical 1] In the formula, Rf ₁ and Rf ₂ each independently represent a fluorine atom or a monovalent organic group containing at least one fluorine atom. R ₁ and R ₂ each independently represent a monovalent organic group or a hydrogen atom having no fluorine atom, and R ₃ to R ₅ each independently represent a hydrogen atom or a monovalent organic group. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of R ₃ and a plurality of R ₄ may be the same or different. [2] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [1], wherein the R ₁ and R ₂ represent a hydrogen atom. [3] The sensitized ray-sensitive or radiation-sensitive resin composition according to [1] or [2] wherein R ₅ represents a monovalent organic group having a cyclic structure. [4] The photosensitive ray-sensitive or radiation-sensitive resin composition according to [3], wherein the R ₅ represents a monovalent organic group having a polycyclic cyclic structure. [5] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [4], wherein the R ₅ represents a polycyclic cycloalkyl group. [6] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5] wherein Rf ₁ and Rf ₂ represent a fluorine atom. [7] The sensitized ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6] wherein R ₃ and R ₄ represent a hydrogen atom. [8] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6] wherein at least one of R ₃ and R ₄ represents an alkyl group. [9] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8] wherein n represents 1. [10] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9] wherein the compound (A) is a phosphonium salt. [11] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10] further comprising a resin having a group which decomposes due to an action of an acid and generates a polar group. [12] The photosensitive ray-sensitive or radiation-sensitive resin composition according to [11], wherein the resin having a group decomposed by an action of an acid and generating a polar group is contained by the following formula (AI) Representation of repeating units. [Chemical 2] In the general formula (AI), Xa ₁ represents a hydrogen atom, a methyl group or a group represented by -CH ₂ -R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group. T represents a single bond or a divalent linking group. Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group. Two of Rx ₁ to Rx ₃ may also be bonded to form a cycloalkyl group. [13] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [12], wherein T in the formula (AI) is a single bond, and Rx ₁ , Rx ₂ and Rx ₃ are an alkyl group, and Rx ₁ The sum of the carbon numbers of the alkyl groups represented by Rx ₂ and Rx ₃ is 4 or more, and two or three of Rx ₁ , Rx ₂ and Rx ₃ are not bonded to form a ring. [14] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [11], [12] or [13] wherein the resin having a group which decomposes due to an action of an acid and generates a polar group is contained A resin of a repeating unit represented by the following general formula (1). [Chemical 3] In the formula (1), R ₃₁ represents a hydrogen atom, an alkyl group or a fluorinated alkyl group, R ₃₂ represents an alkyl group, and R ₃₃ represents a monocyclic alicyclic hydrocarbon structure together with a carbon atom to which R ₃₂ is bonded. The required atomic group. The alicyclic hydrocarbon structure may also replace a part of the carbon atoms constituting the ring by a hetero atom or a group having a hetero atom. [15] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [14], wherein the R ₃₂ is an isopropyl group or a tert-butyl group. [16] A pattern forming method, comprising: forming a sensitized ray-sensitive or radiation-sensitive film by the sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [15] a step of exposing the photosensitive ray-sensitive or radiation-sensitive film; and developing the exposed photosensitive ray-sensitive or radiation-sensitive film by a developing solution containing an organic solvent. [17] The pattern forming method according to [16], wherein the exposure is ArF immersion exposure. [18] A method of producing an electronic component, comprising the pattern forming method according to [16] or [17]. [19] An electronic component manufactured by the method of manufacturing an electronic component according to [18]. [Effects of the Invention]

According to the present invention, it is possible to provide a sensitized ray-sensitive or radiation-sensitive resin composition having a large focal latitude and high sensitivity, particularly in extremely fine patterns (for example, a line width of 50 nm or less), and pattern formation using the same method. Further, according to the present invention, a method of manufacturing an electronic component including the pattern forming method, and an electronic component manufactured by the manufacturing method can be provided.

Hereinafter, embodiments of the present invention will be described in detail. Further, in the expression of the group (atomic group) in the present specification, the unsubstituted or unsubstituted expression includes a group having no substituent (atomic group), and also includes a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present invention, "actinic ray" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (Extreme Ultraviolet (EUV) light), and an X-ray. , electron beam, etc. Further, in the present invention, "light" means actinic rays or radiation. The "exposure" in this specification refers to not only exposure by mercury lamps, far ultraviolet rays represented by excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. The depiction made is also included in the exposure.

[Photosensitive ray-sensitive or radiation-sensitive resin composition] The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention is a sensitized ray-sensitive or radiation-sensitive resin composition containing the compound (A), and is made of light. Irradiation of a ray or a radiation produces a sulfonic acid from the compound (A) represented by the formula (I).

Hereinafter, the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention will be described in detail. The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a sensitized ray-sensitive or radiation-sensitive resin composition for ArF exposure, more preferably a sensitized ray-sensitive or radiation-sensitive resin for ArF immersion exposure. Things. The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may be a negative resist composition for developing an organic solvent, or may be a positive resist composition for alkali development, preferably an organic solvent development. A negative resist composition is used. Further, the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention is typically a chemically amplified resist composition.

<Compound (A)> The radiation-sensitive or sensitizing ray-sensitive resin composition of the present invention contains the compound (A), and is represented by the following formula (I) by irradiation with actinic rays or radiation (A). A sulfonic acid (hereinafter also referred to as "photoacid generator (A)") is produced.

[Chemical 4]

Wherein Rf ₁ and Rf ₂ each independently represent a fluorine atom or a monovalent organic group containing at least one fluorine atom. R ₁ and R ₂ each independently represent a monovalent organic group or a hydrogen atom having no fluorine atom, and R ₃ to R ₅ each independently represent a hydrogen atom or a monovalent organic group. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of R ₃ and a plurality of R ₄ may be the same or different.

In the formula (I), Rf ₁ and Rf ₂ each independently represent a fluorine atom or a monovalent organic group containing at least one fluorine atom. As the monovalent organic group containing at least one fluorine atom, an alkyl group substituted with at least one fluorine atom is preferred. The alkyl group in the alkyl group substituted with at least one fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of Rf ₁ and Rf ₂ include a fluorine atom, 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 , CH ₂ CH ₂ C ₄ F ₉ , wherein preferably, it represents a fluorine atom or CF ₃ , and more preferably represents a fluorine atom.

In the formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom. The monovalent organic group having no fluorine atom is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group, a cycloalkyl group or an aryl group, and still more preferably an alkyl group or a cycloalkyl group. R ₁ and R ₂ preferably represent a hydrogen atom, an alkyl group or a cycloalkyl group, and more preferably represent a hydrogen atom.

In the formula (I), R ₃ to R ₅ each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group may, for example, be an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group or a cycloalkyl group, more preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. . The alkyl group, the cycloalkyl group, and the aryl group may have a substituent. The substituent may, for example, be an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group or a ketone group.

R ₃ and R ₄ preferably represent a hydrogen atom. Further, it is also preferred that at least one of R ₃ and R ₄ represents an alkyl group. The alkyl group may have a substituent, and as the substituent, an alkyl group or a cycloalkyl group is preferred.

R ₅ preferably represents a monovalent organic group having a cyclic structure, more preferably a monovalent organic group having a polycyclic cyclic structure, and more preferably a polycyclic cycloalkyl group. The polycyclic cycloalkyl group is preferably a polycyclic cycloalkyl group having 8 to 20 carbon atoms, more preferably an adamantyl group or a bisadamantyl group, and still more preferably an adamantyl group. The polycyclic cycloalkyl group may have a substituent, and examples of the substituent include a hydroxyl group, an alkoxy group (preferably having 1 to 10 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 10 carbon atoms), and a carboxyl group. It is preferably a hydroxyl group or an alkoxy group. The alkoxy group and the alkoxycarbonyl group may further have a substituent. Examples of the further substituent include a cycloalkyl group (preferably having a carbon number of 3 to 12).

Further, neither R ₃ nor R ₄ is bonded to R ₅ to form a ring.

In the formula (I), n represents an integer of 1 or more. n is preferably an integer of 1 or more and 5 or less, more preferably 1 or 2, and still more preferably 1 . When n represents an integer of 2 or more, a plurality of R ₃ and a plurality of R ₄ may be the same or different.

The compound (A) may be an ionic compound or a nonionic compound, preferably an ionic compound, more preferably an onium salt. When the compound (A) is a phosphonium salt, the compound (A) preferably contains a phosphonium cation and an anion. The anion is preferably an anion represented by the following formula (I-1).

[Chemical 5]

In the formula, Rf ₁ and Rf ₂ each independently represent a fluorine atom or a monovalent organic group containing at least one fluorine atom. R ₁ and R ₂ each independently represent a monovalent organic group or a hydrogen atom having no fluorine atom, and R ₃ to R ₅ each independently represent a hydrogen atom or a monovalent organic group. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of R ₃ and a plurality of R ₄ may be the same or different.

Formula (I-1) of _{Rf 1, Rf 2, R 1} ~ R 5 and n have the meanings as in the general formula (I), the Rf _1, Rf _2, the same as R ₁ ~ R ₅ and n, specific examples and The preferred range is also the same.

As the onium cation, for example, a cation (a moiety other than Z ^- ) in the general formula (ZI) or the general formula (ZII) described below can be preferably used.

As a suitable aspect of the compound (A), for example, a compound represented by the following formula (ZI) or formula (ZII) can be mentioned.

[Chemical 6]

In the above formula (ZI), Z ^- represents an anion represented by the above formula (I-1). R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a carbon number of usually 1 to 30, preferably 1 to 20. Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkyl group (for example, a butyl group and a pentyl group).

Examples of the organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having a carbon number of 1 to 10), and a cycloalkyl group ( It is preferably a carbon number of 3 to 15). It is preferred that at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is an aryl group, and more preferably all three are aryl groups. The aryl group may be a heteroaryl group such as a hydrazine residue or a pyrrole residue, in addition to a phenyl group or a naphthyl group.

The aryl group, the alkyl group, and the cycloalkyl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include a halogen atom such as a nitro group or 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). ～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), and an alkoxycarbonyloxy group. The base (preferably having a carbon number of 2 to 7) or the like is not limited to the substituents.

Further, two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. The linking group may, for example, be an alkyl group (preferably having 1 to 3 carbon atoms), -O-, -S-, -CO- or -SO ₂ -, but is not limited to these linking groups. As a preferable structure in which at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group, paragraph 0046 of the Japanese Patent Laid-Open Publication No. 2004-233661, paragraph 0047, and Japanese Patent Laid-Open No. 2003-35948 The compound exemplified by the formula (I-1) to the formula (I-70) in the specification of the U.S. Patent Application Publication No. 2003/0224288A1, the disclosure of which is incorporated herein by reference. The cationic structure of the compound exemplified in the formula (IA-1) to the formula (IA-54) and the formula (IB-1) to the formula (IB-24).

Further preferred examples of the compound represented by the formula (ZI) include the compounds represented by the formula (ZI-3) or (ZI-4) described below. First, the compound represented by the formula (ZI-3) will be described.

[Chemistry 7]

In the general formula (ZI-3), Z ^- represents an anion represented by the above formula (I-1). R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkenyl group. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ₁ and R ₂ , R ₂ and R ₃ may be bonded to each other to form a ring. R _X and R _y each independently represent alkyl, cycloalkyl, alkenyl, aryl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, or alkoxycarbonyl ring alkyl. R _X and R _y may be bonded to each other to form a ring. The ring formed may have an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or a guanamine bond.

The alkyl group as R ₁ is preferably a linear alkyl group or a branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. Specific examples thereof include a linear alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl or n-octadecyl. a branched alkyl group such as isopropyl, isobutyl, tert-butyl, neopentyl or 2-ethylhexyl. The alkyl group of R ₁ may have a substituent, and examples of the alkyl group having a substituent include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, and the like. .

The cycloalkyl group as R ₁ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a sulfur atom in the ring. Specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like. The cycloalkyl group as R ₁ may have a substituent, and examples of the substituent include an alkyl group and an alkoxy group.

The alkoxy group as R ₁ is preferably an alkoxy group having 1 to 20 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, a third butoxy group, a third pentyloxy group, and a n-butoxy group. The alkoxy group as R ₁ may have a substituent, and examples of the substituent include an alkyl group and a cycloalkyl group.

The cycloalkoxy group of R ₁ is preferably a cycloalkyloxy group having 3 to 20 carbon atoms, and examples thereof include a cyclohexyloxy group, a norbornyloxy group, and an adamantyloxy group. The cycloalkoxy group of R ₁ may have a substituent, and examples of the substituent include an alkyl group and a cycloalkyl group.

The aryl group as R ₁ is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a biphenyl group. The aryl group of R ₁ may have a substituent, and examples of preferred substituents include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group, and an arylthio group. When the substituent is an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, the same ones as the alkyl group, the cycloalkyl group, the alkoxy group and the cycloalkoxy group as the above R ₁ may be mentioned.

Examples of the alkenyl group of R ₁ include a vinyl group and an allyl group.

R ₂ and R _{3 each} represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be bonded to each other to form a ring. Here, at least one of R ₂ and R ₃ represents an alkyl group, a cycloalkyl group, or an aryl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group, and the aryl group for R ₂ and R ₃ are the same as those of the specific examples and preferred examples described for R ₁ . When R ₂ and R ₃ are bonded to each other to form a ring, the total number of carbon atoms which contribute to the formation of the ring contained in R ₂ and R ₃ is preferably 4 to 7, particularly preferably 4 or 5.

R ₁ and R ₂ may be bonded to each other to form a ring. When R ₁ and R ₂ are bonded to each other to form a ring, R ₁ is preferably an aryl group (preferably a phenyl group or a naphthyl group which may have a substituent), and R ₂ is an alkylene group having 1 to 4 carbon atoms ( It is preferably a methylene group or an ethyl group. The preferred substituent is the same as the substituent which the aryl group as R ₁ may have. In another embodiment in which R ₁ and R ₂ are bonded to each other to form a ring, R ₁ is a vinyl group and R ₂ is an alkylene group having 1 to 4 carbon atoms.

The alkyl group represented by R _X and R _y is preferably an alkyl group having 1 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a second group. Base, pentyl, neopentyl, hexyl, heptyl, octyl, decyl, decyl, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen , 18 base, 19 base, 20 base, etc.

The cycloalkyl group represented by R _X and R _y is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

The alkenyl group represented by R _X and R _y is preferably an alkenyl group of 2 to 30, and examples thereof include a vinyl group, an allyl group, and a styryl group.

The aryl group represented by R _X and R _y is, for example, preferably an aryl group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and a phenanthrenyl group. Penarenyl, phenanthracenyl, sulfhydryl, fluorenyl, fluorenyl, benzofluorenyl and the like. It is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

The alkyl moiety and the 2-oxo group an alkoxycarbonyl group by group R _X and R _y is represented by, for example, previously reported as R _X and R _y are exemplified.

As the cycloalkyl moiety 2-oxo-cycloalkyl group and an alkoxycarbonyl group by a cycloalkyl group of R _X and R _y is represented by, for example, previously reported as R _X and R _y are exemplified.

A suitable form of the compound represented by the formula (ZI-3) is, for example, a compound represented by the following formula (ZI-3a) and formula (ZI-3b).

[化8]

In the formula (ZI-3a) and the formula (ZI-3b), R ₁ , R ₂ and R ₃ are as defined in the above formula (ZI-3). Further, Z ^- represents an anion represented by the above formula (I-1).

Y represents an oxygen atom, a sulfur atom or a nitrogen atom, preferably an oxygen atom or a nitrogen atom. When Y is a nitrogen atom, t is 1, and when Y is an oxygen atom or a sulfur atom, t is 0, and R ₅ is absent. m, n, p and q represent an integer, preferably 0 to 3, more preferably 1 or 2, and particularly preferably 1. The alkylene group to which S ⁺ and Y are bonded and the alkylene group to which S ⁺ and the carbonyl group are bonded may have a substituent. Preferred examples of the substituent include an alkyl group.

When Y is a nitrogen atom, R ₅ represents a monovalent organic group, and when Y is an oxygen atom or a sulfur atom, R ₅ is absent. R ₅ is preferably (ZI-3a-1) ~ formula (ZI-3a-3) containing a group represented by the group, and particularly preferably an electron withdrawing group represented by the following formula.

[Chemistry 9]

In the formula (ZI-3a-1) to the formula (ZI-3a-3), R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group of R are the same as those of the specific examples and preferred examples described for R _{1 in} the above formula (ZI-3). In the above (ZI-3a-1) to (ZI-3a-3), * represents a bond to be bonded to a nitrogen atom as Y in the compound represented by the formula (ZI-3a).

When Y is a nitrogen atom, R _{5 is} particularly preferably a group represented by -SO ₂ -R ₄ . R ₄ represents an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group of R ₄ are the same as those of the specific examples and preferred examples described for R _{1 in} the formula (ZI-3).

Specific examples of the cationic moiety of the compound represented by the formula (ZI-3) are listed below.

[化10]

[11]

Next, the compound represented by the formula (ZI-4) will be described.

[化12]

In the general formula (ZI-4), Z ^- represents an anion by the general formula (I-1) represented. R ₁₃ represents a hydrogen atom, a fluorine atom, or a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or a cycloalkyl group which may have a substituent. R ₁₄ represents a hydroxyl group, or an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group which may have a substituent. R ₁₅ represents an alkyl group, a cycloalkyl group, or a naphthyl group which may have a substituent. The two R ₁₅ can be the same or different. Two R _{15 groups} may be bonded to each other to form a ring. The formed cyclone may further have a hetero atom in addition to the sulfur atom in the formula. l represents an integer from 0 to 2. r represents an integer from 0 to 8. When r is an integer of 2 or more, a plurality of R ₁₄ may be the same or different.

In the formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched, and preferably has 1 to 10 carbon atoms. Examples of the cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group. The alkoxy group of R ₁₃ and R ₁₄ is linear or branched, and preferably has 1 to 10 carbon atoms. The alkoxycarbonyl group of R ₁₃ and R ₁₄ is linear or branched, and preferably has 2 to 11 carbon atoms. Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent. Specific examples of the alkyl group of the alkylcarbonyl group of R ₁₄ include the same examples as the alkyl group of the above R ₁₃ to R ₁₅ . The alkylsulfonyl group and the cycloalkylsulfonyl group of R ₁₄ are linear, branched or cyclic, and preferably have 1 to 10 carbon atoms.

Examples of the substituent which the respective groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyl group. Oxyl and the like.

Examples of the ring structure in which two R ₁₅ are bonded to each other include a ring of five or six members in which two R ₁₅ are formed together with a sulfur atom in the formula (ZI-4), and particularly preferably 5 The ring of the member (ie, the tetrahydrothiophene ring or the 2,5-dihydrothiophene ring) may also be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent, and examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, and an alkoxycarbonyl group. Alkoxycarbonyloxy group and the like. There may be a plurality of substituents for the ring structure, and in addition, the groups may be bonded to each other to form a ring.

R ₁₅ in the formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, and a divalent group in which two R ₁₅ are bonded to each other and form a tetrahydrothiophene ring structure together with a sulfur atom. Particularly preferably, two R ₁₅ are bonded to each other and together with a sulfur atom form a divalent group of a tetrahydrothiophene ring structure.

The substituent which R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, or an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom). As l, it is preferably 0 or 1, more preferably 1. R is preferably 0 to 2.

Specific examples of the cationic structure of the compound represented by the formula (ZI-3) or the formula (ZI-4) described above, in addition to the above-mentioned Japanese Patent Laid-Open No. 2004-233661, Japanese Patent No. In addition to the cationic structure of the compound and the like exemplified in the specification of the U.S. Patent Application Publication No. 2003/0224288 A1, and the specification of the U.S. Patent Application Publication No. 2003/0077540 A1, for example, Japanese Patent Laid-Open No. 2011-53360 The cationic structure in the chemical structure and the like exemplified in paragraph 0046, paragraph 0047, paragraph 0072 to paragraph 0077, paragraph 0107 to paragraph 0110 of the publication, paragraph 0135 to paragraph 0137, paragraph 0151 of Japanese Patent Laid-Open No. 2011-53430 The cation structure or the like in the chemical structure or the like exemplified in paragraphs 0196 to 0199.

In the general formula (ZII), Z ^- represents an anion represented by the above formula (I-1). R ₂₀₄ and R ₂₀₅ each independently represent an aryl group, an alkyl group or a cycloalkyl group. The aryl group, the alkyl group and the cycloalkyl group as R ₂₀₄ and R _{205 are the same} as the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the above formula (ZI). The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have a substituent. The substituent may be a substituent which the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the above formula (ZI) may have.

The aryl group of R ₂₀₄ and R ₂₀₅ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R ₂₀₄ and R ₂₀₅ 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 skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, anthracene, benzofuran, and benzothiophene.

The alkyl group and the cycloalkyl group of R ₂₀₄ and R ₂₀₅ are preferably a linear alkyl group or a branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group). a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have a substituent. Examples of the substituent which the aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ and R ₂₀₅ have may be an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), or an aryl group. (e.g., carbon number: 6 to 15), alkoxy group (e.g., carbon number: 1 to 15), a halogen atom, a hydroxyl group, a phenylthio group, or the like. Specific examples of the cation of the compound represented by the general formula (ZII) are shown.

[Chemistry 13]

In the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention, the content of the compound (A) is not particularly limited, and is preferably 0.1% by mass to 30% by mass based on the total solid content of the composition. More preferably, it is 3% by mass to 25% by mass, and further preferably 7% by mass to 20% by mass.

Specific examples of the compound (A) are listed below, but are not limited to these specific examples.

[Chemistry 14]

Further, the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may contain only one kind of the compound (A), may contain two or more kinds of the compound (A), and may contain a compound (in addition to the compound (A). A photoacid generator other than A) (hereinafter also referred to as "photoacid generator (A')"). The photoacid generator (A') may be in the form of a low molecular compound or may be in a form incorporated into a part of the polymer. Further, the form of the low molecular compound and the form incorporated into a part of the polymer may be used in combination. When the photoacid generator (A') is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less. When the photoacid generator (A') is in a form incorporated in a part of the polymer, it may be incorporated into a part of the acid-decomposable resin, or may be incorporated into a resin different from the acid-decomposable resin. . In the present invention, the photoacid generator (A') is preferably in the form of a low molecular compound. When the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains two or more kinds of photoacid generators, the total content of the photoacid generator is preferably within the above range.

When the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention contains two or more kinds of the compound (A), the line width Width Roughness (LWR) of the formed pattern becomes smaller. In other words, it is preferred to contain two or more kinds of compounds (A) having the same anionic structure in the general formula (I) and different cationic structures.

As the photoacid generator (A'), a photoinitiator-based photoinitiator, a photoradical polymerization photoinitiator, a dye-based photo-decolorizer, a photochromic agent, or a micro-resistance can be suitably selected. A known compound which produces an acid by irradiation with actinic rays or radiation used in a reagent or the like, and a mixture thereof.

For example, a diazonium salt, an onium salt, a phosphonium salt, a phosphonium salt, a sulfhydryl sulfonate, an oxime sulfonate, a diazodiazine, a diterpene, and an o-nitrobenzyl sulfonate can be mentioned.

Further, a compound obtained by introducing a compound which generates an acid by irradiation with actinic rays or radiation into a main chain or a side chain of a polymer can be used, for example, the specification of U.S. Patent No. 3,849,137 and the specification of German Patent No. 3914407 Japanese Patent Laid-Open No. Sho 63-63, pp., Japanese Patent Laid-Open No. Sho 55-164824, Japanese Patent Laid-Open No. Sho 62-69263, Japanese Patent Laid-Open No. Sho 63-146038, Japanese Patent Laid-Open No. The compound described in Japanese Laid-Open Patent Publication No. SHO-63-153029, and the like.

Further, a compound which generates an acid by light as described in the specification of U.S. Patent No. 3,779,778 and the specification of European Patent No. 126,712 can also be used.

As a preferred photoacid generator (A'), reference is made to paragraphs [0337] to [0400] of US 2012/0076996 A1, the contents of which are incorporated herein by reference.

<Resin having a group which decomposes due to the action of an acid and generates a polar group> The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a group having a group which decomposes due to the action of an acid and generates a polar group. Resin (hereinafter also referred to as "resin (B)" or "acid-decomposable resin"). The resin (B) is typically a resin which increases in polarity due to the action of an acid and which has reduced solubility in a developing solution containing an organic solvent, and which has an increased solubility in an alkaline developing solution due to the action of an acid. Resin. The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may be in the form of a positive or negative sensitizing ray-sensitive or radiation-sensitive resin composition. The resin (B) has a group which decomposes due to the action of an acid and generates a polar group in the main chain or the side chain, or both the main chain and the side chain (hereinafter also referred to as "acid-decomposable group"). The resin (B) preferably contains a repeating unit having an acid-decomposable group.

(1) The repeating unit acid-decomposable group having an acid-decomposable group is preferably a structure having a group-protecting polar group which is decomposed and desorbed by the action of an acid. The polar group may preferably be a carboxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonic acid group or the like. A group which is preferably an acid-decomposable group is a group obtained by substituting a hydrogen atom of the polar group with a group which is desorbed by an acid. Examples of the group which is desorbed by an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ ) (OR ₃₉ ) and so on. In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. R ₀₁ to 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 or a tertiary alkyl ester group. Further preferred is a tertiary alkyl ester group.

The repeating unit having an acid-decomposable group which may be contained in the resin (B) is preferably a repeating unit represented by the following formula (AI).

[化15]

In the general formula (AI), Xa ₁ represents a hydrogen atom, a methyl group or a group represented by -CH ₂ -R ₉ . The methyl group may have a substituent. R ₉ represents a hydroxyl group or a monovalent organic group. The monovalent organic group may, for example, be an alkyl group having 5 or less carbon atoms or a mercapto group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa ₁ preferably represents 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 (straight chain or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group of T include an alkylene group, a —COO—Rt— group, and an —O—Rt— group. 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 1 to 5 carbon atoms, more preferably a -CH ₂ - group or a -(CH ₂ ) ₃ - group. The alkyl group of Rx ₁ to Rx ₃ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms or a polycyclic cycloalkyl group having 7 to 20 carbon atoms. The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms or a polycyclic cycloalkyl group having 7 to 20 carbon atoms. Particularly preferred is a monocyclic cycloalkyl group having 5 to 6 carbon atoms. Preferably, Rx ₁ is methyl or ethyl, and Rx ₂ is bonded to Rx ₃ to form the cycloalkyl group. In one aspect, it is preferred that T in the formula (AI) is a single bond, Rx ₁ , Rx ₂ and Rx ₃ are an alkyl group, more preferably an alkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ The sum of the carbon numbers is 4 or more, more preferably 5 or more, and particularly preferably 6 or more. In this case, two or three of Rx ₁ , Rx ₂ , and Rx ₃ are not bonded to form a ring.

Specific examples of the preferred repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto. In the formula, Xa ₁ represents any of H, CH ₃ , CF ₃ and CH ₂ OH, and Rxa and Rxb each represent a linear or branched alkyl group having 1 to 4 carbon atoms.

[Chemistry 16]

[化17]

The resin (B) is more preferably a resin containing a repeating unit represented by the following formula (1) as a repeating unit represented by the formula (AI).

[化18]

In the formula (1), R ₃₁ represents a hydrogen atom, an alkyl group or a fluorinated alkyl group, R ₃₂ represents an alkyl group, and R ₃₃ represents a monocyclic alicyclic hydrocarbon structure together with a carbon atom to which R ₃₂ is bonded. The required atomic group. The alicyclic hydrocarbon structure may also substitute a part of a carbon atom constituting the ring by a hetero atom or a group having a hetero atom.

R ₃₁ alkyl groups may have a substituent group, examples of the substituent include a fluorine atom, a hydroxyl group and the like. R ₃₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. R _{32 is} preferably an alkyl group having 3 to 10 carbon atoms, more preferably an alkyl group having 4 to 7 carbon atoms. R _{32 is,} for example, a methyl group, an ethyl group, an isopropyl group or a tert-butyl group, preferably an isopropyl group or a third butyl group, more preferably a tert-butyl group. The monocyclic alicyclic hydrocarbon structure in which R _{33 is} formed together with a carbon atom is preferably a 3-membered ring to an 8-membered ring, more preferably a 5-membered ring or a 6-membered ring. In the monocyclic alicyclic hydrocarbon structure in which R _{33 is} formed together with a carbon atom, examples of the hetero atom which may be a part of the carbon atom constituting the ring include an oxygen atom and a sulfur atom. Examples of the hetero atom-containing group include a carbonyl group. Wait. However, the group having a hetero atom is preferably not an ester group (ester bond). The monocyclic alicyclic hydrocarbon structure in which R _{33 is} formed together with a carbon atom is preferably formed only of a carbon atom and a hydrogen atom.

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

[Chemistry 19]

In the general formula (1 '), the same meaning as R ₃₁ and R _32, respectively, in the general formula R (1) ₃₁ and R _32.

Specific examples of the repeating unit having the structure represented by the general formula (1) are listed below, but are not limited to these specific examples.

[Chemistry 20]

The content of the repeating unit having an acid-decomposable group is preferably from 10 mol% to 80 mol%, more preferably from 15 mol% to 80 mol%, relative to all the repeating units in the resin (B), and further Preferably, it is 25 mol% to 70 mol%, particularly preferably 30 mol% to 60 mol%, and most preferably 35 mol% to 60 mol%.

The repeating unit having an acid-decomposable group contained in the resin (B) may be used alone or in combination of two or more. The combination at the time of use is preferably the following. In the following formula, R each independently represents a hydrogen atom or a methyl group.

[Chem. 21]

(2) The repeating unit resin (B) having at least one selected from the group consisting of a lactone group, a sultone group, a hydroxyl group, a cyano group, and an acid group preferably further contains a group selected from a lactone group and a sultone group. a repeating unit of at least one of a hydroxyl group, a cyano group, and an acid group.

The repeating unit having a lactone group or a sultone group which the resin (B) can contain is demonstrated. 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 lactone structure or sultone structure may be used, and a lactone structure or a sultone structure of a 5-membered ring to a 7-membered ring may be used, and preferably. It is a condensed ring of a lactone structure or a sultone structure of a 5-membered to 7-membered ring in the form of a bicyclic structure or a spiro ring structure. More preferably, it contains a lactone structure represented by any one of the following general formulae (LC1-1) to (LC1-17), general formula (SL1-1), and general formula (SL1-2) or A repeating unit of the sultone structure. Alternatively, the lactone structure or the sultone structure can be directly bonded to the backbone. Preferred examples of the lactone structure or the sultone structure are (LC1-1), (LC1-4), (LC1-5), (LC1-8), and more preferably (LC1-4). LWR and development defects become good by using a specific lactone structure or a sultone structure.

[化22]

[化23]

The lactone moiety or the sultone moiety may have a substituent (Rb ₂ ) or may have no substituent (Rb ₂ ). Preferred 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 an alkoxy group having 2 to 8 carbon atoms. A carbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group or the like. More preferably, it is an alkyl group of 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring. The resin (B) preferably contains a repeating unit having a lactone structure or a sultone structure represented by the following formula (III).

[Chem. 24]

paragraph

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, respectively, an alkylene group, a cycloalkyl group, or a combination thereof is independently represented. When a plurality of Z are present, respectively, a single bond, an ether bond, an ester bond, a guanamine bond, or a urethane bond are independently represented.

[化25]

Urea bond

[Chem. 26] .

Here, R each independently 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 group and the cycloalkyl group of R ₀ may have a substituent. Z is preferably an ether bond or an ester bond, and particularly 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, and particularly preferably a methyl group. The alkyl group and the cycloalkyl group of R _{0 and} the alkyl group of R ₇ may be substituted, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a mercapto group, a hydroxyl group, a methoxy group, and the like. An alkoxy group such as an ethoxy group, an isopropoxy group, a tert-butoxy group or a benzyloxy group; an ethoxy group such as an ethoxy group or a propyloxy group. R _{7 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. The preferred chain alkyl group in R ₀ is preferably a chain alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group and an ethyl group. Prolonged propyl and so on. The cycloalkylene group is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, an extended borneol group, and an adenantyl group. In order to exhibit the effects of the present invention, a chain alkyl group is more preferred, and a methylene group is particularly preferred.

The monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure, and specific examples thereof include the above formula (LC1). -1) - a lactone structure or a sultone structure represented by the formula (LC1-17), the formula (SL1-1), and the formula (SL1-2), among which, particularly preferred is (LC1) -4) The structure indicated. Further, it is more preferable that n _{2 in} (LC1-1) to (LC1-17), (SL1-1), and (SL1-2) is 2 or less. Further, R _{8 is} preferably a monovalent organic group having an unsubstituted lactone structure or a sultone structure, or a lactone structure or a sulfone having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. The monovalent organic group of the ester structure is more preferably a monovalent organic group containing a lactone structure (cyanolactone) or a sultone structure (cyanosultone) having a cyano group as a substituent. In the formula (III), n is preferably 0 or 1.

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

[化27]

In the formula (III-1) and the formula (III-1'), R ₇ , A, R ₀ , Z and n have the same meanings as in the above 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 above formula (III), respectively. When a plurality of R ₉ are present, 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 R ₉ groups may be bonded to form a ring. When a plurality of R ₉ ' are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group. When a plurality of R ₉ ' are present, two R ₉ ' may be bonded to form ring. X and X' each independently represent an alkyl group, an oxygen atom or a sulfur atom. m and m' are the number of substituents, and each independently represents an integer of 0 to 5. m and m' are preferably independently 0 or 1 respectively.

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 the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. These substituents may have a substituent, and examples of the substituent include a hydroxyl group such as a hydroxyl group such as a methoxy group such as a methoxy group or an ethoxy group, a cyano group or a fluorine atom. R ₉ and R ₉ ' are more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and further preferably a cyano group. Examples of the alkylene group of X and X' include a methylene group and an ethylidene group. X and X' are preferably an oxygen atom or a methylene group, more preferably a methylene group. When m and m' are 1 or more, it is preferred that at least one of R ₉ and R ₉ ' is substituted at the α-position or the β-position of the carbonyl group of the lactone, and particularly preferably at the α-position.

Specific examples of the repeating unit having a lactone structure or a sultone structure represented by the general formula (III-1) or the general formula (III-1') include Japanese Patent Laid-Open Publication No. 2013-178370 The structure described in paragraphs [0150] to [0151] of the publication.

With respect to the content of the repeating unit represented by the formula (III), when it is contained in a plurality, it is preferably 15 mol% to 60 mol%, more preferably, based on all the repeating units in the resin (B). 20 mol% to 60 mol%, further preferably 30 mol% to 50 mol%. Further, the resin (B) may contain a repeating unit having the lactone structure or the sultone structure in addition to the unit represented by the formula (III).

The repeating unit having a lactone group or a sultone group usually has an optical isomer, and any optical isomer can be used. Further, one optical isomer may be used alone, or a plurality of optical isomers may be used in combination. When an optical isomer is mainly used, its optical purity (enantiomeric excess (ee)) is preferably 90% or more, more preferably 95% or more. With respect to the content of the repeating unit having a lactone structure or a sultone structure other than the repeating unit represented by the general formula (III), when it is contained in a plurality, it is preferably, in total, with respect to all the repeating units in the resin. 15 mol% to 60 mol%, more preferably 20 mol% to 50 mol%, further preferably 30 mol% to 50 mol%. In order to enhance the effect of the present invention, two or more lactone or sultone repeating units selected from the group (III) may be used in combination. When it is used in combination, it is preferred to select two or more kinds of lactone or sultone repeating units in which n is 0 in the general formula (III).

The resin (B) preferably contains a repeating unit having a hydroxyl group or a cyano group other than the general formula (AI). Thereby, the substrate adhesion and the developer affinity are 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. Examples of the repeating unit having such a structure include repeating units represented by the following formula (AIIa) to formula (AIId).

[化28]

In the general formula (AIIa) to the general 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 each independently represent a hydrogen atom, a hydroxyl group or a cyano group. Wherein at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group, and the remainder is a hydrogen atom. More preferably, two of R ₂ c to R ₄ c are a hydroxyl group, and the remainder is a hydrogen atom.

The content 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%, still more preferably 10, based on all the repeating units in the resin (B). Mol% ~ 25 mol%.

Specific examples of the repeating unit having a hydroxyl group or a cyano group are listed below, but the present invention is not limited to these specific examples.

[化29]

The resin (B) preferably contains a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonylamino group, a sulfonyl fluorenylene group, a bis-sulfonyl fluorenylene group, and an aliphatic alcohol substituted with an α-position electron-donating group (for example, hexafluoroisopropanol group). More preferably, it contains a repeating unit having a carboxyl group. By containing a repeating unit having an acid group, the resolution in the use of the contact hole is increased. The repeating unit having an acid group is preferably a repeating unit in which an acid group is directly bonded to a main chain of the resin as a repeating unit formed of acrylic acid or methacrylic acid, or a main chain of the resin via a linking group. a repeating unit having an acid group bonded thereto, and a polymerization initiator or a chain transfer agent having an acid group for introducing into the terminal of the polymer chain, and the linking group may have a monocyclic or polycyclic ring. Cyclic hydrocarbon structure. Particularly preferred is a repeating unit formed of acrylic acid or methacrylic acid.

The content of the repeating unit having an acid group is preferably from 0 mol% to 20 mol%, more preferably from 3 mol% to 15 mol%, still more preferably 5 mol%, based on all the repeating units in the resin (B). ~10 mol%.

Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto. In a specific example, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

[化30]

As the repeating unit having at least one selected from the group consisting of a lactone group, a hydroxyl group, a cyano group, and an acid group, it is further preferred to have a repeating unit selected from at least two of a lactone group, a hydroxyl group, a cyano group, and an acid group. It is preferably a repeating unit having a cyano group and a lactone group. Particularly preferred is a repeating unit having a structure in which a lactone structure of the above (LCI-4) is substituted with a cyano group.

(3) Repeating unit having an alicyclic hydrocarbon structure and exhibiting no acid decomposition property The resin (B) may further contain a repeating unit having an alicyclic hydrocarbon structure and exhibiting no acid decomposition property. Thereby, the elution of the low molecular component from the resist film into the liquid immersion liquid can be reduced during the immersion exposure. Examples of such a repeating unit include 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, and (meth)acrylic acid. A repeating unit formed by cyclohexyl ester or the like.

(4) Recurring unit having no hydroxyl group or cyano group The resin (B) of the present invention preferably further contains any one having no hydroxyl group or cyano group and represented by the formula (III) unit.

[化31]

paragraph

In the general formula (III), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no hydroxyl group or cyano group. Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group.

The cyclic structure of R ₅ may include a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) and a cycloalkenyl group having 3 to 12 carbon atoms.

The polycyclic hydrocarbon group includes a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. Further, the crosslinked cyclic hydrocarbon ring also contains, for example, a fused ring in which a plurality of 5-membered cycloalkane rings to 8 membered cycloalkane rings are condensed. Preferred examples of the crosslinked cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctyl group, and a tricyclo[5.2.1.0 ^2,6 ]decyl group. As a more preferable crosslinked cyclic hydrocarbon ring, a norbornyl group and an adamantyl group are mentioned.

The alicyclic hydrocarbon group may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a protecting group-protected hydroxyl group, a protecting group-protected amine group, and the like. Preferred examples of the halogen atom include a bromine atom, a chlorine atom and a fluorine atom. Preferred examples of the alkyl group include a methyl group, an ethyl group, a butyl group and a tert-butyl group. The alkyl group may further have a substituent, and examples of the substituent which may be further provided include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amine group protected by a protective group.

Examples of the protective group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms. Examples of a preferred substituted methyl group include a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, and a third. Butoxymethyl, 2-methoxyethoxymethyl, as a preferred substituted ethyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl, as Examples of the preferred mercapto group include an aliphatic fluorenyl group having 1 to 6 carbon atoms such as a mercapto group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl sulfonyl group, an isobutyl fluorenyl group, a pentamidine group, and a trimethyl ethane group. The carbonyl group may, for example, be an alkoxycarbonyl group having 1 to 4 carbon atoms.

The content of the repeating unit represented by the formula (III) is preferably from 0 mol% to 40 mol% with respect to all the repeating units in the resin (B), without any of a hydroxyl group and a cyano group. More preferably, it is 0% by mole to 20% by mole. Specific examples of the repeating unit represented by the general formula (III) are listed below, but the present invention is not limited to these specific examples. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[化32]

The resin (B) may also contain a repeating unit represented by the following formula (nI) or formula (nII).

[化33]

In the formula (nI) and the formula (nII), R ₁₃ ' to R ₁₆ ' independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group or an alkane. An oxycarbonyl group, an alkylcarbonyl group, a group having a lactone structure, or a group having an acid-decomposable group. X ₁ and X ₂ each independently represent a methylene group, an ethyl group, an oxygen atom or a sulfur atom. n represents an integer of 0 to 2.

Examples of the acid-decomposable group in the group having an acid-decomposable group of R ₁₃ ' to R ₁₆ ' include a cumyl ester group, an enol ester group, an acetal ester group, and a tertiary alkyl ester group. A tertiary alkyl ester group represented by -C(=O)-OR ₀ . In the formula, examples of R ₀ include a tertiary alkyl group such as a third butyl group and a third pentyl group, an isobornyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, and a 1-isobutoxy group. Ethyl, 1-cyclohexyloxyethyl, etc. 1-alkoxyethyl, 1-methoxymethyl, 1-ethoxymethyl, etc. alkoxymethyl, 3-oxoalkyl, tetra Hydropyranyl, tetrahydrofuranyl, trialkyldecyl ester, 3-oxocyclohexyl ester, 2-methyl-2-adamantyl, mevalonate residues, and the like. Among R ₁₃ ' to R ₁₆ ', at least one of them is preferably a group having an acid-decomposable group. Examples of the halogen atom in R ₁₃ ' to R ₁₆ ' include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. The alkyl group of R ₁₃ ' to R ₁₆ ' is more preferably a group represented by the following formula (F1).

[化34]

In the formula (F1), R ₅₀ to R ₅₅ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. Wherein at least one of R ₅₀ to R ₅₅ represents an alkyl group in which a fluorine atom or at least one hydrogen atom is substituted with a fluorine atom. Rx represents a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, a decyl group or an alkoxycarbonyl group), preferably a hydrogen atom. R ₅₀ to R _{55 are} preferably all fluorine atoms.

The following specific examples are given as the repeating unit represented by the above formula (nI) or the formula (nII), but the present invention is not limited to these compounds. Among them, a repeating unit represented by (II-f-16) to (II-f-19) is preferred.

[化35]

[化36]

[化37]

[化38]

[39]

[化40]

[化41]

In addition to the repeating structural unit, in order to adjust the dry etching resistance or the standard developer suitability, the substrate adhesion, the resist profile, and the resolving power, heat resistance, sensitivity, etc. which are generally necessary characteristics of the resist The resin (B) may contain various repeating structural units.

Examples of such a repeating structural unit include repeating structural units corresponding to the following monomeric bodies, but are not limited to these repeating structural units.

Thereby, the properties required for the resin (B), in particular, the following properties can be finely adjusted: (1) solubility in a coating solvent, (2) film forming property (glass transition temperature), (3) Alkali developability, (4) film thinning (hydrophobicity, alkali-soluble group selection), (5) adhesion of the unexposed portion to the substrate, and (6) dry etching resistance.

Examples of such a monovalent body include acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. A compound having one addition polymerizable unsaturated bond or the like.

In addition, if it is an addition polymerizable unsaturated compound copolymerizable with the monomer of the various repeating structural unit, it can copolymerize.

In the resin (B), in order to adjust the dry etching resistance or standard developer suitability of the resist, the substrate adhesion, the resist profile, and the resolving power and heat resistance as a general necessary property of the resist And sensitivity, etc., and it is suitable to set the molar ratio of each repeating structural unit.

When the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is used for ArF exposure, the resin (B) preferably does not have an aromatic group from the viewpoint of transparency of ArF light. Further, from the viewpoint of compatibility with a hydrophobic resin to be described later, the resin (B) preferably has no fluorine atom or ruthenium atom.

As the resin (B), a resin in which all repeating units contain a (meth) acrylate-based repeating unit is preferred. In this case, it is possible to use a resin in which all repeating units are methacrylate-based repeating units, all repeating units are acrylate-based repeating units, and all repeating units are composed of methacrylate-based repeating units and acrylate-based repeating units. Any resin of the formed resin, but preferably the acrylate-based repeating unit is 50 mol% or less of all the repeating units. More preferably, the (meth)acrylate-based repeating unit having an acid-decomposable group represented by the general formula (AI) is 20% by mole to 50% by mole, and a (meth)acrylate having a lactone group Repeating unit 20% by mole to 50% by mole, (meth)acrylate-based repeating unit having an alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group, 5 mol% to 30 mol%, and other (methyl) Acrylate-based repeating unit 0% by mole to 20% by mole of copolymerized polymer.

When the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light (EUV or the like) having a wavelength of 50 nm or less, the resin (B) is preferably In addition to the repeating unit represented by the general formula (AI), a hydroxystyrene-based repeating unit is further contained. Further, it is preferably an acid-decomposable repeating unit such as a hydroxystyrene-based repeating unit and a hydroxystyrene-based repeating unit protected by an acid-decomposing group or a tertiary alkyl (meth)acrylate.

Preferred repeating units having an acid-decomposable group include, for example, a third butoxycarbonyloxystyrene, a 1-alkoxyethoxystyrene, or a tertiary alkyl (meth)acrylate. The repeating unit or the like is more preferably a repeating unit formed of 2-alkyl-2-adamantyl (meth)acrylate and dialkyl (1-adamantyl)methyl (meth)acrylate.

The resin (B) can be synthesized according to a conventional method such as radical polymerization. For example, as a general synthesis method, a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and then heated to carry out polymerization is used, and the monomer species and the initiator are used for 1 hour to 10 hours. The dropwise addition of the solution to the heating solvent, etc., is preferably a dropwise addition polymerization method. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, and ketones such as methyl ethyl ketone and methyl isobutyl ketone, such as ethyl acetate. A solvent, a guanamine solvent such as dimethylformamide or dimethylacetamide, and a sensitizing ray of the present invention dissolved as described later with propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or cyclohexanone Or a solvent that senses the radioactive resin composition. More preferably, it is preferably polymerized using the same solvent as that used in the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation of particles during storage can be suppressed. The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. The polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.) 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. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), and the like. The initiator is added in an additional step or in a stepwise manner, and after completion of the reaction, it is introduced into a solvent, and the desired polymer is recovered by a method such as powder recovery 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. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, and more preferably from 60 ° C to 100 ° C.

The weight average molecular weight of the resin (B) is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000, more preferably in terms of polystyrene equivalent by gel permeation chromatography (GPC). It is 3,000 to 15,000, and particularly preferably 3,000 to 11,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance or dry etching resistance can be prevented, and deterioration of developability or viscosity can be prevented, and film formability can be deteriorated.

In the present invention, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (Mw/Mn) of the resin are measured by GPC (solvent: tetrahydrofuran, column: manufactured by Tosoh Corporation). TSK gel Multipore HXL-M, column temperature: 40 ° C, flow rate: 1.0 mL / min, detector: RI) is defined by the polystyrene conversion value.

The degree of dispersion (molecular weight distribution) is usually from 1 to 3, preferably from 1 to 2.6, more preferably from 1 to 2, particularly preferably from 1.4 to 1.7. The smaller the molecular weight distribution, the more excellent the resolution and the resist shape.

In the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention, the amount of the resin (B) in the entire composition is preferably 50% by mass to 99% by mass, more preferably 60% by total solid content. Mass% to 95% by mass. Further, in the present invention, the resin (B) may be used alone or in combination of two or more.

Specific examples of the resin (B) are shown below, but are not limited to these specific examples.

[化42]

<Hydrophobic Resin (HR)> The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a hydrophobic resin. Further, the hydrophobic resin is preferably different from the resin (B). The hydrophobic resin is preferably designed to be present in a biased manner at the interface. However, unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule, and it is not helpful to uniformly mix the polar substance/nonpolar substance. Examples of the effect of adding the hydrophobic resin include controlling the static/dynamic contact angle with respect to water on the surface of the resist film, improving the liquid immersion compliance, and suppressing outgas.

In view of the fact that the hydrophobic resin is present in the surface layer of the film, the hydrophobic resin preferably has at least one of a "fluorine atom", a "deuterium atom", and a "CH ₃ partial structure contained in a side chain portion of the resin". It is preferable to have two or more types. When the hydrophobic resin contains a fluorine atom and/or a ruthenium atom, the fluorine atom and/or the ruthenium atom in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin contains a fluorine atom, it is preferably a resin having a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group, or a fluorine atom-containing aryl group as a partial structure containing a fluorine atom. The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear alkyl group or a branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may further have a fluorine atom. Substituents other than the substituents. The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may further have a substituent other than a fluorine atom. The aryl group containing a fluorine atom may be substituted with a fluorine atom by at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group, and may further have a substituent other than a fluorine atom.

The alkyl group containing a fluorine atom, the cycloalkyl group containing a fluorine atom, and the aryl group containing a fluorine atom are preferably a group represented by the following formula (F2) to formula (F4), but The invention is not limited to this.

[化43]

In the general formulae (F2) to (F4), R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight chain or branched). Wherein 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 each independently represent a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably, It has a carbon number of 1 to 4). Preferably, R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are each a fluorine atom. R ₆₂ , R ₆₃ and R _{68 are} preferably an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom (preferably having 1 to 4 carbon atoms), and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. 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 a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-bis(trifluoromethyl)phenyl group. Specific examples of the group represented by the general formula (F3) include those exemplified in US 2012/0251948 A1 [0500]. 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, -CH(CF ₃ )OH or the like, preferably -C(CF ₃ ) ₂ OH. The partial structure containing a fluorine atom may be directly bonded to the main chain, and further, may be selected from an alkyl group, a phenyl group, an ether bond, a thioether bond, a carbonyl group, an ester bond, a guanamine bond, or an amide group. A group in a group consisting of an ester bond and a urea-based bond, or a combination of two or more of these groups, is bonded to the main chain.

The hydrophobic resin may also contain a ruthenium atom. It is preferably a resin having an alkyl fluorenyl group structure (preferably a trialkyl decyl group) or a cyclic siloxane structure as a partial structure containing a ruthenium atom. The partial structure and the like described in paragraphs [0304] to [0307] of JP-A-2013-178370 can be cited as the alkyl fluorenyl structure or the cyclic oxime structure. Examples of the repeating unit having a fluorine atom or a ruthenium atom are exemplified in US 2012/0251948 A1 [0519].

Further, as described above, it is also preferred that the hydrophobic resin contains a CH ₃ moiety structure in the side chain portion. Here, the partial structure in a side chain CH ₃ partially hydrophobic resin contained (hereinafter, also referred to as "partial structure a side chain CH ₃ ') contains a partial structure CH ₃ ethyl, propyl and the like contained. On the other hand, a methyl group directly bonded to the main chain of the hydrophobic resin (for example, an α-methyl group having a repeating unit of a methacrylic acid structure) is biased toward the surface of the hydrophobic resin due to the influence of the main chain. The contribution is small, and thus is set to be not included in the CH ₃ partial structure in the present invention.

More specifically, the hydrophobic resin is derived from a repeating unit of a monomer having a polymerizable moiety having a carbon-carbon double bond, for example, a repeating unit represented by the following general formula (M), and R ₁₁ to When R ₁₄ is CH ₃ "self", the CH _{3 is} not included in the CH ₃ moiety structure contained in the side chain moiety in the present invention. On the other hand, the CH ₃ partial structure existing from the CC main chain via some atoms is set to correspond to the CH ₃ partial structure in the present invention. For example, when R ₁₁ is ethyl (CH ₂ CH ₃ ), it is assumed to have "one" CH ₃ partial structure in the present invention.

[化44]

In the above formula (M), R ₁₁ to R ₁₄ each independently represent a side chain moiety. Examples of R ₁₁ to R ₁₄ as a side chain moiety include a hydrogen atom and a monovalent organic group. Examples of the monovalent organic group of R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, and an alkylaminocarbonyl group. And a cycloalkylaminocarbonyl group, an arylaminocarbonyl group or the like, and the groups may further have a substituent.

The hydrophobic resin is preferably a resin having a repeating unit having a CH ₃ partial structure in a side chain portion, more preferably a repeating unit represented by the following formula (II), and a formula (III) At least one repeating unit (x) of the indicated repeating units is taken as such a repeating unit.

Hereinafter, the repeating unit represented by the general formula (II) will be described in detail.

[化45]

In the above formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₂ represents an organic group having one or more CH ₃ partial structures and being stable to an acid. More specifically, the organic group which is stable to the acid is preferably an organic group which does not have the "acid-decomposable group" described in the resin (B).

The alkyl group of X _b1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a methyl group is preferable. X _b1 is preferably a hydrogen atom or a methyl group. Examples of R ₂ include an alkyl group having at least one CH ₃ partial structure, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group may further have an alkyl group as a substituent. R _{2 is} preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures. The organic group having one or more CH ₃ partial structures of R ₂ and being stable to an acid preferably has two or more and ten or less CH ₃ partial structures, more preferably two or more and eight or less. The structure of the CH ₃ part. Preferred specific examples of the repeating unit represented by the formula (II) are listed below. Furthermore, the present invention is not limited to this.

[Chem. 46]

The repeating unit represented by the general formula (II) is preferably a (non-acid-decomposable) repeating unit which is stable to an acid, and specifically, preferably does not have a decomposition due to an action of an acid and generates a polar group. The repeating unit of the base. Hereinafter, the repeating unit represented by the general formula (III) will be described in detail.

[化47]

paragraph

In the above formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₃ represents an organic group having one or more CH ₃ partial structures and being stable to an acid. n represents an integer of 1 to 5. The alkyl group of X _b2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a hydrogen atom is preferred. X _{b2 is} preferably a hydrogen atom. R ₃ is an organic group which is stable to an acid, and more specifically, it is preferably an organic group which does not have the "acid-decomposable group" described in the resin (B).

Examples of R ₃ include an alkyl group having one or more CH ₃ partial structures. The organic group having one or more CH ₃ partial structures of R ₃ and being stable to an acid preferably has one or more and ten or less CH ₃ partial structures, and more preferably one or more and eight or less. Further, the CH ₃ partial structure preferably further has one or more and four or less CH ₃ partial structures. n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

Preferred specific examples of the repeating unit represented by the formula (III) are listed below. Furthermore, the present invention is not limited to this.

[48]

The repeating unit represented by the formula (III) is preferably a (non-acid-decomposable) repeating unit which is stable to an acid, and specifically, preferably does not have a decomposition due to an action of an acid and generates a polar group. The repeating unit of the base.

When the hydrophobic resin contains a CH ₃ partial structure in a side chain portion, and further, particularly when there is no fluorine atom or a ruthenium atom, the repeating unit represented by the general formula (II), with respect to all the repeating units of the hydrophobic resin, The content of at least one repeating unit (x) in the repeating unit represented by the formula (III) is preferably 90 mol% or more, more preferably 95 mol% or more. The content is usually 100 mol% or less with respect to all the repeating units of the hydrophobic resin.

The hydrophobic resin contains at least one of 90 mol% or more of the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III), with respect to all the repeating units of the hydrophobic resin. Repeating unit (x), the surface free energy of the hydrophobic resin is increased. As a result, it is difficult for the hydrophobic resin to be biased toward the surface of the resist film, and the static/dynamic contact angle of the resist film with respect to water can be surely improved, and the liquid immersion liquid followability can be improved.

Further, the hydrophobic resin may have at least one selected from the group consisting of (i) containing a fluorine atom and/or a ruthenium atom, and (ii) a side chain moiety having a CH ₃ moiety structure. ) to the base in the group of (z) below. (x) an acid group, (y) a group having a lactone structure or a sultone structure, an acid anhydride group, or a quinone imine group, (z) a group decomposed by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamino group, a sulfonyl fluorenylene group, or an alkyl sulfonyl group. Methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indolyl, bis(alkylsulfonyl) a methylene group, a bis(alkylsulfonyl) fluorenylene group, a tris(alkylcarbonyl)methylene group, a tris(alkylsulfonyl)methylene group, and the like. Preferred examples of the acid group include a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, and a bis(alkylcarbonyl)methylene group.

Examples of the repeating unit having an acid group (x) include a repeating unit in which an acid group is directly bonded to a main chain of the resin, such as a repeating unit formed of acrylic acid or methacrylic acid, or a resin via a linking group. A repeating unit or the like having an acid group bonded to the main chain may be further introduced into the end of the polymer chain by using a polymerization initiator having an acid group or a chain transfer agent during polymerization, and any of them is preferred. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a germanium atom. The content of the repeating unit having an acid group (x) is preferably from 1 mol% to 50 mol%, more preferably from 3 mol% to 35 mol%, relative to all repeating units in the hydrophobic resin. Good is 5% by mole to 20% by mole. Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

[化49]

[化50]

As the group having a lactone structure or a sultone structure, an acid anhydride group, or a quinone imine group (y), a group having a lactone structure or a sultone structure is particularly preferable. The repeating unit containing these groups is, for example, a repeating unit in which the group is directly bonded to the main chain of the resin, such as a repeating unit formed of acrylate or methacrylate. Alternatively, the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced to the end of the resin by using a polymerization initiator or a chain transfer agent having the group at the time of polymerization. The repeating unit containing a group having a lactone structure may, for example, be the same as the repeating unit having a lactone structure or a sultone structure described in the previous resin (B).

The content of the repeating unit containing a group having a lactone structure or a sultone structure, an acid anhydride group, or a quinone group is preferably from 1 mol% to 100 mol% based on all repeating units in the hydrophobic resin. More preferably, it is 3 mol% to 98 mol%, and further preferably 5 mol% to 95 mol%.

The repeating unit having a group (z) which is decomposed by the action of an acid in the hydrophobic resin is the same as the repeating unit having an acid-decomposable group exemplified in the resin (B). The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a germanium atom. The content of the repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin is preferably from 1 mol% to 80 mol%, more preferably 10, based on all the repeating units in the hydrophobic resin. Molar% to 80% by mole, and more preferably 20% by mole to 60% by mole. The hydrophobic resin may further contain a repeating unit represented by the following formula (III).

[化51]

In the paragraph

In the general formula (III), R _c31 represents a hydrogen atom, an alkyl group (which may be substituted by a fluorine atom or the like), a cyano group or a -CH ₂ -O-Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. R _{c31 is} preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly 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. These groups may be substituted by a group containing a fluorine atom or a halogen atom. L _c3 represents a single bond or a divalent linking group.

The alkyl group of R _c32 in the formula (III) is preferably a linear alkyl group having 3 to 20 carbon atoms or a branched alkyl group. The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms. 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 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and 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 ether bond, a phenylene group or an ester bond (a group represented by -COO-).

The content of the repeating unit represented by the formula (III) is preferably from 1 mol% to 100 mol%, more preferably from 10 mol% to 90 mol%, based on all the repeating units in the hydrophobic resin. Further preferably, it is 30 mol% to 70 mol%. The hydrophobic resin preferably further contains a repeating unit represented by the following formula (CII-AB).

[化52]

In the formula (CII-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 containing two carbon atoms (CC) bonded and forming an alicyclic structure.

The content of the repeating unit represented by the general formula (CII-AB) is preferably from 1 mol% to 100 mol%, more preferably from 10 mol% to 90 mol, based on all the repeating units in the hydrophobic resin. Ear %, further preferably 30% by mole to 70% by mole.

Specific examples of the repeating unit represented by the general formula (III) and the general formula (CII-AB) are listed below, but the present invention is not limited to these specific examples. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

[化53]

When the hydrophobic resin contains a fluorine atom, the content of the fluorine atom is preferably from 5% by mass to 80% by mass, and more preferably from 10% by mass to 80% by mass based on the weight average molecular weight of the hydrophobic resin. Further, among all the repeating units contained in the hydrophobic resin, the repeating unit containing a fluorine atom is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%. When the hydrophobic resin contains a ruthenium atom, the content of the ruthenium atom is preferably from 2% by mass to 50% by mass, and more preferably from 2% by mass to 30% by mass based on the weight average molecular weight of the hydrophobic resin. Further, among all the repeating units contained in the hydrophobic resin, the repeating unit containing a halogen atom is preferably from 10 mol% to 100 mol%, more preferably from 20 mol% to 100 mol%.

On the other hand, in particular, when the hydrophobic resin contains a CH ₃ moiety structure in the side chain portion, it is also preferred that the hydrophobic resin has substantially no fluorine atom or ruthenium atom, and in this case, specifically, The content of the repeating unit containing a fluorine atom or a ruthenium atom in all the repeating units in the hydrophobic resin is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, and is preferably It is 0% by mole, that is, no fluorine atom or germanium atom. Further, the hydrophobic resin preferably contains substantially only a repeating unit containing only an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, in all the repeating units of the hydrophobic resin, the repeating unit containing only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is preferably 95 mol% or more, more preferably It is 97 mol% or more, further preferably 99 mol or more, and desirably 100 mol%.

The standard polystyrene-equivalent weight average molecular weight of the hydrophobic resin is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 15,000. Further, the hydrophobic resin 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 contain a hydrophobic resin or may not contain a hydrophobic resin, and when it contains a hydrophobic resin, the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention The content of the total solid content in the composition of the hydrophobic resin in the composition is preferably from 0.01% by mass to 10% by mass, more preferably from 0.05% by mass to 8% by mass, even more preferably from 0.1% by mass to 7% by mass.

The amount of impurities such as the metal of the hydrophobic resin is naturally small, and the residual monomer or oligomer component is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass, still more preferably 0.05% by mass to ～ 1% by mass. Thereby, a composition which does not have a foreign matter in the liquid or does not have a change in sensitivity or the like with time can be obtained. Further, the molecular weight distribution (Mw/Mn, also referred to as dispersion degree) is preferably in the range of 1 to 5, from the viewpoints of the resolution, the resist shape, the side wall of the resist pattern, the roughness, and the like. It is 1 to 3, and more preferably in the range of 1 to 2.

The hydrophobic resin can also be used in various commercial products, and can also be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a batch polymerization method in which a monomer species and a starter are dissolved in a solvent and heated to carry out polymerization is used, and the monomer species and the start are carried out for 1 hour to 10 hours. The solution of the agent is added dropwise to a dropping polymerization method or the like in a heating solvent, and preferably a dropping polymerization method. The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.), and the purification method after the reaction are the same as those described in the resin (B), but in the synthesis of the hydrophobic resin, the concentration of the reaction is preferred. It is 30% by mass to 50% by mass. Specific examples of the hydrophobic resin are shown below. Moreover, the molar ratio (corresponding to each repeating unit from the left side), the weight average molecular weight, and the dispersion degree of the repeating unit in each resin are shown in the following table.

[54]

[化55]

[Table 1]

[化56]

[化57]

[Table 2]

<Acid Diffusion Control Agent> The sensitized ray or radiation sensitive resin composition of the present invention preferably further contains an acid diffusion controlling agent. The acid diffusion controlling agent captures an acid generated from a photoacid generator or the like at the time of exposure, and suppresses the reaction of the acid-decomposable resin (resin (B)) in the unexposed portion caused by the excess acid generated. The agent (quencher) works. As the acid diffusion controlling agent, a basic compound; a low molecular compound having a nitrogen atom and having a group which is desorbed by an action of an acid; and a basic compound which is reduced or disappeared by irradiation with actinic rays or radiation; Or, for a photoacid generator, it becomes a weakly acidic phosphonium salt.

The basic compound is preferably a compound having a structure represented by the following general formula (A) to formula (E).

[化58]

In the general formula (A) and the general formula (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may 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. Preferably, the carbon number is 3 to 20) or the aryl group (carbon number is 6 to 20), and here, 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 be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

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 groups in the general formula (A) and the general formula (E) are more preferably unsubstituted.

Preferred examples of the compound include anthracene, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. Further preferred examples include compounds. 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, an alkylamine derivative having a hydroxyl group and/or an ether bond, An aniline derivative of a hydroxyl group and/or an ether bond. Specific examples of preferred compounds include the compounds exemplified in US 2012/0219913 A1 [0379]. Further, preferred examples of the basic compound include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group.

The amine compound may be a primary, secondary or tertiary amine compound, preferably an amine compound having at least one alkyl group bonded to a nitrogen atom. The amine compound is more preferably a tertiary amine compound. The amine compound is a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (preferably, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. The carbon number 6 to 12) may also be bonded to the nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain to form an alkyloxy group. The number of the oxyalkylene groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxyalkylene groups, an oxy-ethyl group (-CH ₂ CH ₂ O-) or an oxy-propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. Further preferably, the oxy group is an 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. The ammonium salt compound is preferably a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. It can also be bonded to a nitrogen atom for a carbon number of 6 to 12). The ammonium salt compound preferably has an oxygen atom in the alkyl chain to form an alkyloxy group. The number of the oxyalkylene groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxyalkylene groups, an oxy-ethyl group (-CH ₂ CH ₂ O-) or an oxy-propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. Further preferably, the oxy group is an ethyl group.

The anion of the ammonium salt compound may, for example, be a halogen atom, a sulfonate, a borate or a phosphate. Among them, a halogen atom or a sulfonate is preferred. Further, the following compounds are also preferred as the basic compound.

[化59]

As the basic compound, in addition to the above-mentioned compound, Japanese Patent Laid-Open Publication No. 2011-22560 [0180] to [0225], Japanese Patent Laid-Open Publication No. 2012-137735 (0218) to [0219], and international publication may be used. The compound or the like described in the manual WO2011/158687A1 [0416] to [0438]. These basic compounds 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 contain a basic compound or may not contain a basic compound. When a basic compound is contained, the content of the basic compound is based on the solid content of the composition. It is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass. The ratio of use of the photoacid generator (including the photoacid generator (A')) and the basic compound in the composition is preferably a photoacid generator/basic compound (mole ratio) = 2.5 to 300. In other words, in terms of the sensitivity and the resolution, it is preferable that the molar amount is 2.5 or more, and the decrease in the resolution due to the coarseness of the resist pattern caused by the elapse of time after the post-exposure heat treatment is suppressed. Preferably, it is 300 or less. The photoacid generator/basic compound (mole ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

A low molecular compound having a nitrogen atom and having a group which is desorbed by an action of an acid (hereinafter also referred to as "compound (C)") is preferably an amine derivative having a group which is desorbed by an action of an acid on a nitrogen atom. Things. The group which is detached by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiminal ether group. Carbamate group, half amine acetal ether group. The molecular weight of the compound (C) is preferably from 100 to 1,000, more preferably from 100 to 700, particularly preferably from 100 to 500. The compound (C) may also have a carbamate group having a protective group on a nitrogen atom. The protective group constituting the urethane group can be represented by the following formula (d-1).

[60]

In the formula (d-1), R _b each independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 10), a cycloalkyl group (preferably having a carbon number of 3 to 30), or an aryl group. It is preferably a carbon number of 3 to 30), an aralkyl group (preferably having a carbon number of 1 to 10), or an alkoxyalkyl group (preferably having a carbon number of 1 to 10). R _b may be bonded to each other to form a ring. The alkyl group, cycloalkyl group, aryl group or aralkyl group represented by R _b may be a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, a pendant oxy group, or the like, an alkoxy group, Halogen atom substitution. The same is true for the alkoxyalkyl group represented by R _b .

R _{b is} preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group. More preferably, it is a linear or branched alkyl group or a cycloalkyl group. Examples of the ring formed by linking two R _{b to} each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof. The specific structure of the group represented by the general formula (d-1) includes the structure disclosed in US 2012/0135348 A1 [0466], but is not limited thereto.

The compound (C) is particularly preferably one having a structure represented by the following formula (6).

[化61]

In the formula (6), R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two R _a may be the same or different, and two R _a may be bonded to each other and form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula. The meaning of R _{b is the} same as R _b in the above formula (d-1), and preferred examples are also the same. l represents an integer of 0 to 2, and m represents an integer of 1 to 3, and satisfies l+m=3. In the general formula (6), R _a is a alkyl, cycloalkyl, aryl, aralkyl groups may be substituted with the following groups, which groups may be substituted with a alkyl group of R _b, cycloalkyl, aryl The groups described in the aralkyl group are the same.

Specific examples of the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group of the R _a (the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group may be substituted by the group) may be exemplified The same group as the specific example described for R _b . Specifically, the particularly preferred compound (C) in the present invention is shown, but the present invention is not limited thereto.

[化62]

[化63]

The compound represented by the formula (6) can be synthesized in accordance with JP-A-2007-298569, JP-A-2009-199021, and the like. In the present invention, the compound (C) may be used alone or in combination of two or more. The content of the compound (C) in the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 0.001% by mass to 20% by mass, and more preferably 0.001% by mass, based on the total solid content of the composition. ～10% by mass, and more preferably 0.01% by mass to 5% by mass.

A basic compound (hereinafter also referred to as "compound (PA)") which is reduced or disappeared by irradiation with actinic rays or radiation is a compound having a proton-receptive functional group and having actinic rays It is decomposed by irradiation of radiation, and produces a compound in which the proton acceptor declines or disappears, or changes from proton acceptor to acid.

The term "proton acceptor functional group" refers to a functional group having a group or an electron which can electrostatically interact with a proton, and for example, a functional group having a macrocyclic structure such as a cyclic polyether, or having a non-helpful π total A functional group of a nitrogen atom of a non-shared electron pair of a yoke. The nitrogen atom having an unshared electron pair which does not contribute to π conjugate is, for example, a nitrogen atom having a partial structure represented by the following formula.

[化64] Non-shared electronic pair

Preferred examples of the partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary amine to a tertiary amine, a pyridine, an imidazole, and a pyrazine structure.

The compound (PA) is decomposed by irradiation with actinic rays or radiation to cause a compound having a decrease or disappearance of proton acceptor or a change from proton acceptor to acid. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acidity means a change in proton acceptor property due to the addition of a proton in the proton acceptor functional group, specifically It means that when a proton-addition product is formed from a compound (PA) having a proton-receptive functional group and a proton, the equilibrium constant in the chemical equilibrium is reduced. Proton acceptability can be confirmed by performing pH measurement.

In the present invention, the acid dissociation constant pKa of the compound which is produced by decomposition of the compound (PA) by actinic radiation or radiation preferably satisfies pKa<-1, more preferably -13<pKa<-1, and further It is preferably -13 < pKa < -3.

In the present invention, the acid dissociation constant pKa is expressed as an acid dissociation constant pKa in an aqueous solution, and is described, for example, in Chemical Fact (II) (Revised 4th Edition, 1993, edited by Nippon Chemical Society, Maruzen Co., Ltd.). The lower the value, the greater the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C using an infinitely diluted aqueous solution, and the following software package 1 can also be used to calculate The value of the database based on Hammett's substituent constants and well-known literature values. The values of pKa described in the present specification both indicate values obtained by calculation using the software package.

Software Package 1: Advanced Chemistry Development (ACD/Labs) Solaris System Software Version 8.14 (Software V8.14 for Solaris) (1994-2007 ACD/Labs).

The compound (PA) produces, for example, the proton adduct which is produced by decomposition of a compound represented by the following formula (PA-1) by irradiation with actinic rays or radiation. The compound represented by the formula (PA-1) is a compound having a proton acceptor functional group and an acidic group, and the proton acceptor is decreased, disappeared, or self-protonated compared with the compound (PA). The body changes to acidity.

[化65]

In the formula (PA-1), Q represents -SO ₃ H, -CO ₂ H, or -W ₁ NHW ₂ R _f . Here, R _f represents an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), W ₁ and W. ₂ independently represents -SO ₂ - or -CO-. A represents a single bond or a divalent linking group. X represents -SO ₂ - or -CO-. n represents 0 or 1. B represents a single bond, an oxygen atom, or -N(R _x )R _y -. Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x may be bonded to R _y to form a ring, or may be bonded to R to form a ring. R represents a monovalent organic group having a proton acceptor functional group.

The general formula (PA-1) will be described in more detail. The divalent linking group in A is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferably, it is an alkylene group having at least one fluorine atom, preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. The alkyl group may have a linking group such as an oxygen atom or a sulfur atom. In particular, the alkylene group is preferably an alkylene group substituted by a fluorine atom in an amount of from 30% to 100% of the number of hydrogen atoms, and more preferably a carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferred, and a perfluoroextended ethyl group, a perfluoroextended propyl group, or a perfluorobutylene group is more preferred.

The monovalent organic group in R _x is preferably an organic group having 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent. The alkyl group in R _x may have a substituent, preferably a linear alkyl group having 1 to 20 carbon atoms and a branched alkyl group, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. The cycloalkyl group in R _x may have a substituent, preferably a monocyclic cycloalkyl group having a carbon number of 3 to 20 or a polycyclic cycloalkyl group, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the ring. The aryl group in R _x may have a substituent, and preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. The aralkyl group in R _x may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group. The alkenyl group in R _x may have a substituent, and may be linear or branched. The alkenyl group preferably has 3 to 20 carbon atoms. Examples of such an alkenyl group include a vinyl group, an allyl group, and a styryl group.

Examples of the substituent when R _x further has a substituent include a halogen atom, a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aryl group, a decyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. , amidyl, cyano, carboxy, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, heterocyclooxy, decyloxy, amine, nitro, fluorenyl and heterocyclic Wait.

The divalent organic group in R _y is preferably an alkylene group. Examples of the ring structure in which R _x and R _y can be bonded to each other include a ring of 5 to 10 members containing a nitrogen atom, and particularly preferably a ring of 6 members.

The proton acceptor functional group in R may be a group having a nitrogen-containing heterocyclic aromatic structure such as azacrown ether, primary amine to tertiary amine, pyridine or imidazole, as described above. The organic group having such a structure is preferably an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, and preferably an organic group having 4 to 30 carbon atoms.

a proton acceptor functional group in R or an alkyl group containing an ammonium group, a cycloalkyl group, an aryl group, an arylalkyl group, an alkyl group in a alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group which are the same as the above R _x are the same.

When B is -N(R _x )R _y -, it is preferred that R and R _x are bonded to each other to form a ring. By forming a ring structure, stability is improved, and the storage stability of the composition using the same is improved. The number of carbon atoms forming the ring is preferably from 4 to 20, and may be a monocyclic ring or a polycyclic ring, and may contain an oxygen atom, a sulfur atom or a nitrogen atom in the ring. Examples of the one-ring structure include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring containing a nitrogen atom. The polycyclic structure includes a structure including a combination of two or more monocyclic structures.

As -W ₁ NHW ₂ R _f represented by Q is R _f, is preferably an alkyl group having a carbon number of fluorine atom may be 1 to 6, further preferably a carbon number of a perfluoroalkyl group having 1 to 6. Further, as W ₁ and W ₂ , at least one of them is preferably -SO ₂ -, and more preferably both W ₁ and W ₂ are -SO ₂ -. From the viewpoint of the hydrophilicity of the acid group, Q is particularly preferably -SO ₃ H or -CO ₂ H. The compound in which the Q site of the compound represented by the formula (PA-1) is a sulfonic acid can be synthesized by using a general sulfoximation reaction. For example, it can be obtained by reacting one sulfonium halide moiety of the bis sulfonium halide compound with an amine compound to form a sulfonamide bond, and then hydrolyzing another sulfonium halide moiety. Or a method of reacting a cyclic sulfonic anhydride with an amine compound to cause ring opening.

The compound (PA) is preferably an ionic compound. The proton acceptor functional group may be contained in any of the anion portion and the cation portion, but is preferably contained in the anion site. The compound (PA) is preferably a compound represented by the following formula (4) to formula (6).

[化66]

In the general formulae (4) to (6), the meanings of A, X, n, B, R, R _f , W ₁ and W ₂ and A, X, n, B in the formula (PA-1) , R, R _f , W ₁ and W _{2 are the} same. [C] ⁺ represents a counter cation. As the counter cation, a phosphonium cation is preferred. More specifically, the phosphonium cation described as S ⁺ (R ₂₀₁ )(R ₂₀₂ )(R ₂₀₃ ) in the general formula (ZI), and I ⁺ (R ₂₀₄ in the general formula (ZII)) can be cited. The phosphonium cation described by (R ₂₀₅ ) is a preferred example. Specific examples of the compound (PA) include the compounds exemplified in US2011/0269072A1 [0280].

Further, in the present invention, a compound (PA) other than the compound which produces the compound represented by the formula (PA-1) can be suitably selected. For example, a compound having a proton acceptor moiety in the cation moiety as an ionic compound can also be used. More specifically, a compound represented by the following formula (7) or the like can be given.

[67]

In the formula, A represents a sulfur atom or an iodine atom. m represents 1 or 2, and n represents 1 or 2. Wherein, when A is a sulfur atom, m+n=3, and when A is an iodine atom, m+n=2. R represents an aryl group. R _N represents an aryl group substituted with a proton acceptor functional group. X ^- represents a counter anion. Specific examples of X ^- may be the same as those of the photoacid generator (A). Specific examples of the aryl group of R and R _N include a phenyl group.

Specific examples of the proton acceptor functional group possessed by R _N are the same as the proton acceptor functional group described in the above formula (PA-1). Hereinafter, specific examples of the ionic compound having a proton acceptor moiety in the cation moiety include the compounds exemplified in US2011/0269072A1 [0291]. In addition, such a compound can be synthesized by, for example, the method described in JP-A-2007-230913 and JP-A-2009-122623.

The compound (PA) may be used alone or in combination of two or more. The content of the compound (PA) is preferably from 0.1% by mass to 10% by mass, and more preferably from 1% by mass to 8% by mass based on the total solid content of the composition.

In the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention, a sulfonium salt which is relatively weakly acidic for a photoacid generator can be used as an acid diffusion controlling agent. When a photoacid generator is used in combination with a sulfonium salt which produces an acid which is relatively weakly acidic to an acid generated from a photoacid generator, the photoacid generator is irradiated by actinic radiation or radiation. The acid produced in the reaction with the unreacted sulfonium salt having a weak acid anion releases a weak acid by salt exchange and produces a sulfonium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid having a lower catalytic activity, so that in the appearance, the acid is deactivated and the acid diffusion can be controlled.

The onium salt which is relatively weakly acidic to the photoacid generator is preferably a compound represented by the following formula (d1-1) to formula (d1-3).

[化68]

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (wherein a fluorine atom is not substituted on the carbon adjacent to S), R ⁵² In the organic group, Y ³ is a linear, branched or cyclic alkyl or aryl group, Rf is a hydrocarbon group containing a fluorine atom, and M ^{+ is} independently a ruthenium or osmium cation.

Preferable examples of the phosphonium cation or the phosphonium cation represented by M ⁺ include a phosphonium cation in the above formula (ZI) and a phosphonium cation in the above formula (ZII).

A preferred example of the anion portion of the compound represented by the formula (d1-1) is a structure exemplified in paragraph [0198] of JP-A-2012-242799. A preferred example of the anion portion of the compound represented by the formula (d1-2) is a structure exemplified in paragraph [0201] of JP-A-2012-242799. Preferred examples of the anion portion of the compound represented by the formula (d1-3) include those exemplified in paragraph [0209] and paragraph [0210] of JP-A-2012-242799.

The onium salt which is relatively weakly acidic with respect to the photoacid generator may be (C) a compound having a cationic site and an anion site in the same molecule, and the cationic site and the anion site are linked by a covalent bond (hereinafter, Also known as "salt salt (C)"). The onium salt (C) is preferably a compound represented by any one of the following formula (C-1) to formula (C-3).

[化69]

In the general formulae (C-1) to (c-3), R ₁ , R ₂ and R ₃ represent a substituent having 1 or more carbon atoms. L ₁ represents a divalent linking group or a single bond linking a cationic moiety to an anionic moiety. -X ^- represents an anion moiety selected from the group consisting of -COO ^- , -SO ₃ ^- , -SO ₂ ^- , -N ^- -R ₄ . R ₄ represents a carbonyl group at a point of attachment to an adjacent N atom: -C(=O)-, sulfonyl group: -S(=O) ₂ -, sulfinylene group: -S(=O)- A monovalent substituent. R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. Further, in (C-3), two of R ₁ to R ₃ may be bonded to form a double bond with the N atom.

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, and an alkylaminocarbonyl group. A cycloalkylaminocarbonyl group, an arylaminocarbonyl group or the like. Preferred are an alkyl group, a cycloalkyl group, and an aryl group.

The L _{1 which is a} divalent linking group may, for example, be a linear alkyl group or a branched alkyl group, a cycloalkyl group, an extended aryl group, a carbonyl group, an ether bond, an ester bond, a guanamine bond or a urethane. A bond, a urea bond, and a combination of two or more of these. L _{1 is more} preferably an alkyl group, an aryl group, an ether bond, an ester bond, or a combination of two or more of these. Preferred examples of the compound represented by the formula (C-1) include paragraphs [0037] to [0039] of JP-A-2013-6827, and JP-A-2013-8020. The compound exemplified in paragraph [0027] to paragraph [0029]. Preferred examples of the compound represented by the formula (C-2) include the compounds exemplified in paragraphs [0012] to [0013] of JP-A-2012-189977. Preferred examples of the compound represented by the formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP-A-2012-252124.

The content of the cerium salt which is relatively weakly acidic with respect to the photoacid generator is preferably from 0.5% by mass to 10.0% by mass, more preferably from 0.5% by mass to 8.0% by mass, based on the solid content of the composition. Preferably, it is 1.0% by mass to 8.0% by mass.

<Solvent> The solvent to be used in the preparation of the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention by dissolving the above components may, for example, be an alkyl diol monoalkyl ether carboxylate or a stretch. Alkyl glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having a carbon number of 4 to 10), a monoketone compound (preferably carbon) which may contain a ring An organic solvent such as 4 to 10), an alkylene carbonate, an alkyl alkoxyacetate or an alkyl pyruvate.

As the alkylene glycol monoalkyl ether carboxylate, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate is preferably exemplified. , propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate. The alkylene glycol monoalkyl ether is preferably exemplified by propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

Examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate, and butyl lactate. As the alkyl alkoxypropionate, for example, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-methoxy Ethyl propyl propionate.

As the cyclic lactone, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, and β-methyl-γ-butane are preferably exemplified. Ester, γ-valerolactone, γ-caprolactone, γ-octanolactone, α-hydroxy-γ-butyrolactone.

Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, 3,3-dimethyl-2-butanone, 2-pentanone, and 3-pentanone. 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl 3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3- Heptone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone , 2-fluorenone, 3-fluorenone, 5-fluorenone, 2-nonanone, 3-fluorenone, 4-fluorenone, 5-hexen-2-one, 3-penten-2-one, ring Pentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-three Methylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone.

As the alkylene carbonate, for example, propylene carbonate, ethylene carbonate, ethyl carbonate, and butyl carbonate are preferable. As the alkyl alkoxyacetate, for example, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, and 2-(2-ethoxyethoxy)acetic acid acetate are preferably exemplified. Ester, 3-methoxy-3-methylbutyl acetate, 1-methoxy-2-propyl acetate. Examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate. The solvent which can be preferably used is a solvent having a boiling point of 130 ° C or higher at normal temperature and normal pressure. Specific examples thereof include cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and ethyl 3-ethoxypropionate. Ethyl pyruvate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, and propyl carbonate. In the present invention, the solvent may be used singly or in combination of two or more.

In the present invention, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group in the structure can be used as the organic solvent. The solvent containing a hydroxyl group and a solvent containing no hydroxyl group can be appropriately selected from the above-exemplified compounds. The solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether or an alkyl lactate, more preferably propylene glycol. Monomethyl ether, ethyl lactate. Further, as the solvent containing no hydroxyl group, an alkylene glycol monoalkyl ether acetate, an alkyl alkoxypropionate, a monoketone compound which may contain a ring, a cyclic lactone, an alkyl acetate is preferable. Ester, etc., among them, particularly preferred are propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, preferably propylene glycol Monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone. The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent containing 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. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferable.

The solvent is preferably a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate. More preferably, it is a mixed solvent containing at least propylene glycol monomethyl ether acetate and cyclohexanone, or a mixed solvent containing at least propylene glycol monomethyl ether acetate and γ-butyrolactone. Particularly preferred is a mixed solvent of at least three solvents of propylene glycol monomethyl ether acetate, cyclohexanone, and γ-butyrolactone. The solid content concentration of the radiation sensitive or sensitizing ray resin composition of the present invention is preferably from 1% by mass to 40% by mass, more preferably from 1% by mass to 30% by mass, even more preferably from 3% by mass to 20% by mass. %.

<Interacting Agent> The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a surfactant. When a surfactant is contained, it is preferable to contain a fluorine-based surfactant and/or a lanthanoid surfactant (a fluorine-based surfactant, a lanthanoid surfactant, and a surfactant containing both a fluorine atom and a ruthenium atom) Any one or two or more.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains the surfactant, and when an exposure light source of 250 nm or less, particularly 220 nm or less is used, sensitivity, resolution, and adhesion are provided. A resist pattern with less development defects. Examples of the fluorine-based surfactant and/or the lanthanum-based surfactant include the surfactants described in [0276] of the specification of the U.S. Patent Application Publication No. 2008/0248425, for example, Eftop EF301, EF303. (New Akita Chemicals Co., Ltd.), Fluorad FC430, 431, 4430 (manufactured by Sumitomo 3M), Megafac F171, F173, F176, F189, F113, F110 , F177, F120, R08 (made by Di Love (DIC) (share)), Surflon S-382, SC101, 102, 103, 104, 105, 106 (made by Asahi Glass (share)), Toli (Troysol) S-366 (manufactured by Troy Chemical), GF-300, GF-150 (manufactured by East Asia Synthetic Chemicals Co., Ltd.), Surflon S-393 (Seimi Chemical) Manufacturing), Eftop EF121, EF122A, EF122B, EF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Mitsubishi Materials Electronics (Jemco), PF636, PF656, PF6320, PF6520 (Union) (OMNOVA) Manufacturing), FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (Ni Ousi (Neos) (NR)) and the like. Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a lanthanoid surfactant.

Further, as the surfactant, in addition to the known surfactants as described above, the following surfactants may be used, which are utilized by a short-chain polymerization method (also referred to as a short-chain polymer method). Or a fluoroaliphatic group-derived polymer derived from a fluoroaliphatic compound produced by an oligomerization method (also referred to as an oligomer method). The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991. As the polymer having a fluoroaliphatic group, a monomer having a fluoroaliphatic group and (poly(oxyalkylene))acrylate and/or (poly(oxyalkylene))methacrylate are preferred. The copolymer can be subjected to block copolymerization even if it is irregularly distributed. Further, examples of the poly(oxyalkylene) group include a poly(oxyethylidene) group, a poly(oxypropyl) group, a poly(oxybutylene) group, and the like, and may also be, for example, poly(( a block-linked structure in which an oxy-ethyl group is bonded to an oxy-propyl group and an oxy-ethyl group, or a block-connected polymer having a poly(oxyethyl group and an oxy-propyl group) has a chain length different in the same chain length. An alkyl-like unit. Further, the copolymer of a monomer having a fluoroaliphatic group and a poly(oxyalkylene) acrylate (or methacrylate) may be not only a binary copolymer but also two or more different fluorines. A ternary system or more copolymer obtained by simultaneously copolymerizing an aliphatic group-based monomer or two or more different poly(oxyalkylene) acrylates (or methacrylates).

For example, as a commercially available surfactant, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Di Ai Sheng (share)), having a C ₆ F ₁₃ group can be cited. An interpolymer of acrylate (or methacrylate) with (poly(oxyalkylene)) acrylate (or methacrylate) having a C ₃ F ₇ group of acrylate (or methacrylate) and A copolymer of poly(oxyethyl)ethyl acrylate (or methacrylate) and (poly(oxypropyl)) acrylate (or methacrylate).

Further, in the present invention, a surfactant other than the fluorine-based surfactant and/or the lanthanoid surfactant described in [0280] of the specification of the US Patent Application Publication No. 2008/0248425 may be used.

These surfactants can be used singly or in combination of several types. The radiation sensitive or sensitizing ray resin composition of the present invention may contain a surfactant or may not contain a surfactant, and when it contains a surfactant, it is relative to the total solid of the sensitized ray-sensitive or radiation-sensitive resin composition. The content of the component (the total amount other than the solvent), the content of the surfactant is preferably 0.0001% by mass to 2% by mass, more preferably 0.0001% by mass to 2% by mass, even more preferably 0.0005% by mass to 1% by mass.

<Dissolution preventing compound having a molecular weight of 3,000 or less which is decomposed by the action of an acid and having an increased solubility in an alkaline developing solution> The molecular weight which is decomposed by the action of an acid and which has an increased solubility in an alkaline developing solution is 3000. The following dissolution preventing compound (hereinafter also referred to as "dissolution preventing compound") is preferably such as "Proceeding of SPIE", 2724, 355 in order not to lower the permeability at 220 nm or less. An alicyclic compound or an aliphatic compound containing an acid-decomposable group, such as a cholic acid derivative containing an acid-decomposable group, as described in (1996). The acid-decomposable group or the alicyclic structure may be the same as the acid-decomposable group or the alicyclic structure described in the resin (B).

Further, when the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is exposed by a KrF excimer laser or the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with an electron beam, The dissolution preventing compound is preferably a structure containing a phenolic hydroxyl group substituted with a phenol compound by an acid decomposition group. The phenol compound preferably contains one to nine phenol skeletons, and more preferably contains two to six phenol skeletons.

The amount of the dissolution preventing compound added is preferably from 3% by mass to 50% by mass, and more preferably from 5% by mass to 40% by mass based on the solid content of the composition.

Specific examples of the dissolution preventing compound are shown below, but the present invention is not limited to these specific examples.

[化70]

[71]

<Other Additives> The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a dye, a plasticizer, a photosensitizer, a light absorbing agent, and a solubility promoting effect on the developer, if necessary. A compound (for example, a phenol compound having a molecular weight of 1,000 or less, an alicyclic compound having a carboxyl group or an aliphatic compound) or the like.

Such a phenolic compound having a molecular weight of 1,000 or less can be referred to, for example, a method described in Japanese Patent Application Laid-Open No. Hei-4-122938, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei. Easy to synthesize. Specific examples of the alicyclic compound having a carboxyl group or an aliphatic compound include a carboxylic acid derivative having a steroid structure such as cholic acid, deoxycholic acid or lithocholic acid, an adamantanecarboxylic acid derivative, and adamantane II. The carboxylic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, etc. are not limited to these compounds.

[Pattern Forming Method] Next, a pattern forming method of the present invention will be described. The pattern forming method of the present invention includes at least: (1) a step of forming a sensitized ray-sensitive or radiation-sensitive film using a sensitizing ray-sensitive or radiation-sensitive resin composition; (2) a sensitizing sensation or a feeling a step of exposing the radiation film; and (3) developing the exposed photosensitive radiation or radiation sensitive film with a developing solution containing an organic solvent.

The exposure in the step (2) may be a liquid immersion exposure. The pattern forming method of the present invention preferably comprises (4) a heating step after (2) the exposing step. The pattern forming method of the present invention may include a plurality of (2) exposure steps. The pattern forming method of the present invention may include a plurality of (4) heating steps.

The photosensitive ray-sensitive or radiation-sensitive linear film of the present invention is formed by using the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention, and more specifically, preferably by sensitizing the present invention. A film formed by coating a radiation or radiation sensitive resin composition on a substrate. In the pattern forming method of the present invention, the step of forming a film (photosensitive ray or radiation sensitive film) on the substrate, the step of exposing the film, and the developing step can be carried out by a generally known method. .

It is also preferred to include a pre-heating step (PB: Prebake) after film formation and before the exposure step. Further, it is also preferred to include a post-exposure heating step (PEB: Post Exposure Bake) after the exposure step and before the development step. PB and PEB are preferably carried out at a heating temperature of 70 ° C to 130 ° C, more preferably at 80 ° C to 120 ° C. The heating time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, and still more preferably from 30 seconds to 90 seconds. The heating can be carried out by a device provided in a usual exposure/developer, or by using a hot plate or the like. The reaction of the exposed portion is promoted by baking, and the sensitivity or pattern outline is improved.

The wavelength of the light source used in the exposure apparatus of the present invention is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., and preferably wavelengths of 250 nm or less. Far-ultraviolet light, more preferably far-ultraviolet light with a wavelength below 220 nm, especially far-ultraviolet light with a wavelength of 1 nm to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser ( 193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., preferably KrF excimer laser, ArF excimer laser, EUV or electron beam, preferably It is an ArF excimer laser.

Further, a liquid immersion exposure method can be applied in the step of performing exposure in the present invention. The liquid immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a deformation illumination method.

When immersion exposure is performed, the step of washing the surface of the film with a water-based chemical solution may be performed after (A) forming a film on the substrate and before performing the exposure, and/or (B) may be performed by liquid immersion. After the step of exposing the film to the film, the step of washing the surface of the film with the aqueous solution is performed before the step of heating the film. The liquid immersion liquid is preferably transparent to the exposure wavelength, and in order to minimize the deformation of the optical image projected on the film, the temperature coefficient of the refractive index is as small as possible, especially when the exposure light source is an ArF excimer. In the case of the emission (wavelength: 193 nm), in addition to the above viewpoints, water is preferably used from the viewpoints of easiness of obtaining, ease of handling, and the like. When water is used, it is also possible to add an additive (liquid) which reduces the surface tension of water and increases the interfacial activity in a minute ratio. Preferably, the additive does not dissolve the resist layer on the wafer and may ignore the effects on the optical coating on the lower surface of the lens element. As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples thereof include methanol, ethanol, and isopropyl alcohol. By adding an alcohol having a refractive index substantially equal to that of water, it is possible to obtain an advantage that the refractive index change of the entire liquid can be minimized even if the concentration of the alcohol component in the water evaporates to cause a change in the concentration.

On the other hand, when a substance which is opaque to light of 193 nm or an impurity whose refractive index is different from that of water is mixed, deformation of an optical image projected on the resist is caused, and therefore, as water to be used, Distilled water is preferred. Further, pure water filtered by an ion exchange filter or the like can also be used. The electric resistance of the water used as the liquid immersion liquid is preferably 18.3 M?cm or more, and the TOC (organic matter concentration) is desirably 20 ppb or less, and desirably, the degassing treatment is performed.

In addition, the lithographic performance can be improved by increasing the refractive index of the liquid immersion liquid. From this point of view, an additive such as a refractive index-increasing additive may be added to water or heavy water (D ₂ O) may be used instead of water.

The resist film formed by using the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention at a temperature of 23 ° C ± 3 ° C and a humidity of 45% ± 5% has a receding contact angle of 70 or more, and is suitable for passage via The exposure of the liquid immersion medium is preferably 75 or more, more preferably 75 to 85.

If the receding contact angle is too small, it is not suitable for exposure by a liquid immersion medium, and the effect of reducing water mark (watermark) defects cannot be sufficiently exhibited. In order to achieve a preferred receding contact angle, it is preferred to contain the hydrophobic resin (HR) in the sensitized ray- or radioactive composition. Alternatively, a liquid immersion liquid poorly soluble film (hereinafter also referred to as "top coat layer") formed of the hydrophobic resin (HR) may be provided on the upper layer of the resist film. The function required for the top coat layer is coating suitability to the upper layer portion of the resist film, and poor solubility of the liquid immersion liquid. The top coat layer is preferably not mixed with the composition film, and can be uniformly applied to the upper layer of the composition film. Specifically, examples of the top coat layer include a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, a ruthenium-containing polymer, a fluorine-containing polymer, and the like. In the viewpoint that the impurities are eluted from the top coat layer into the liquid immersion liquid, the optical lens is contaminated, it is preferred that the polymer contained in the top coat layer has a small residual monomer component.

When the top coat is peeled off, a developer may be used, and a release agent may also be used. As the release agent, a solvent having a small penetration into the film is preferred. In view of the fact that the stripping step can be carried out simultaneously with the development step of the film, it is preferably peeled off by a developing solution containing an organic solvent. The absence of a difference in refractive index between the top coat and the liquid immersion liquid increases the resolution. When water is used as the liquid immersion liquid, the top coat layer preferably has a refractive index close to that of the liquid immersion liquid. From the viewpoint of bringing the refractive index close to the liquid immersion liquid, it is preferred to contain a fluorine atom in the top coat layer. Further, from the viewpoint of transparency and refractive index, a film is preferred. The top coat layer is preferably not mixed with the film and is not mixed with the liquid immersion liquid. From this point of view, when the liquid immersion liquid is water, the solvent used in 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 A water-insoluble medium. Further, when the liquid immersion liquid is an organic solvent, the top coat layer may be water-soluble or may be water-insoluble. Hereinafter, the top coat composition for forming the top coat layer will be described.

The solvent used in the top coat composition in the present invention is preferably an organic solvent. More preferably, it is an alcohol solvent. When the solvent is an organic solvent, it is preferably a solvent which does not dissolve the resist film. As the solvent which can be used, an alcohol solvent, a fluorine solvent or a hydrocarbon solvent is preferably used, and a non-fluorine alcohol solvent is more preferably used. The alcohol solvent is preferably a primary alcohol from the viewpoint of coatability, and more preferably a primary alcohol having 4 to 8 carbon atoms. As the primary alcohol having 4 to 8 carbon atoms, a linear, branched or cyclic alcohol can be used, and examples thereof include 1-butanol, 1-hexanol, 1-pentanol and 3-methyl-. 1-butanol, 2-ethylbutanol, perfluorobutyltetrahydrofuran, and the like. Further, as the resin for the top coat composition, a resin having an acidic group described in JP-A-2009-134177 and JP-A-2009-91798 can be preferably used. The weight average molecular weight of the water-soluble resin is not particularly limited, but is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 500,000, and particularly preferably from 10,000 to 100,000. Here, the weight average molecular weight of the resin means a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-Methyl-2-Pyrrolidone (NMP)).

The pH of the top coat composition is not particularly limited, but is preferably 0 to 10, more preferably 0 to 8, and particularly preferably 1 to 7.

The concentration of the resin in the top coat composition is preferably from 0.1% by mass to 10% by mass, more preferably from 0.2% by mass to 5% by mass, even more preferably from 0.3% by mass to 3% by mass. The top coat material may contain a component other than the resin, but the proportion of the resin in the solid content of the top coat composition is preferably 80% by mass to 100% by mass, and more preferably 90% by mass to 100% by mass. The mass% is particularly preferably from 95% by mass to 100% by mass. The solid content concentration of the top coat composition in the present invention is preferably from 0.1 to 10, more preferably from 0.2 to 6% by mass, still more preferably from 0.3 to 5% by mass. By setting the solid content concentration to the above range, the top coat composition can be uniformly applied onto the resist film.

In the pattern forming method of the present invention, the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention can be used to form a sensitized ray-sensitive or radiation-sensitive film (typically a resist film) on a substrate, and A top coat layer is formed on the resist film using the top coat composition. The film thickness of the resist film is preferably 10 nm to 100 nm, and the film thickness of the top coat layer is preferably 10 nm to 200 nm, more preferably 20 nm to 100 nm, and particularly preferably 40 nm to 80 nm. . As a method of applying a sensitizing ray-sensitive or radiation-sensitive resin composition on a substrate, spin coating is preferred, and the number of revolutions is preferably from 1,000 rpm to 3,000 rpm. For example, a photosensitive ray-sensitive or radiation-sensitive resin composition is applied to a substrate such as a substrate for precision integrated circuit component by an appropriate coating method such as a spinner or a coater (for example: 矽/二The ruthenium oxide coating is applied and dried to form a resist film. Further, a known anti-reflection film may be applied in advance. Further, it is preferred to dry the resist film before forming the top coat layer. Then, the top coat composition can be applied onto the obtained resist film by the same method as the formation of the resist film, and dried to form a top coat layer. The resist film having the top coat layer on the upper layer is usually irradiated with actinic rays or radiation through a mask, preferably baked (heated), and developed. Thereby, a good pattern can be obtained.

In the immersion exposure step, the liquid immersion liquid is required to follow the action of scanning the exposure head on the wafer at a high speed to form an exposure pattern, thereby moving on the wafer, so that the liquid immersion liquid in the dynamic state is for the resist film. The contact angle becomes important, and the resist is required to have no residual liquid droplets and follow the high-speed scanning performance of the exposure head.

In the present invention, the substrate on which the film is formed is not particularly limited, and an inorganic substrate such as ruthenium, SiN, SiO ₂ or TiN, a coated inorganic substrate such as spin-on glass (SOG), or the like can be used. The manufacturing steps, the manufacturing steps of the circuit substrate such as a liquid crystal or a thermal head, and the substrate generally used in the lithography step of other photosensitive etching processes. Further, an antireflection film may be formed between the resist film and the substrate as needed. As the antireflection film, a known organic or inorganic antireflection film can be suitably used.

The developing solution used in the step of developing the resist film formed using the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is not particularly limited, and for example, an alkaline developing solution or an organic solvent-containing material can be used. Developer (hereinafter also referred to as organic developer).

When the pattern forming method of the present invention has a step of performing development using an alkaline developing solution, the alkaline developing solution which can be used is not particularly limited, and an aqueous solution of 2.38 mass% of tetramethylammonium hydroxide is usually preferable. Further, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution for use. 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. As the eluent in the rinsing treatment after the alkali development, pure water may be used, and an appropriate amount of a surfactant may be added and used. In addition to the above, as the alkaline developing solution, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine can be used. Secondary amines such as ethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine, tetraethylammonium hydroxide and hydroxide Tetrapropylammonium, tetrabutylammonium hydroxide, tetraamylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, Tetraalkylammonium hydroxide such as methyltributylammonium hydroxide or dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide or triethylbenzyl hydroxide A quaternary ammonium salt such as a quaternary ammonium salt or an alkaline aqueous solution such as a cyclic amine such as pyrrole or piperidine.

Further, after the development treatment or the rinsing treatment, the treatment of removing the developer or eluent adhering to the pattern by the supercritical fluid can be performed.

When the pattern forming method of the present invention has a step of performing development using an organic developing solution, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, an ether solvent, or the like can be used as the organic developer. A polar solvent and a hydrocarbon solvent.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, and 1-hexyl. Ketone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetamidine acetone, acetone acetone, violet Ketone, diacetone alcohol, acetamethanol, acetophenone, methylnaphthyl ketone, isophorone, propyl carbonate, and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, and propylene glycol monomethyl ether. Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxy Butyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Wait.

Examples of the alcohol-based solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, and An alcohol such as sterol, or a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethyl A glycol ether solvent such as diol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol.

Examples of the ether solvent include dioxane, tetrahydrofuran, and the like, in addition to the glycol ether solvent.

As the amide-based solvent, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine, or the like can be used. 1,3-dimethyl-2-imidazolidinone and the like.

Examples of the hydrocarbon-based solvent include an aromatic hydrocarbon solvent such as toluene or xylene, and an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane. The solvent may be mixed in a plurality of types, or may be used in combination with a solvent or water other than the above. However, in order to sufficiently obtain the effects of the present invention, it is preferred that the entire water content of the developer is less than 10% by mass, and more preferably substantially no moisture. In other words, the amount of the organic solvent to be used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and preferably 95% by mass or more and 100% by mass or less based on the total amount of the developer.

In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

The vapor pressure of the organic developer is preferably 5 kPa or less at 20 ° C, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the organic developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, and temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is changed. good.

In the organic developer, an appropriate amount of a surfactant may be added as needed. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based surfactant and/or a lanthanoid surfactant can be used. Examples of the fluorosurfactant and/or the lanthanum-based surfactant include JP-A-62-36663, JP-A-61-226746, and JP-A-61-226745. Japanese Patent Laid-Open Publication No. SHO-62-170950, Japanese Patent Laid-Open Publication No. SHO-63-34540, Japanese Patent Laid-Open No. Hei No. Hei. Japanese Patent Publication No. 54432, Japanese Patent Laid-Open No. Hei 9-5988, U.S. Patent No. 5,405, 720, U.S. Patent No. 5,360, 692, U.S. Patent No. 5,529, 881, U.S. Patent No. 5,296,330, U.S. Patent No. 5,436,098, The surfactant described in the specification of Japanese Patent No. 5,576,143, the specification of U.S. Patent No. 5,294,511, and the specification of U.S. Patent No. 5,824,451 is preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, but a fluorine-based surfactant or a lanthanoid surfactant is more preferably used.

The amount of the surfactant to be used is usually 0.001% by mass to 5% by mass, preferably 0.005% by mass to 2% by mass, and more preferably 0.01% by mass to 0.5% by mass based on the total amount of the developer.

The organic developer may also contain a basic compound. Specific examples and preferred examples of the basic compound which may be contained in the organic developing solution used in the present invention, and specific examples of the basic compound which may be contained in the sensitizing ray-sensitive or radiation-sensitive resin composition and The preferred examples are the same.

As a developing method, for example, a method of immersing a substrate in a tank filled with a developing solution for a fixed period of time (dipping method), and a method of developing by depositing a developing solution on the surface of the substrate by a surface tension and stationary for a fixed period of time can be applied. Puddle method; a method of spraying a developer onto a surface of a substrate (spray method); a method of continuously ejecting a developer onto a substrate rotating at a fixed speed while scanning a developer discharge nozzle at a fixed speed (dynamic dispensing) Law) and so on.

When the various developing methods include a step of ejecting the developing solution from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developing solution (the flow rate per unit area of the ejected developing solution) is preferably 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, further preferably 1 mL/sec/mm ² or less. The flow rate does not particularly have a lower limit, but it is preferably 0.2 mL/sec/mm ² or more in consideration of the treatment amount.

By setting the discharge pressure of the developer to be ejected to the above range, the defects of the pattern caused by the resist residue after development can be remarkably reduced.

The details of this mechanism are not clear, but it is considered that the reason is that the pressure applied to the resist film by the developer is reduced by setting the discharge pressure to the above range, and the resist film and resist are used. The situation in which the pattern is unintentionally cut or collapsed is suppressed.

Further, the discharge pressure (mL/sec/mm ² ) of the developer is a value at the exit of the developing nozzle in the developing device.

As a method of adjusting the discharge pressure of the developer, for example, a method of adjusting the discharge pressure by a pump or the like, or a method of changing the discharge pressure by adjusting the pressure by supply from the pressurizing tank, or the like may be mentioned.

Further, after the step of developing using a developing solution containing an organic solvent, the step of stopping the development while replacing the solvent with another solvent may be employed.

In the pattern forming method of the present invention, a step of developing using a developing solution containing an organic solvent (organic solvent developing step) and a step of developing using an alkaline aqueous solution (alkali developing step) may be used in combination. Thereby, a finer pattern can be formed. In the present invention, the portion having a weak exposure intensity is removed by the organic solvent developing step, and the portion having a high exposure intensity is also removed by performing the alkali developing step. In this way, by performing the multiple development process for performing multiple developments, only the region of the medium exposure intensity can be patterned without being dissolved, so that a more fine pattern can be formed (Japanese Patent Laid-Open Publication No. 2008-292975 [0077] ] the same mechanism). In the pattern forming method of the present invention, the order of the alkali developing step and the organic solvent developing step is not particularly limited.

Preferably, after the step of developing using a developing solution containing an organic solvent, the step of washing using an eluent is included. The eluent used in the rinsing step after the step of performing development using a developing solution containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. As the eluent, it is preferred to use at least one organic solvent containing a group selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. Eluent. Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent are the same as those exemplified in the developer containing the organic solvent.

After the step of performing development using a developer containing an organic solvent, it is more preferred to use at least one organic solvent containing a group selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. The step of washing the eluent is preferably a step of washing with an eluent containing an alcohol solvent or an ester solvent, and particularly preferably a step of washing with a rinse containing a monohydric alcohol. A step of washing with an eluent containing a monohydric alcohol having 5 or more carbon atoms is carried out.

Here, examples of the monohydric alcohol used in the elution step include linear, branched, and cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, and 3-methyl- can be used. 1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, Cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, etc., as a particularly preferred monohydric alcohol having 5 or more carbon atoms, 1 can be used. -hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

The respective components may be used in combination of a plurality of types, or may be used in combination with an organic solvent other than the above. The water content in the eluent is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. Good development characteristics can be obtained by setting the water content to 10% by mass or less.

The vapor pressure of the eluent used after the step of performing development using a developing solution containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less. Preferably, it is 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the eluent to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling caused by the penetration of the eluent is suppressed, and the size in the wafer surface is reduced. The uniformity is better.

In the eluent, an appropriate amount of surfactant can also be added for use. In the elution step, the wafer subjected to development using a developer containing an organic solvent is subjected to a cleaning treatment using the eluent containing an organic solvent. The method of the cleaning treatment is not particularly limited, and for example, a method of continuously ejecting the eluent onto a substrate rotating at a fixed speed (a spin coating method) and a method of immersing the substrate in a tank filled with the eluent for a fixed time can be applied. (dipping method), a method of spraying the eluent onto the surface of the substrate (spraying method), etc., wherein the cleaning treatment is preferably performed by a spin coating method, and the substrate is rotated at 2000 rpm to 4000 rpm after washing. Rotate while removing the eluent from the substrate. In addition, it is also preferred to include a heating step (Post Bake) after the rinsing step. The developer and the eluent remaining between the patterns and the inside of the pattern are removed by baking. The heating step after the rinsing step is usually carried out at 40 ° C to 160 ° C, preferably 70 ° C to 95 ° C, for usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The pattern forming method of the present invention can also be suitably used for guiding pattern formation in Directed Self-Assembly (DSA) (for example, refer to "ACS Nano" Vol. 4 No. 8 4815 Page - 4823). Further, the present invention relates to a method of manufacturing an electronic component including the pattern forming method (preferably a negative type) of the present invention, and an electronic component manufactured by the manufacturing method. The electronic component of the present invention is an electronic component that is suitably mounted on an electric and electronic device (a home appliance, an office automation (OA), a media-related device, an optical device, a communication device, or the like).

Various materials used in the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention (for example, developer, eluent, antireflection film-forming composition, and top coat layer forming composition) Preferably, the material does not contain impurities such as metals. The content of the metal component contained in the materials is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less, and particularly preferably substantially no more than the mass of each of the materials. Contains (below the detection limit of the measuring device). As a method of removing impurities such as metals from the various materials, for example, filtration using a filter is exemplified. As the filter pore diameter, the pore size is preferably 50 nm or less, more preferably 10 nm or less, further preferably 5 nm or less. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon. In the filter filtration step, a plurality of filters may be connected in series or in parallel. When a plurality of filters are used, a filter having a different aperture and/or material may be used in combination. Alternatively, the various materials may be filtered multiple times, and the step of filtering a plurality of times may also be a cyclic filtration step. In addition, as a method of reducing impurities such as metals contained in the various materials, a method of selecting a raw material having a small metal content as a raw material constituting each material, and filtering a raw material constituting each material may be mentioned. The preferable conditions in the filter filtration of the raw materials constituting the various materials are the same as those described above. In addition to the filter filtration, the adsorbent material may be used to remove impurities, and the filter may be used in combination with the adsorbent material. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as tannin or zeolite, or an organic adsorbent such as activated carbon can be used. [Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited thereto.

[Synthesis Example 1: Synthesis of Compound A1] Compound A1 was synthesized by the method shown below.

[化72]

<Synthesis of A1-2> 18 g (100 mmol) of A1-1 (adamantanol) was dissolved in 160 g of methane chloride in a three-necked flask, and 14.9 g (115 mmol) of diisopropyl B was added. Amine (iPr ₂ NEt) and cooled to -20 °C. Then, 30.8 g (110 mmol) of trifluoromethanesulfonic acid (Tf ₂ O) was added dropwise to the reaction mixture using a dropping funnel. Further, after stirring at -20 ° C for 1 hour, the reaction liquid was added to a three-necked flask to which 400 g of saturated sodium hydrogencarbonate water and 300 g of hexane were added, and stirred at room temperature (25 ° C) for 10 minutes. . Then, the organic phase was separated, washed with a saturated aqueous solution of ammonium chloride, water, and brine, and concentrated to give 31 g of the objective compound A1-2.

<Synthesis of A1-4> 20 g (270 mmol) of A1-3 (2-methyl-1-propanol) was dissolved in 200 g of tetrahydrofuran (THF) in a three-necked flask, and 38.4 g (297 mmol) was added. Diisopropylethylamine and cooled to 0 °C. Then, 32.5 g (284 mmol) of methanesulfonium chloride (MsCl) was added dropwise to the reaction mixture using a dropping funnel. Further, after stirring at 0 ° C for 1 hour, the reaction liquid was added to a three-necked flask to which 300 g of saturated sodium hydrogencarbonate water was added, and the mixture was stirred at room temperature (25 ° C) for 10 minutes. Then, 300 g of ethyl acetate was added, and the organic phase was separated, washed with water and saturated brine, and concentrated. The obtained crude product was subjected to distillation purification (5 mmHG, external temperature 100 ° C) to obtain 26 g of the objective compound A1-4.

<Synthesis of A1-5> 20 g (134 mmol) of A1-4 was dissolved in 300 g of tetrahydrofuran (THF) and 20 g of 1,3-dimethyl-2-imidazolidinone in a three-necked flask (1) , 3-Dimethyl-2-imidazolidinone, DMI), and cooled to -78 °C. Then, 50.6 ml (134 mmol) of n-BuLi (2.65 M/hexane solution) was added dropwise to the reaction solution by means of a syringe. Further, after stirring at -78 ° C for 30 minutes, a solution obtained by dissolving 27.9 g (89.3 mmol) of A1-2 in 50 g of THF was added dropwise to the reaction mixture using a dropping funnel. After warming to 0 ° C and stirring for 1 hour, the reaction liquid was added to a three-necked flask to which 1 L of hexane and 500 g of a saturated aqueous ammonium chloride solution were added, and the mixture was stirred at room temperature (25 ° C) for 30 minutes. The organic phase was then separated and washed with water and saturated brine and concentrated. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 20/1) to obtain 20.4 g of the objective compound A1-5.

<Synthesis of A1-6> 11.6 g (37 mmol) of A1-5 was dissolved in 60 g of THF in a three-necked flask and cooled to -78 °C. Then, 58 ml (111 mmol) of bis(trimethyldecyl)amino sodium (NaHMDS) (1.9 M/hexane solution) was added dropwise to the reaction solution by means of a syringe. Further, after stirring at -78 ° C for 30 minutes, 35 g (111 mmol) of N-Fluorobenzenesulfonimide (NFSi) was added in portions to the reaction mixture. After stirring at -78 ° C for 2 hours, the reaction liquid was added to a three-necked flask to which 500 g of hexane and 300 g of a saturated aqueous ammonium chloride solution were added, and stirred at room temperature (25 ° C) for 30 minutes. The organic phase was then separated and washed with water and saturated brine and concentrated. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 60/1) to obtain 5.0 g of the objective compound A1-6.

<Synthesis of A1> 2.0 g (5.7 mmol) of A1-6 was added to a three-necked flask, dissolved in 20 g of acetonitrile, and cooled to 0 °C. 0.85 g (5.7 mmol) of NaI was added to the reaction mixture, and the mixture was heated to an internal temperature of 40 ° C and stirred for 1 hour. Further, after the internal temperature was room temperature (25 ° C), 50 g of methyl chloride, 50 g of water was added, and 1.96 g (5.7 mmol) of triphenylsulfonium bromide (TPS-Br) was added. Stir for 2 hours. The organic phase was separated, washed with 200 g of water and the organic phase was concentrated. The obtained concentrate was washed with 100 g of a hexane/ethyl acetate = 2/1 solution to obtain 2.85 g of the target compound A1. ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 1.36-1.40 (2H, m), 1.47 (6H, brs), 1.57-1.69 (6H, m), 1.92 (2H, brs), 2.21-2.40 ( 2H, m), 7.66-7.81 (15H, m) The compound A2 to the compound A16 described later were synthesized by the same synthesis method as the compound A1.

[Synthesis Example 2: Synthesis of Resin (1)] 102.3 parts by mass of cyclohexanone was heated to 80 ° C under a nitrogen stream. While stirring the solution, 22.2 parts by mass of the monomer represented by the following structural formula M-1 and 22.8 parts by mass of the monomer represented by the following structural formula M-2 were added dropwise for 5 hours, and the following structural formula was obtained. 6.6 parts by mass of the monomer represented by M-3, 189.9 parts by mass of cyclohexanone, and dimethyl ester of 2.2'-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] 2.40 parts by mass Solution. After completion of the dropwise addition, the mixture was further stirred at 80 ° C for 2 hours. After the reaction liquid was allowed to stand for cooling, it was reprecipitated by an excess of hexane/ethyl acetate (mass ratio: 9:1), and filtered, and the obtained solid was vacuum-dried to obtain 41.1 parts by mass of the resin (1).

[化73]

The weight average molecular weight (Mw: polystyrene conversion) obtained by GPC (carrier: tetrahydrofuran (THF)) of the obtained resin (1) was Mw=9500, and the degree of dispersion was Mw/Mn=1.62. The composition ratio as determined by ¹³ C-NMR was 40/50/10 in terms of molar ratio. The same operation as in Synthesis Example 2 was carried out, and the resin (2) to the resin (12) described later were synthesized as an acid-decomposable resin.

<Preparation of Resist> The components shown in Table 3, which will be described later, were dissolved in a solvent, and a solution having a solid concentration of 4% by mass was prepared for each component, and filtered using a polyethylene filter having a pore diameter of 0.05 μm. A sensitizing ray-sensitive or sensitizing radioactive resin composition is prepared. The sensitizing ray-sensitive or sensitized radioactive resin composition was evaluated by the following method, and the results are shown in Table 3. Regarding each component in Table 3, the ratio when a plurality of materials were used was a mass ratio.

<Pattern Forming Method> An organic anti-reflection film ARC29SR (manufactured by Nissan Chemical Co., Ltd.) was applied onto a silicon wafer, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 95 nm. A photosensitive ray-sensitive or radiation-sensitive resin composition (resist composition) is applied onto the anti-reflection film, and baked at 100 ° C for 60 seconds (pre-baking (PB: Prebake)) to form a film. A resist film with a thickness of 100 nm. ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY bias), with a line width of 50 The resulting wafer is exposed by a 1:1 line of nm and a 6% halftone mask of the spatial pattern. The liquid immersion liquid is ultrapure water. It was then heated at 105 ° C for 60 seconds (PEB: Post Exposure Bake). Subsequently, development was carried out by coating with butyl acetate for 30 seconds, and rinsing was carried out by coating with an eluent [methyl isobutyl carbinol (MIBC)] for 30 seconds. Then, the wafer was rotated at 4000 rpm for 30 seconds, thereby forming a 1:1 line and space pattern with a line width of 50 nm.

<Evaluation> (Defth of Focus) (DOF: Depth of Focus) In the exposure/development conditions of the <pattern forming method>, the exposure amount of the line pattern having a line width of 50 nm is formed in the focus direction. Exposure and development were carried out under the condition that the exposure focus was changed in units of 10 nm, and the spatial line width of each pattern obtained by measuring the scanning electron microscope SEM (S-9380) was measured using a line width length measuring electron microscope (S-9380) ( CD), drawing each CD, and setting the focus corresponding to the minimum value or the maximum value of the obtained curve as the best focus. When the focus is changed centering on the best focus, the range of variation of the focus of the allowable line width of 50 nm ± 10%, that is, the focus latitude (nm). The greater the value of the focus latitude, the better.

(Sensitivity Evaluation) An organic antireflection film ARC29SR (manufactured by Nissan Chemical Co., Ltd.) was applied onto a wafer, and baked at 205 ° C for 60 seconds to form an antireflection film having a film thickness of 95 nm. A resist composition was applied onto the antireflection film, and baked at a temperature of 90 ° C for 60 seconds (prebaking (PB: Prebake)) to form a resist film having a film thickness of 100 nm. The resulting wafer was exposed using a liquid immersion exposure machine (manufactured by ASML Corporation; XT1700i) through a halftone mask having a pitch of 138 nm and a light-shielding portion of 50 nm. The liquid immersion liquid is ultrapure water. It was then heated at a temperature of 85 ° C for 60 seconds (PEB: Post Exposure Bake). The resulting wafer was developed with butyl acetate for 30 seconds to form a line and space pattern. The line-space pattern obtained by observing the obtained line and space pattern using a line width length-measurement scanning electron microscope SEM (Hitachi, S-9380) was used to obtain an exposure amount having a spatial width of 35 nm as the sensitivity (mJ/cm ² ). The smaller the value of the sensitivity, the better.

[table 3]

The abbreviations in the table use the following. <Compound A (photoacid generator (A))>

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<Other photoacid generator>

[化75]

[化76]

<Resin (B)>

[化77]

Further, the composition ratio (molar ratio; corresponding from the left), the weight average molecular weight (Mw), and the degree of dispersion (Mw/Mn) of each repeating unit are shown in Table 4 below. These were determined by the same method as the resin (1).

[Table 4]

<Acid Diffusion Control Agent (Basic Compound)> As the acid diffusion controlling agent, the following compounds were used.

[化78]

<Hydrophobic Resin> As the hydrophobic resin, the following resins were used.

[化79]

[化80]

Table 5 shows the composition ratio (molar ratio; corresponding from the left), weight average molecular weight (Mw), and dispersion (Mw/Mn) of each repeating unit. These were determined by the same method as the resin (1).

[table 5]

<Interacting Agent> W-1: Megafac F176 (manufactured by Di Ai Sheng (Stock)) (Fluorine) W-2: Megafac R08 (manufactured by Di Ai Sheng (Stock)) (Fluorine and Bismuth) W-3: PF6320 (Europe) Manufactured by OMNOVA Solutions Inc. (Fluorine) W-4: Troysol S-366 (manufactured by Troy Chemical Co., Ltd.) [Solvent] A1: Propylene glycol monomethyl ether acetate ( PGMEA) A2: cyclohexanone A3: γ-butyrolactone B1: propylene glycol monomethyl ether (PGME)

According to the results shown in Table 3, Example 1 to the compound (A) was contained as compared with the photosensitive ray-sensitive or radiation-sensitive resin composition of Comparative Example 1 to Comparative Example 4 containing no compound (A). The sensitized ray-sensitive or radiation-sensitive resin composition of Example 19 had a large focus latitude and high sensitivity. Further, the sensitizing ray-sensitive or radiation-sensitive resin composition of Examples 7 and 15 and the focus of the sensitizing ray-sensitive or radiation-sensitive resin composition of Example 2 and Examples 9 to 15 were obtained. The sensitizing ray-sensitive or radiation-sensitive resin composition of the seventh embodiment and the fifteenth embodiment contains the following resin, that is, the resin has decomposition due to the action of an acid and generates polarity. a radical of the radical, wherein T in the formula (AI) is a single bond, Rx ₁ , Rx ₂ and Rx ₃ are alkyl groups, and the sum of the carbon numbers of the alkyl groups represented by Rx ₁ , Rx ₂ and Rx ₃ 4 or more, and 2 or 3 of Rx ₁ , Rx ₂ , and Rx ₃ are not bonded to form a ring; and the sensitized ray-sensitive or radiation-sensitive resin composition of the second embodiment and the second to fifth embodiments The substance contains a resin having a group which decomposes due to the action of an acid and generates a polar group, and R ₃₂ in the formula (1) is an isopropyl group or a tert-butyl group. [Industrial availability]

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method using the same can satisfy a large focus latitude and high sensitivity particularly in pattern formation of extremely fine (for example, a line width of 50 nm or less).

The present invention has been described with reference to the specific embodiments thereof, and it is obvious to those skilled in the art that various changes or modifications may be made without departing from the spirit and scope of the invention. The present application is based on Japanese Patent Application No. 2014-136327, filed on Jan.

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Claims (18)

A resin composition containing a compound (A) and a compound represented by the following formula (I) by irradiation with actinic rays or radiation, having a sensitizing ray or a radiation sensitization (A) will produce sulfonic acid, In the formula, Rf ₁ and Rf ₂ each independently represent a fluorine atom or a monovalent organic group containing at least one fluorine atom; and R ₁ and R ₂ each independently represent a monovalent organic group or a hydrogen atom having no fluorine atom, R ₃ to R ₅ each independently represent a hydrogen atom or a monovalent organic group; n represents an integer of 1 or more; and when n represents an integer of 2 or more, a plurality of R ₃ and a plurality of R ₄ may be the same or different. . The resin composition according to claim ₁ , wherein the R ₁ and R ₂ represent a hydrogen atom. The resin composition according to claim 2, wherein the R ₅ represents a monovalent organic group having a cyclic structure. The resin composition according to claim 3, wherein the R ₅ represents a monovalent organic group having a polycyclic cyclic structure. The resin composition according to claim 4, wherein the R ₅ represents a polycyclic cycloalkyl group. The resin composition according to claim 2, wherein the Rf ₁ and Rf ₂ represent a fluorine atom. The resin composition according to claim 2, wherein R ₃ and R ₄ represent a hydrogen atom. The resin composition according to claim 2, wherein at least one of R ₃ and R ₄ represents an alkyl group. The resin composition according to claim 2, wherein the n represents 1. The resin composition according to claim 2, wherein the compound (A) is a phosphonium salt. The resin composition according to any one of claims 1 to 10, further comprising a resin having a group which decomposes due to the action of an acid and generates a polar group. The resin composition according to claim 11, wherein the resin having a group decomposed by an action of an acid and generating a polar group contains a repeating unit represented by the following formula (AI). In the formula (AI), Xa ₁ represents a hydrogen atom, a methyl group or a group represented by -CH ₂ -R ₉ ; R ₉ represents a hydroxyl group or a monovalent organic group; and T represents a single bond or a divalent linking group; Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group; and two of Rx ₁ to Rx ₃ may be bonded to each other to form a cycloalkyl group. The resin composition according to claim 12, wherein T in the formula (AI) is a single bond, and Rx ₁ , Rx ₂ and Rx ₃ are an alkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ The total number of carbon atoms of the alkyl group is 4 or more, and two or three of Rx ₁ , Rx ₂ and Rx ₃ are not bonded to form a ring. The resin composition according to claim 11, wherein the resin having a group decomposed by an action of an acid and generating a polar group is a resin containing a repeating unit represented by the following formula (1). In the formula (1), R ₃₁ represents a hydrogen atom, an alkyl group or a fluorinated alkyl group, R ₃₂ represents an alkyl group, and R ₃₃ represents a monocyclic alicyclic hydrocarbon structure together with a carbon atom to which R ₃₂ is bonded. The desired alicyclic hydrocarbon structure may also be substituted by a hetero atom or a group having a hetero atom to form a part of a carbon atom constituting the ring. The resin composition according to claim 14, wherein the R ₃₂ is an isopropyl group or a tert-butyl group. A pattern forming method, comprising: a step of forming a photosensitive ray-sensitive or radiation-sensitive film by the resin composition according to any one of claims 1 to 10; a step of exposing the radiation or radiation sensitive film; and developing the exposed photosensitive radiation or radiation sensitive film with a developer containing an organic solvent. The pattern forming method according to claim 16, wherein the exposure is ArF immersion exposure. A method of manufacturing an electronic component, comprising the pattern forming method according to claim 16 of the patent application.