WO2016002634A1

WO2016002634A1 - Actinic ray-sensitive or radiation-sensitive resin composition, pattern-forming method, electronic device production method, and electronic device

Info

Publication number: WO2016002634A1
Application number: PCT/JP2015/068392
Authority: WO
Inventors: 研由後藤; 祥平片岡; 啓太加藤
Original assignee: 富士フイルム株式会社
Priority date: 2014-07-01
Filing date: 2015-06-25
Publication date: 2016-01-07
Also published as: JP6438954B2; JPWO2016002634A1; TW201610569A

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. In the formula, Rf₁ and Rf₂ each represent a fluorine atom or a monovalent organic group comprising at least one fluorine atom. R₁ and R₂ each represent a hydrogen atom or a monovalent organic group not having a fluorine atom, and R₃-R₅ each represent a hydrogen atom or a monovalent organic group. n represents a positive integer. When n is an integer with a value of at least 2, the plurality of R₃ and the plurality of R₄ can each be the same or different.

Description

Actinic ray-sensitive or radiation-sensitive resin composition, pattern formation method, electronic device manufacturing method, and electronic device

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method. More specifically, the present invention relates to an actinic ray used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, a further photofabrication process, a lithographic printing plate, and an acid curable composition. The present invention relates to a photosensitive or radiation-sensitive resin composition and a pattern forming method. The present invention also relates to an electronic device manufacturing method including the pattern forming method and an electronic device manufactured by the method.

The chemically amplified resist composition generates an acid in the exposed area by irradiation with actinic rays or radiation such as ArF, and reacts with the developer in the irradiated and non-irradiated areas of the active ray or radiation by a reaction using this acid as a catalyst. It is a pattern forming material that changes the solubility and forms a pattern on a substrate.

Various compounds have been developed for photoacid generators, which are the main constituents of chemically amplified resist compositions (for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2004-2252 International Publication No. 2009/051088

However, the present inventors have examined the compositions containing the photoacid generators described in Patent Documents 1 and 2, and in particular, in forming a very fine pattern (for example, a line width of 50 nm or less), the focus tolerance (DOF) : Depth Of Focus) and further improvement in sensitivity was desired.

In view of the above circumstances, the present invention is an actinic ray-sensitive or radiation-sensitive resin composition having a large focus tolerance and high sensitivity, particularly in the formation of extremely fine patterns (for example, a line width of 50 nm or less). It is an object of the present invention to provide a pattern forming method. Another object of the present invention is to provide an electronic device manufacturing method including the pattern forming method and an electronic device manufactured by the manufacturing method.

That is, the present invention is as follows.

[1]
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (A) that generates a sulfonic acid represented by the following general formula (I) upon irradiation with actinic rays or radiation.

Where
Rf ₁ and Rf ₂ each independently represents a fluorine atom or a monovalent organic group containing at least one fluorine atom.
R ₁ and R ₂ each independently represents a monovalent organic group or hydrogen atom having no fluorine atom, and R ₃ to R ₅ each independently represents 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, the plurality of R ₃ and the plurality of R ₄ may be the same or different.
[2]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein R ₁ and R ₂ represent a hydrogen atom.
[3]
The actinic 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 actinic ray-sensitive or radiation-sensitive resin composition according to [3], wherein R ₅ represents a monovalent organic group having a polycyclic ring structure.
[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to [4], wherein R ₅ represents a polycyclic cycloalkyl group.
[6]
The actinic 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 actinic 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 actinic 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 actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein n represents 1.
[10]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the compound (A) is an onium salt.
[11]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10], further comprising a resin having a group that decomposes by the action of an acid to generate a polar group.
[12]
The actinic ray-sensitive or radiation-sensitive resin composition according to [11], wherein the resin having a group that decomposes by the action of an acid to generate a polar group contains a repeating unit represented by the following general formula (AI): .

In 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 represents an alkyl group or a cycloalkyl group.
Two of Rx ₁ to Rx ₃ may combine to form a cycloalkyl group.
[13]
T in the general formula (AI) is a single bond, Rx ₁ , Rx ₂ and Rx ₃ are alkyl groups, and the total number of carbon atoms of the alkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ is 4 or more. The actinic ray-sensitive or radiation-sensitive resin composition according to [12], wherein two or three of Rx ₁ , Rx ₂ and Rx ₃ are not bonded to form a ring.
[14]
The resin according to [11], [12] or [13], wherein the resin having a group that decomposes by the action of an acid to generate a polar group is a resin having a repeating unit represented by the following general formula (1): Actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (1),
R ₃₁ represents a hydrogen atom, an alkyl group or a fluorinated alkyl group,
R ₃₂ represents an alkyl group,
R ₃₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R ₃₂ is bonded.
In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.
[15]
The actinic ray-sensitive or radiation-sensitive resin composition according to [14], wherein R ₃₂ is an isopropyl group or a t-butyl group.
[16]
A step of forming an actinic ray-sensitive or radiation-sensitive film from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [15],
A pattern forming method comprising: exposing the actinic ray sensitive or radiation sensitive film; and developing the exposed actinic ray sensitive or radiation sensitive film with a developer containing an organic solvent.
[17]
The pattern forming method according to [16], wherein the exposure is ArF immersion exposure.
[18]
An electronic device manufacturing method including the pattern forming method according to [16] or [17].
[19]
[18] An electronic device manufactured by the method for manufacturing an electronic device according to [18].

According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition having a large focus tolerance and high sensitivity, particularly in the formation of a very fine pattern (for example, a line width of 50 nm or less), and a pattern forming method using the same It became possible to provide. Further, according to the present invention, it is possible to provide an electronic device manufacturing method including the pattern forming method and an electronic device manufactured by the manufacturing method.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
In addition, in the description of a group (atomic group) in this specification, the description which does not describe substitution or unsubstituted includes what has a substituent with what does not have a substituent. 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, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, “light” means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays and EUV light, but also drawing with electron beams and ion beams. Are also included in the exposure.

[Actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises an actinic ray-sensitive or sensitive compound containing a compound (A) that generates a sulfonic acid represented by the general formula (I) upon irradiation with an actinic ray or radiation. It is a radiation resin composition.

Hereinafter, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention will be described in detail.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably for ArF exposure, and more preferably for ArF immersion exposure.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may be a negative resist composition for organic solvent development or a positive resist composition for alkali development, but for organic solvent development. The negative resist composition is preferable. The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a chemically amplified resist composition.

<Compound (A)>
The radiation-sensitive or actinic ray-sensitive resin composition of the present invention comprises a compound (A) that generates a sulfonic acid represented by the following general formula (I) by irradiation with actinic rays or radiation (hereinafter referred to as “photoacid generator”). (A) ").

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

In general formula (I), Rf ₁ and Rf ₂ each independently represent a fluorine atom or a monovalent organic group containing at least one fluorine atom.
The monovalent organic group containing at least one fluorine atom is preferably an alkyl group substituted with at least one fluorine atom. 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, and 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 and CH ₂ CH ₂ C ₄ F ₉ are mentioned, among which it is preferable to represent a fluorine atom or CF _3, and it is more preferable to represent a fluorine atom.

In general formula (I), R ₁ and R ₂ each independently represents a monovalent organic group having no hydrogen atom or 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 general formula (I), R ₃ to R ₅ each independently represents a hydrogen atom or a monovalent organic group.
Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, and 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. preferable. The alkyl group, cycloalkyl group, and aryl group may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, and a ketone group.

R ₃ and R ₄ preferably represent a hydrogen atom.
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 the substituent is preferably an alkyl group or a cycloalkyl group.

R ₅ preferably represents a monovalent organic group having a cyclic structure, more preferably represents a monovalent organic group having a polycyclic ring structure, and more preferably represents 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 diamantyl 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), a carboxyl group. Group, and a hydroxyl group or an alkoxy group is preferable. The alkoxy group and the alkoxycarbonyl group may further have a substituent, and examples of the further substituent include a cycloalkyl group (preferably having 3 to 12 carbon atoms).

Note that R ₃ and R ₄ are not bonded to R ₅ to form a ring.

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

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

Formula _Rf 1 of (I-1) _{_{_{in, Rf 2, R 1 ~ R}}} 5, and n, _Rf 1 in formula _{_{(I), Rf 2, R}} 1 ~ R 5, and be a n synonymous Specific examples and preferred ranges are also the same.

The onium cation, for example, the general formula (ZI) or (ZII) in cation described below (Z ^- portions other than) may be preferably mentioned.

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

In the general formula (ZI),
Z ⁻ represents an anion represented by the general formula (I-1).
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two _{members out} of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

_Examples of the organic group for 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 1 to 10 carbon atoms), a cycloalkyl group (having 3 carbon atoms). To 15 are preferred).
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. The aryl group may be a heteroaryl group such as an indole residue or a pyrrole residue in addition to a phenyl group or a naphthyl group.

These aryl groups, alkyl groups and cycloalkyl groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

Two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include, but are not limited to, an alkylene group (preferably having 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like.
Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0046 and 0047 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, US Compounds exemplified as Formulas (I-1) to (I-70) in Patent Application Publication No. 2003 / 0224288A1, and Formulas (IA-1) to (I) in US Patent Application Publication No. 2003 / 0077540A1 And cation structures such as compounds exemplified as formulas (IA-54) and formulas (IB-1) to (IB-24).

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

In general formula (ZI-3),
Z ⁻ represents an anion represented by the general 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 represents 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 connected to each other to form a ring.
R _X and R _y each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group. To express.
R _X and R _y may combine with 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 an amide bond.

The alkyl group as R ₁ is preferably a linear or 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. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And branched alkyl groups such as a linear alkyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group. 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, and an ethoxycarbonylmethyl group. Can be mentioned.

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 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 include a methoxy group, an ethoxy group, an isopropyloxy group, a t-butyloxy group, a t-amyloxy group, and an n-butyloxy 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 as R ₁ is preferably a cycloalkoxy group having 3 to 20 carbon atoms, and examples thereof include a cyclohexyloxy group, a norbornyloxy group, and an adamantyloxy group. The cycloalkoxy group as 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 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 groups as the alkyl group, cycloalkyl group, alkoxy group and cycloalkoxy group as R ₁ described above can be used.

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

R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ₂ and R ₃ may be connected to each other to form a ring. However, 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, cycloalkyl group and aryl group for R ₂ and R ₃ include those similar to the specific examples and preferred examples described above for R ₁ . When R ₂ and R ₃ are connected to each other to form a ring, the total number of carbon atoms that contribute to the formation of the ring contained in R ₂ and R ₃ is preferably 4 to 7, and is preferably 4 or 5 It is particularly preferred that

R ₁ and R ₂ may be connected to each other to form a ring. When R ₁ and R ₂ are connected to each other to form a ring, R ₁ is an aryl group (preferably a phenyl group or a naphthyl group which may have a substituent), and R ₂ has 1 to 4 carbon atoms. An alkylene group (preferably a methylene group or an ethylene group) is preferable, and examples of the preferable substituent include the same substituents that the aryl group as R ₁ may have. As another form in the case where R ₁ and R ₂ are connected to each other to form a ring, it is also preferable that 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, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group. , Pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl Groups and the like.

The cycloalkyl group represented by R _X and R _y is preferably a cycloalkyl group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like.

The alkenyl group represented by R _X and R _y is preferably 2 to 30 alkenyl groups such as a vinyl group, an allyl group, and a styryl group.

As the aryl group represented by R _X and R _y , for example, an aryl group having 6 to 20 carbon atoms is preferable. Specifically, a phenyl group, a naphthyl group, an azulenyl group, an acenaphthylenyl group, a phenanthrenyl group, a penalenyl group, a phenyl group, Examples thereof include a nantracenyl group, a fluorenyl group, an anthracenyl group, a pyrenyl group, and a benzopyrenyl group. Preferred are a phenyl group and a naphthyl group, and more preferred is a phenyl group.

The alkyl group moiety of the 2-oxoalkyl group and alkoxycarbonylalkyl group represented by R _X and R _y, for example, those previously listed as R _X and R _y.

The cycloalkyl moiety of the 2-oxocycloalkyl group and alkoxycarbonyl cycloalkyl group represented by R _X and R _y, for example, those previously listed as R _X and R _y.

Preferred examples of the compound represented by the general formula (ZI-3) include compounds represented by the following general formulas (ZI-3a) and (ZI-3b).

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

Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and is preferably an oxygen atom or a nitrogen atom. t is 1 when Y is a nitrogen atom, is 0 when Y is an oxygen atom or a sulfur atom, and R ₅ does not exist.
m, n, p and q represent integers, preferably 0 to 3, more preferably 1 or 2, and particularly preferably 1. The alkylene group linking S ⁺ and Y and the alkylene group linking S ⁺ and the carbonyl group may have a substituent, and preferred substituents include an alkyl group.

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

In the formulas (ZI-3a-1) to (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, cycloalkyl group and aryl group for R include those similar to the specific examples and preferred examples described above for R ₁ in formula (ZI-3).
In the above (ZI-3a-1) to (ZI-3a-3), * represents a bond connected to a nitrogen atom as Y in the compound represented by the general 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, cycloalkyl group and aryl group for R ₄ include those similar to the specific examples and preferred examples described above for R _{1 in} formula (ZI-3).

Specific examples of the cation moiety of the compound represented by the general formula (ZI-3) are given below.

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

In general formula (ZI-4),
Z ⁻ represents an anion represented by the general formula (I-1).
R ₁₃ represents a hydrogen atom, a fluorine atom, or an optionally substituted hydroxyl group, alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, or cycloalkyl group.
R ₁₄ represents a hydroxyl group or an optionally substituted alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylsulfonyl group, cycloalkylsulfonyl group, or cycloalkyl group. To express.
R ₁₅ represents an alkyl group, a cycloalkyl group, or a naphthyl group, which may have a substituent. Two R ₁₅ may be the same or different. Two R ₁₅ may be bonded to each other to form a ring. The ring formed may further have a hetero atom in addition to the sulfur atom in the formula.
l represents an integer of 0-2.
r represents an integer of 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 general formula (ZI-4), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched, and those having 1 to 10 carbon atoms are preferable.
Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group.
The alkoxy group for R ₁₃ and R ₁₄ is preferably linear or branched and has 1 to 10 carbon atoms.
The alkoxycarbonyl group for R ₁₃ and R ₁₄ is preferably linear or branched and 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.
The alkyl group of the alkyl group of R _14, include the same specific examples and the alkyl group as R _{13 ~} R ₁₅ described above.
The alkylsulfonyl group and cycloalkylsulfonyl group for R ₁₄ are linear, branched, or cyclic and preferably have 1 to 10 carbon atoms.

Examples of the substituent that each of the above 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 alkoxycarbonyloxy group. Etc.

As the ring structure formed by bonding two R ₁₅ to each other, for example, a 5-membered or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the general formula (ZI-4), particularly preferable Includes a 5-membered ring (that is, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. This divalent R ₁₅ may have a substituent. 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, an alkoxycarbonyl group. Group, alkoxycarbonyloxy group and the like. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.

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

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

Specific examples of the cation structure possessed by the compound represented by the general formula (ZI-3) or (ZI-4) described above include the above-mentioned JP-A-2004-233661, JP-A-2003-35948, In addition to cationic structures such as compounds exemplified in US Patent Application Publication No. 2003 / 0224288A1 and US Patent Application Publication No. 2003 / 0077540A1, for example, paragraphs 0046 and 0047 of JP2011-53360A Cation structures in chemical structures and the like exemplified in 0072-0077 and 0107-0110, and cation structures in chemical structures exemplified in paragraphs 0135 to 0137, 0151 and 0196 to 0199 of JP2011-53430, etc. Is mentioned.

In general formula (ZII),
Z ⁻ represents an anion represented by the general formula (I-1).
R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ are the same as the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the above general formula (ZI).
The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the general formula (ZI) may have.

The aryl group for R ₂₀₄ and R ₂₀₅ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ₂₀₄ and R ₂₀₅ may be an aryl group having a heterocyclic structure having 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, indole, benzofuran, and benzothiophene.

As the alkyl group and cycloalkyl group represented by R ₂₀₄ and R ₂₀₅ , a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 to 15 carbon atoms). ), Aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups, and the like.
Specific examples of the cation of the compound represented by formula (ZII) are shown.

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

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

Further, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain only one type of compound (A), may contain two or more types of compounds (A), and may contain compound (A). In addition, a photoacid generator other than the compound (A) (hereinafter also referred to as photoacid generator (A ′)) may be included.
The photoacid generator (A ′) may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in 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 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the photoacid generator (A ′) is incorporated in a part of the polymer, it may be incorporated in a part of the acid-decomposable resin described above, or incorporated in a resin different from the acid-decomposable resin. It may be.
In the present invention, the photoacid generator (A ′) is preferably in the form of a low molecular compound.
When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains two or more photoacid generators, the total content of the photoacid generator is preferably within the above range.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains two or more kinds of compounds (A), the LWR of the pattern to be formed becomes smaller, so that in the general formula (I) It is preferable to contain two or more compounds (A) having the same anion structure and different cation structures.

As the photoacid generator (A ′), a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, an actinic ray used for a micro resist, etc. Alternatively, known compounds that generate an acid upon irradiation with radiation and a mixture thereof can be appropriately selected and used.

Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

Further, a compound in which a compound capable of generating an acid upon irradiation with actinic rays or radiation is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent 3914407, etc. JP, 63-26653, JP, 55-164824, JP, 62-69263, JP, 63-146038, JP, 63-163452, JP, 62 The compounds described in JP-A-153833 and JP-A-63-146029 can be used.

Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712, etc. can also be used.

As a preferable photoacid generator (A ′), the description in paragraphs [0337] to [0400] of US2012 / 0076996A1 can be referred to, and the contents thereof are incorporated in the present specification.

<Resin having a group that decomposes by the action of an acid to generate a polar group>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is further referred to as a resin (hereinafter referred to as “resin (B)” or “acid-decomposable resin”) that has a group that decomposes by the action of an acid to generate a polar group. ) Is preferably included.
The resin (B) is typically a resin whose polarity is increased by the action of an acid and the solubility in a developer containing an organic solvent is decreased, and the solubility in an alkali developer is increased by the action of an acid. Resin.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention can take the form of positive and negative actinic ray-sensitive or radiation-sensitive resin compositions. The resin (B) has a group (hereinafter also referred to as “acid-decomposable group”) that decomposes by the action of an acid to generate a polar group in the main chain or the side chain, or in both the main chain and the side chain. The resin (B) preferably contains a repeating unit having an acid-decomposable group.

(1) Repeating unit having an acid-decomposable group The acid-decomposable group preferably has a structure protected by a group capable of decomposing and leaving a polar group by the action of an acid.
Preferred examples of the polar group include a carboxy group, a fluorinated alcohol group (preferably hexafluoroisopropanol), and a sulfonic acid group.
A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these polar groups is substituted with a group capable of leaving with an acid.
Examples of the group leaving with 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 the like.
In the formula, R ₃₆ to R ₃₉ each independently represents 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 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

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

In 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. Examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl 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 represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
Two of Rx ₁ to Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene 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 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 combining 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. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group is preferable.
In one embodiment, T in the general formula (AI) is a single bond, and Rx ₁ , Rx ₂ and Rx ₃ are preferably alkyl groups, and the alkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ The total number of carbon atoms is more preferably 4 or more, still 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.

Although the specific example of the repeating unit which has a preferable acid-decomposable group is shown below, this invention is not limited to this. In the formula, Xa ₁ represents any of H, CH ₃ , CF ₃ , and CH ₂ OH, and Rxa and Rxb each represents a linear or branched alkyl group having 1 to 4 carbon atoms.

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

In general formula (1),
R ₃₁ represents a hydrogen atom, an alkyl group or a fluorinated alkyl group,
R ₃₂ represents an alkyl group,
R ₃₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R ₃₂ is bonded.
In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.

The alkyl group for R ₃₁ may have a substituent, and examples of the substituent include a fluorine atom and a hydroxyl group.
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, and 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 t-butyl group, preferably an isopropyl group or a t-butyl group, and more preferably a t-butyl group.
The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
In the monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom, examples of the hetero atom capable of substituting a part of the carbon atoms constituting the ring include an oxygen atom and a sulfur atom, and a group having a hetero atom Examples of the carbonyl group include a carbonyl group. However, the group having a hetero atom is preferably not an ester group (ester bond).
The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably formed only from the carbon atom and the hydrogen atom.

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

In General Formula (1 ′), R ₃₁ and R ₃₂ have the same meanings as those in General Formula (1).

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

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

The repeating unit having an acid-decomposable group contained in the resin (B) may be one type, or two or more types may be used in combination. As the combination in the case of using together, the following are preferable. In the following formula, each R independently represents a hydrogen atom or a methyl group.

(2) A repeating unit having at least one group selected from a lactone group, a sultone group, a hydroxyl group, a cyano group, and an acid group The resin (B) is further composed of a lactone group, a sultone group, a hydroxyl group, a cyano group, and an acid group. It is preferable to have a repeating unit having at least one selected group.

The repeating unit having a lactone group or a sultone group that can be contained in the resin (B) will be described.
The resin (B) preferably contains a repeating unit having a lactone structure or a sultone (cyclic sulfonate ester) structure.
Any lactone group or sultone group can be used as long as it has a lactone structure or a sultone structure, but it is preferably a 5- to 7-membered lactone structure or a sultone structure, and a 5- to 7-membered lactone A structure in which another ring structure is condensed to form a bicyclo structure or a spiro structure in the structure or sultone structure is preferable. It is more preferable to have a repeating unit having a lactone structure or a sultone structure represented by any of the following general formulas (LC1-1) to (LC1-17), (SL1-1) and (SL1-2). A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures or sultone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), and more preferably (LC1-4). By using a specific lactone structure or sultone structure, LWR and development defects are improved.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, and carboxyl groups. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferred are an alkyl group having 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, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .
The resin (B) preferably contains a repeating unit having a lactone structure or a sultone structure represented by the following general formula (III).

In formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
When there are a plurality of R _{0 s} , each R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
When there are a plurality of Z, each is independently a single bond, ether bond, ester bond, amide bond, urethane bond

Or urea bond

Represents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group each independently.
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 0-2.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.
The alkylene group and cycloalkylene group represented by 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 for 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 alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a mercapto group, and a hydroxy group. Group, alkoxy group such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group, and acetoxy group such as acetyloxy group and propionyloxy group. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
The preferred chain alkylene group for R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. A preferred cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.

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 is represented by the general formula (LC1-1) described above as a specific example. Examples include a lactone structure or a sultone structure represented by (LC1-17), (SL1-1), and (SL1-2), and a structure represented by (LC1-4) is particularly preferable. Further, n ₂ in (LC1-1) to (LC1-17), (SL1-1) and (SL1-2) is more preferably 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) or a sultone structure (cyanosultone) having a cyano group as a substituent is more preferable.
In general formula (III), it is preferable that n is 0 or 1.

As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III-1) or (III-1 ′) is more preferable.

In the general formulas (III-1) and (III-1 ′),
R ₇ , A, R ₀ , Z, and n are as defined in the general formula (III).
R ₇ ′, A ′, R ₀ ′, Z ′ and n ′ are respectively synonymous with R ₇ , A, R ₀ , Z and n in the general formula (III).
R ₉ is each independently in the presence of two or more groups, an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, and when a plurality of bonded two R _9, ring May be formed.
When there are a plurality of R ₉ ′, each independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, and when there are a plurality of R ₉ ′, two R ₉ ′ are bonded. , May form a ring.
X and X ′ each independently represents an alkylene 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 each independently 0 or 1.

The alkyl group for 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 cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. These groups may have a substituent, and examples of the substituent include an alkoxy group such as a hydroxy group, a methoxy group, and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom. R ₉ and R ₉ ′ are more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.
Examples of the alkylene group for X and X ′ include a methylene group and an ethylene 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, at least one of R ₉ and R ₉ ′ is preferably substituted at the α-position or β-position of the carbonyl group of the lactone, particularly preferably at the α-position.

Specific examples of the group having a lactone structure represented by the general formula (III-1) or (III-1 ′) or the repeating unit having a sultone structure include paragraphs [0150] to JP-A-2013-178370. The structure described in [0151] can be mentioned.

The content of the repeating unit represented by the general formula (III) is preferably 15 to 60 mol%, more preferably 20 to 60 mol in total with respect to all the repeating units in the resin (B) when plural types are contained. %, More preferably 30 to 50 mol%.
Resin (B) may also contain a repeating unit having the above-mentioned lactone structure or sultone structure in addition to the unit represented by formula (III).

The repeating unit having a lactone group or a sultone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
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) is 15 to 60 mol% in total with respect to all the repeating units in the resin when a plurality of types are contained. More preferably, it is 20 to 50 mol%, still more preferably 30 to 50 mol%.
In order to enhance the effect of the present invention, two or more kinds of lactone or sultone repeating units selected from general formula (III) can be used in combination. When using together, it is preferable to select and use 2 or more types from the lactone or sultone repeating unit in which n is 0 in general formula (III).

The resin (B) preferably has a repeating unit other than the general formula (AI) having a hydroxyl group or a cyano group. This improves the substrate adhesion and developer compatibility. 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 these structures include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (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 represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. More preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the rest are hydrogen atoms.

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

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

Resin (B) preferably has a repeating unit having an acid group. Examples of the acid group include a carboxy group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron withdrawing group at the α-position. It is more preferable to have a repeating unit. By containing the repeating unit having an acid group, the resolution in the contact hole application is increased. The repeating unit having an acid group includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acid group in the main chain of the resin through a linking group. Either a repeating unit that is bonded, or a polymerization initiator or chain transfer agent having an acid group, is introduced at the end of the polymer chain during polymerization, and the linking group is a monocyclic or polycyclic cyclic hydrocarbon structure. You may have. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

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

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

The repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group and an acid group is more preferably a repeating unit having at least two selected from a lactone group, a hydroxyl group, a cyano group and an acid group. Preferably, it is a repeating unit having a cyano group and a lactone group. Particularly preferred is a repeating unit having a structure in which a cyano group is substituted on the lactone structure of (LCI-4).

(3) Repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability The resin (B) may further have a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. Good. This can reduce the elution of low molecular components from the resist film to the immersion liquid during immersion exposure. Examples of such repeating units include repeating units of 1-adamantyl (meth) acrylate, diamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and cyclohexyl (meth) acrylate.

(4) Repeating unit having neither a hydroxyl group nor a cyano group The resin (B) of the present invention further contains a repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group. It is preferable.

In general formula (III), R ₅ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a 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 an acyl group.

The cyclic structure possessed by R ₅ includes 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 ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. As the bridged cyclic hydrocarbon ring, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic ring Examples include hydrocarbon rings. The bridged cyclic hydrocarbon ring also includes, for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and the substituent which may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino protected with a protecting group The group can be mentioned.

Examples of the protecting 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 alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferable acyl groups include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The content of the repeating unit represented by the general formula (III) having neither a hydroxyl group nor a cyano group is preferably 0 to 40 mol%, more preferably based on all repeating units in the resin (B). 0 to 20 mol%.
Specific examples of the repeating unit represented by the general formula (III) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

Resin (B) may contain a repeating unit represented by the following general formula (nI) or general formula (nII).

In general formula (nI) and general formula (nII),
R ₁₃ ′ to R ₁₆ ′ each independently have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, or a lactone structure. Represents a group or a group having an acid-decomposable group.
X ₁ and X ₂ each independently represent a methylene group, an ethylene 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 as R ₁₃ ′ to R ₁₆ ′ include cumyl ester group, enol ester group, acetal ester group, tertiary alkyl ester group, etc. A tertiary alkyl ester group represented by —C (═O) —O—R ₀ is preferred.
In the formula, R ₀ is a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy 1-alkoxyethyl group such as ethyl group, alkoxymethyl group such as 1-methoxymethyl group and 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- Examples thereof include an oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue, and the like.
At least one of R ₁₃ ′ to R ₁₆ ′ 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 represented by R ₁₃ ′ to R ₁₆ ′ is more preferably a group represented by the following general formula (F1).

In general formula (F1),
R ₅₀ to R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R ₅₀ to R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Rx is a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, an acyl group, or an alkoxycarbonyl group), and preferably a hydrogen atom.
R ₅₀ to R ₅₅ are preferably all fluorine atoms.

Specific examples of the repeating unit represented by the general formula (nI) or the general formula (nII) include the following specific examples, but the present invention is not limited to these compounds. Of these, repeating units represented by (II-f-16) to (II-f-19) are preferred.

Resin (B) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general necessary characteristics of resist, in addition to the above repeating structural units. For this purpose, various repeating structural units can be included.

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

Thereby, the performance required for the resin (B), in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

In the resin (B), the content molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and the general required performance of the resist, resolving power, heat resistance, sensitivity. It is set appropriately in order to adjust etc.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure, the resin (B) preferably has no aromatic group from the viewpoint of transparency to ArF light. Moreover, it is preferable that resin (B) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin mentioned later.

Resin (B) is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units. More preferably, 20-50 mol% of (meth) acrylate-based repeating units having an acid-decomposable group represented by general formula (AI), 20-50 mol% of (meth) acrylate-based repeating units having a lactone group, A copolymer having 5 to 30 mol% of (meth) acrylate repeating units having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and further containing 0 to 20 mol% of other (meth) acrylate repeating units. .

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high-energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (B) is: In addition to the repeating unit represented by formula (AI), it is preferable to further have a hydroxystyrene-based repeating unit. More preferably, it has a hydroxystyrene-based repeating unit, an acid-decomposable repeating unit such as a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and a (meth) acrylic acid tertiary alkyl ester.

Preferred examples of the repeating unit having an acid-decomposable group include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, (meth) acrylic acid tertiary alkyl ester repeating units, and the like. 2-alkyl- More preferred are repeating units of 2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

The resin (B) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the actinic-ray sensitive or radiation sensitive resin composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is carried out using the same solvent as that used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferable initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 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, even more as a polystyrene converted value by GPC (gel permeation chromatography) method. Preferably it is 3,000 to 15,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

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

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

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

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

<Hydrophobic resin (HR)>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a hydrophobic resin. The hydrophobic resin is preferably different from the resin (B).
Hydrophobic resins are preferably designed to be unevenly distributed at the interface, but unlike surfactants, they do not necessarily have hydrophilic groups in the molecule and contribute to uniform mixing of polar / nonpolar substances. You don't have to.
Examples of the effects of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, improvement of immersion liquid followability, and suppression of outgas.

The hydrophobic resin has at least one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have two or more types.
When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin may be contained in the main chain of the resin or in the side chain. It may be.

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

Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R ₅₇ to R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). Provided that at least one of R ₅₇ to R ₆₁ , at least one of R ₆₂ to R ₆₄ , and at least one of R ₆₅ to R ₆₈ are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms).
All of R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are preferably fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include those exemplified in US2012 / 0251948A1 [0500].
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, —CH (CF ₃ ) OH and the like are mentioned, and —C (CF ₃ ) ₂ OH is preferable.
The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more.

The hydrophobic resin may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Examples of the alkylsilyl structure or the cyclic siloxane structure include partial structures described in paragraphs [0304] to [0307] of JP2013-178370A.
Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in US2012 / 0251948A1 [0519].

Further, as described above, the hydrophobic resin preferably includes a CH ₃ partial structure in the side chain portion.
Here, the CH ₃ partial structure of the side chain portion in the hydrophobic resin (hereinafter also simply referred to as “side chain CH ₃ partial structure”) includes a CH ₃ partial structure of an ethyl group, a propyl group, or the like. Is.
On the other hand, methyl groups directly bonded to the main chain of the hydrophobic resin (for example, α-methyl groups of repeating units having a methacrylic acid structure) contribute to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Since it is small, it is not included in the CH ₃ partial structure in the present invention.

More specifically, when the hydrophobic resin includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M) In the case where R ₁₁ to R ₁₄ are CH ₃ “as is”, the CH ₃ is not included in the CH ₃ partial structure of the side chain moiety in the present invention.
Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone shall apply to CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed that it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R ₁₁ to R ₁₄ each independently represents a side chain portion.
Examples of R ₁₁ to R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.
Examples of the monovalent organic group for R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion. As such a repeating unit, the repeating unit represented by the following general formula (II) and the following general unit It is more preferable to have at least one repeating unit (x) among the repeating units represented by the formula (III).

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

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, more specifically, the organic group that is stable against an acid is preferably an organic group that does not have the “acid-decomposable group” described in the resin (B).

The alkyl group of _Xb1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and 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, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above 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 acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.
Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.

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

In the above general formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an acid-stable organic group having one or more CH ₃ partial structures, n represents an integer of 1 to 5.
The alkyl group of _Xb2 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, and a trifluoromethyl group, and a hydrogen atom is preferable.
X _b2 is preferably a hydrogen atom.
Since R ₃ is an organic group that is stable against an acid, more specifically, R ₃ is preferably an organic group that does not have the “acid-decomposable group” described in the resin (B).

R ₃ includes an alkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.
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 general formula (III) are given below. Note that the present invention is not limited to this.

The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II) and the general formula ( The content of at least one repeating unit (x) among the repeating units represented by III) is preferably 90 mol% or more, more preferably 95 mol% or more, based on all repeating units of the hydrophobic resin. It is more preferable. Content is 100 mol% or less normally with respect to all the repeating units of hydrophobic resin.

The hydrophobic resin contains at least one repeating unit (x) among the repeating units represented by the general formula (II) and the repeating unit represented by the general formula (III) as all repeating units of the hydrophobic resin. On the other hand, the surface free energy of hydrophobic resin increases by containing 90 mol% or more. As a result, the hydrophobic resin is less likely to be unevenly distributed on the surface of the resist film, so that the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved.

In addition, the hydrophobic resin includes the following groups (x) to (z) regardless of whether (i) it contains a fluorine atom and / or a silicon atom, or (ii) contains a CH ₃ partial structure in the side chain portion. It may have at least one group selected from
(X) an acid group,
(Y) a group having a lactone structure or a sultone structure, an acid anhydride group, or an acid imide group,
(Z) a group decomposable 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 sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
The content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the hydrophobic resin. It is.
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.

As the group having a lactone structure or sultone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure or a sultone structure is particularly preferable.
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.
Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure or a sultone structure described above in the section of the resin (B).

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

Examples of the repeating unit having a group (z) that is decomposed by the action of an acid in the hydrophobic resin include the same repeating units as those having an acid-decomposable group listed for the resin (B). The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin, the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 10%, based on all repeating units in the hydrophobic resin. 80 mol%, more preferably 20 to 60 mol%.
The hydrophobic resin may further have a repeating unit represented by the following general formula (III).

In general formula (III):
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with 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 an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, 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 with a group containing a fluorine atom or a silicon atom.
L _c3 represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
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 may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with 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 general formula (III) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. 30 to 70 mol% is more preferable.
The hydrophobic resin preferably further has a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

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

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

When the hydrophobic resin has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin. Further, the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol% in all repeating units contained in the hydrophobic resin.
When the hydrophobic resin has a silicon atom, the content of silicon atom is preferably 2 to 50% by mass, more preferably 2 to 30% by mass with respect to the weight average molecular weight of the hydrophobic resin. Further, the repeating unit containing a silicon atom is preferably 10 to 100 mol%, and more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin.

On the other hand, in the case where the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, it is also preferred that the hydrophobic resin does not substantially contain a fluorine atom and a silicon atom. The content of the repeating unit having an atom or silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, more preferably 1 mol% or less, based on all repeating units in the hydrophobic resin. More preferably, it is ideally 0 mol%, ie it does not contain fluorine and silicon atoms. Moreover, it is preferable that hydrophobic resin is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, it is preferable that the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is 95 mol% or more in the total repeating units of the hydrophobic resin. 97 mol% or more is more preferable, 99 mol% or more is further preferable, and ideally 100 mol%.

The standard polystyrene equivalent weight average molecular weight of the hydrophobic resin is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.
Moreover, the hydrophobic resin may be used alone or in combination.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a hydrophobic resin, but when it is contained, the content of the hydrophobic resin in the composition is the sensitivity of the present invention. The amount is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and still more preferably 0.1 to 7% by mass based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.

Naturally, the hydrophobic resin has a small amount of impurities such as metals, and the residual monomer or oligomer component is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, 0.05 to 1% by mass is even more preferred. Thereby, a composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1-2.

As the hydrophobic resin, various commercially available products can be used, and can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.
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 for the resin (B). However, in the synthesis of the hydrophobic resin, the reaction concentration Is preferably 30 to 50% by mass.
Specific examples of the hydrophobic resin are shown below. The following table shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

<Acid diffusion control agent>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains an acid diffusion controller. The acid diffusion controller acts as a quencher that traps the acid generated from the photoacid generator during exposure and suppresses the reaction of the acid-decomposable resin (resin (B)) in the unexposed area due to excess generated acid. To do. Examples of the acid diffusion controller include a basic compound, a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, a basic compound whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, or An onium salt that is a weak acid relative to the photoacid generator can be used.

Preferred examples of the basic compound include compounds having structures represented by the following general formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with 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.

Regarding the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
Specific examples of preferred compounds include those exemplified in US2012 / 0219913A1 [0379].
Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably 6 to 12 carbon atoms may be bonded to the nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. In addition to the alkyl group, the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable.
The following compounds are also preferable as the basic compound.

As the basic compound, in addition to the above-mentioned compounds, JP2011-22560A [0180] to [0225], JP2012-137735A [0218] to [0219], International Publication Pamphlet WO2011 / 158687A1 [ [0416] to [0438] can also be used.
These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a basic compound. When it is contained, the content of the basic compound is based on the solid content of the composition. The content is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass.
The use ratio of the photoacid generator (including the photoacid generator (A ′)) and the basic compound in the composition is photoacid generator / basic compound (molar ratio) = 2.5 to 300. Is preferred. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The photoacid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.

A low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (C)”) is an amine derivative having a group on the nitrogen atom that is leaving by the action of an acid. It is preferable that
As the group capable of leaving by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, and a hemiaminal ether group are preferable, and a carbamate group and a hemiaminal ether group are particularly preferable. .
The molecular weight of the compound (C) is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
Compound (C) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
R _b each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group. (Preferably having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R _b may be connected to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _b are substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo group, an alkoxy group, and a halogen atom. May be. The same applies to the alkoxyalkyl group represented by _Rb .

R _b is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two R _b to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
Specific examples of the group represented by the general formula (d-1) include, but are not limited to, the structures disclosed in US2012 / 0135348 A1 [0466].

It is particularly preferable that the compound (C) has a structure represented by the following general formula (6).

In General 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 Ras may be the same or different, and two _Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
R _b has the same meaning as R _b in formula (d-1), and preferred examples are also the same.
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as R _a are the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as R _b may be substituted. It may be substituted with a group similar to the group described above.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of R _a (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above group) , R _b includes the same groups as the specific examples described above.
A particularly preferred compound (C) in the present invention is specifically shown, but the present invention is not limited thereto.

The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the compound (C) can be used singly or in combination of two or more.
The content of the compound (C) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 0.001 to 20% by mass, more preferably based on the total solid content of the composition. The amount is 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

A basic compound whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (PA)”) has a proton acceptor functional group and is irradiated with actinic rays or radiation. Is a compound whose proton acceptor properties are degraded, disappeared, or changed from proton acceptor properties to acidic properties.

The proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron. For example, a functional group having a macrocyclic structure such as a cyclic polyether or a π-conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

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

The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Means that when a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.
Proton acceptor property can be confirmed by measuring pH.

In the present invention, the acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1. More preferably, −13 <pKa <−3.

In the present invention, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution. For example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.) It shows that acid strength is so large that this value is low. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett The values based on the substituent constants and the known literature database can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. Since the compound represented by the general formula (PA-1) has an acidic group together with the proton acceptor functional group, the proton acceptor property is reduced or disappeared compared to the compound (PA), or the proton acceptor property is reduced. It is a compound that has changed to acidic.

In general 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), and W ₁ and W ₂ each 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 R _x 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 preferred is an alkylene group having at least one fluorine atom, and the preferred carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

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, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. It may be.
The cycloalkyl group in R _x may have a substituent, and is preferably a monocyclic cycloalkyl group or a polycyclic cycloalkyl group having 3 to 20 carbon atoms, and an oxygen atom, a sulfur atom, It may have a nitrogen atom.
The aryl group for R _x may have a substituent, and preferably has 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 has 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, may be linear, or may be branched. The alkenyl group preferably has 3 to 20 carbon atoms. Examples of such alkenyl groups include vinyl groups, allyl groups, and styryl groups.

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, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Examples include carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, nitro group, hydrazino group, and heterocyclic group.

Preferred _examples of the divalent organic group for R _y include an alkylene group.
Examples of the ring structure that R _x and R _y may be bonded to each other include a 5- to 10-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring.

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

The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkyl group in the alkenyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group in R include a proton acceptor functional group or an ammonium group. Are the same as the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group mentioned above.

When B is —N (R _x ) R _y —, R and R _x are preferably bonded to each other to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.
Examples of the monocyclic 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. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures.

As _{R f} in _-W 1 _NHW 2 _{R f} represented by Q, preferred is an alkyl group which may have a fluorine atom of 1 to 6 carbon atoms, more preferably perfluoroalkyl of 1 to 6 carbon atoms It is a group. Further, as W ₁ and W ₂ , at least one is preferably —SO ₂ —, and more preferably, both W ₁ and W ₂ are —SO ₂ —.
Q is particularly preferably —SO ₃ H or —CO ₂ H from the viewpoint of the hydrophilicity of the acid group.
Of the compounds represented by the general formula (PA-1), a compound in which the Q site is a sulfonic acid can be synthesized by using a general sulfonamidation reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring-opening by reacting with an amine compound.

The compound (PA) is preferably an ionic compound. The proton acceptor functional group may be contained in either the anion portion or the cation portion, but is preferably contained in the anion portion.
Preferred examples of the compound (PA) include compounds represented by the following general formulas (4) to (6).

In the general formulas (4) to (6), A, X, n, B, R, R _f , W ₁ and W ₂ have the same meanings as those in the general formula (PA-1).
C ⁺ represents a counter cation.
The counter cation is preferably an onium cation. More specifically, the sulfonium cation described as S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ) in general formula (ZI) described above, I ⁺ (R ₂₀₄ ) (R ₂₀₅ ) in general formula (ZII) As a preferable example, an iodonium cation described as
Specific examples of the compound (PA) include the compounds exemplified in US2011 / 0269072A1 [0280].

In the present invention, a compound (PA) other than the compound that generates the compound represented by the general formula (PA-1) can be appropriately selected. For example, an ionic compound that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

In the formula, A represents a sulfur atom or an iodine atom.
m represents 1 or 2, and n represents 1 or 2. However, 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 ⁻ include the same anions as those of the photoacid generator (A) described above.
Specific examples of the aryl group of R and R _N is a phenyl group are preferably exemplified.

Specific examples of the proton acceptor functional group R _N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).
Specific examples of the ionic compound having a proton acceptor site in the cation moiety include the compounds exemplified in US2011 / 0269072A1 [0291].
Such a compound can be synthesized with reference to methods described in, for example, JP-A-2007-230913 and JP-A-2009-122623.

A compound (PA) may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the compound (PA) is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, based on the total solid content of the composition.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, an onium salt that becomes a weak acid relative to the photoacid generator can be used as an acid diffusion controller.
When a photoacid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the photoacid generator are used in combination, the photoacid generator is irradiated with actinic rays or radiation. When the generated acid collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

The onium salt that is a weak acid relative to the photoacid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ represents a hydrocarbon group which may have a substituent, and Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. Each of the M ⁺ is independently a sulfonium or iodonium cation.

Preferable examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cation in the general formula (ZI) described above and the iodonium cation in the general formula (ZII) described above.

Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include the structures exemplified in paragraph [0198] of JP2012-242799A.
Preferable examples of the anion moiety of the compound represented by the general formula (d1-2) include the structures exemplified in paragraph [0201] of JP2012-242799A.
Preferable examples of the anion moiety of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.

An onium salt that is a weak acid relative to the photoacid generator is (C) a compound having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety being linked by a covalent bond (Hereinafter also referred to as “onium salt (C)”).
The onium salt (C) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

In general formulas (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 the cation moiety and the anion moiety.
-X ^- it ^{^is,} -COO ^_-, -SO 3 _- represents an anion portion selected from _{^{_{-R 4 -, -SO 2 -,}}} -N. R ₄ is a group having a carbonyl group: —C (═O) —, a sulfonyl group: —S (═O) ₂ —, and a sulfinyl group: —S (═O) — at the site of connection with the adjacent N atom. Represents a valent substituent.
R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In (C-3), two of R ₁ to R ₃ may be combined 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 alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.

L ₁ as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L ₁ is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.
Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.
Preferable examples of the compound represented by the general formula (C-2) include compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.
Preferable examples of the compound represented by the general formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.

The content of the onium salt that is a weak acid relative to the photoacid generator is preferably 0.5 to 10.0% by mass, based on the solid content of the composition, and preferably 0.5 to 8.0. More preferably, it is more preferably 1.0% to 8.0% by mass.

<Solvent>
Examples of the solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition of the present invention by dissolving the above-described components include alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether. , Alkyl lactic acid ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may contain a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, pyruvic acid Mention may be made of organic solvents such as alkyl.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Preferred examples of the alkylene glycol monoalkyl ether include 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.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferred examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 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-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3- Methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methyl Preferred is cycloheptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid Examples include -2- (2-ethoxyethoxy) ethyl and propylene carbonate.
In the present invention, the above solvents may be used alone or in combination of two or more.

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, propylene glycol monomethyl ether, More preferred is ethyl lactate. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate and 2-heptanone are most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate. 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 is more preferable. A mixed solvent containing at least three kinds of propylene glycol monomethyl ether acetate, cyclohexanone and γ-butyrolactone is particularly preferable.
The solid content concentration of the radiation-sensitive or actinic ray-sensitive resin composition of the present invention is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and 3 to 20% by mass. Is more preferable.

<Surfactant>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a surfactant. When it contains, it contains either fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, surfactant having both fluorine atom and silicon atom), or two or more kinds It is preferable to do.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains the above-mentioned surfactant, adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It is possible to provide a resist pattern with less.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, F-top EF301, EF303, (Shin-Akita Kasei Co., Ltd.) ), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Surflon S-382 SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toagosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), Ftop EF121, EF122A, E 122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G, 204G 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

For example, as commercially available surfactants, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), acrylates having C ₆ F ₁₃ groups (or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), and acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly ( And a copolymer with oxypropylene)) acrylate (or methacrylate).

In the present invention, surfactants other than the fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may also be used.

These surfactants may be used alone or in several combinations.
The radiation-sensitive or actinic ray-sensitive resin composition of the present invention may or may not contain a surfactant, but when it contains a surfactant, its content is actinic ray-sensitive or radiation-sensitive. It is preferably 0.0001 to 2% by mass, more preferably 0.0001 to 2% by mass, and particularly preferably 0.0005 to 1% by mass with respect to the total solid content (total amount excluding the solvent) of the resin composition. .

<Dissolution-inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase the solubility in an alkaline developer>
As a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “dissolution inhibiting compound”), which is decomposed by the action of an acid to increase the solubility in an alkaline developer, it does not decrease the permeability of 220 nm or less. Preferred are alicyclic or aliphatic compounds containing acid-decomposable groups, such as cholic acid derivatives containing acid-decomposable groups described in OF SPIE, 2724, 355 (1996). Examples of the acid-decomposable group and alicyclic structure are the same as those described for the resin (B).

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, the phenolic hydroxyl group of the phenol compound is an acid-decomposable group as a dissolution inhibiting compound. Those containing a structure substituted with are preferred. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.

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

Specific examples of dissolution inhibiting compounds are shown below, but the present invention is not limited to these.

<Other additives>
In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a compound (for example, molecular weight) that further promotes solubility in dyes, plasticizers, photosensitizers, light absorbers, and developers as necessary. 1000 or less phenolic compounds, alicyclic or aliphatic compounds having a carboxyl group) and the like can be contained.

Such a phenol compound having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

[Pattern formation method]
Next, the pattern forming method of the present invention will be described.
The pattern forming method of the present invention comprises:
(1) forming an actinic ray-sensitive or radiation-sensitive film using the actinic ray-sensitive or radiation-sensitive resin composition;
(2) exposing the actinic ray-sensitive or radiation-sensitive film, and
(3) a step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer containing an organic solvent;
At least.

The exposure in the step (2) may be immersion exposure.
The pattern forming method of the present invention preferably includes (4) a heating step after (2) the exposure step.
The pattern formation method of this invention may include the (2) exposure process in multiple times.
The pattern formation method of this invention may include the (4) heating process in multiple times.

The actinic ray-sensitive or radiation-sensitive film of the present invention is formed using the above-described actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and more specifically, on a substrate, A film formed by applying the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferable. In the pattern forming method of the present invention, a step of forming a film (actinic ray-sensitive or radiation-sensitive film) on a substrate, a step of exposing the film, and a developing step are performed by generally known methods. It can be carried out.

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

Although there is no restriction | limiting in the light source wavelength used for the exposure apparatus in this invention, Infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, an electron beam, etc. can be mentioned, Preferably it is 250 nm or less. More preferably 220 nm or less, particularly preferably far ultraviolet light having a wavelength of 1 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., KrF excimer laser, ArF excimer laser, EUV or electron beam are preferable, and ArF excimer laser is more preferable.

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

In the case of performing immersion exposure, (A) after forming a film on the substrate, before the exposure step and / or (B) after exposing the film via the immersion liquid, Prior to the heating step, a step of washing the surface of the membrane with an aqueous chemical may be performed.
The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
When water is used, an additive (liquid) that reduces the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one which does not dissolve the resist layer on the wafer and can ignore the influence 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 include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.

On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.
The electrical resistance of the water used as the immersion liquid is preferably 18.3 MΩcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

The receding contact angle of the resist film formed by using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, and is passed through an immersion medium. And is preferably 75 ° or more, more preferably 75 to 85 °.

If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to realize a preferable receding contact angle, it is preferable to include the above-described hydrophobic resin (HR) in the actinic ray-sensitive or radiation-sensitive composition. Alternatively, an immersion liquid hardly soluble film (hereinafter also referred to as “top coat”) formed of the above-described hydrophobic resin (HR) may be provided on the upper layer of the resist film. The necessary functions for the top coat are appropriate application to the upper layer of the resist film and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the composition film and can be uniformly applied to the upper layer of the composition film.
Specific examples of the topcoat include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, fluorine-containing polymers, and the like. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed at the same time as the film development processing step, it is preferable that the peeling step can be performed with a developer containing an organic solvent.
The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. When water is used as the immersion liquid, the top coat is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.
The topcoat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used in the top coat is hardly soluble in the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and is not water-soluble. It is preferable that the medium be a sex medium. Further, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble. Hereinafter, the topcoat composition used for forming the topcoat layer will be described.

The solvent used in the top coat composition in the present invention is preferably an organic solvent. More preferred is an alcohol solvent.
When the solvent is an organic solvent, it is preferably a solvent that does not dissolve the resist film. As the solvent that 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. As the alcohol solvent, a primary alcohol is preferable from the viewpoint of applicability, and a primary alcohol having 4 to 8 carbon atoms is more preferable. As the primary alcohol having 4 to 8 carbon atoms, a linear, branched, or cyclic alcohol can be used, and preferably, for example, 1-butanol, 1-hexanol, 1-pentanol and 3-methyl- Examples include 1-butanol, 2-ethylbutanol, and perfluorobutyltetrahydrofuran.
As the resin for the top coat composition, resins having an acidic group described in JP-A-2009-134177 and JP-A-2009-91798 can also 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, particularly preferably from 10,000 to 100,000. Here, the weight average molecular weight of the resin indicates 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 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.3 to 3% by mass.
The topcoat material may contain components other than the resin, but the ratio of the resin to the solid content of the topcoat composition is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably Is from 95 to 100% by weight.
The solid content concentration of the top coat composition in the present invention is preferably 0.1 to 10, more preferably 0.2 to 6% by mass, and further preferably 0.3 to 5% by mass. preferable. By setting the solid content concentration within the above range, the topcoat composition can be uniformly applied onto the resist film.

In the pattern forming method of the present invention, an actinic ray-sensitive or radiation-sensitive film (typically a resist film) is formed on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and A topcoat layer can be formed on the resist film using the topcoat composition. The thickness of the resist film is preferably 10 to 100 nm, and the thickness of the topcoat layer is preferably 10 to 200 nm, more preferably 20 to 100 nm, and particularly preferably 40 to 80 nm.
As a method for applying the actinic ray-sensitive or radiation-sensitive resin composition on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.
For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater. Dry to form a resist film. In addition, a known antireflection film can be applied in advance. Further, it is preferable to dry the resist film before forming the top coat layer.
Next, the top coat composition can be applied on the obtained resist film by the same means as the resist film forming method and dried to form a top coat layer.
The resist film having the top coat layer as an 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 process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

In the present invention, the substrate on which the film is formed is not particularly limited, and an inorganic substrate such as silicon, SiN, SiO ₂ or TiN, a coated inorganic substrate such as SOG, a semiconductor manufacturing process such as an IC, a liquid crystal, or a thermal head For example, a substrate generally used in a circuit board manufacturing process or other photofabrication lithography process can be used. Furthermore, if necessary, an antireflection film may be formed between the resist film and the substrate. As the antireflection film, a known organic or inorganic antireflection film can be appropriately used.

The developer used in the step of developing the resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is not particularly limited, but for example, a developer containing an alkali developer or an organic solvent (Hereinafter also referred to as an organic developer) can be used.

When the pattern forming method of the present invention includes a step of developing using an alkali developer, usable alkali developers are not particularly limited, but generally, 2.38% by mass of tetramethylammonium hydroxide. An aqueous solution is desirable. In addition, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.
In addition to the above, examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, Tetraalkylammonium hydroxide such as trimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, quaternary ammonium salts such as trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide An alkaline aqueous solution of cyclic amines such as pyrrole and pihelidine can be used.

Further, after the developing process or the rinsing process, it is possible to perform a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid.

When the pattern forming method of the present invention includes a step of developing using an organic developer, examples of the organic developer include ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and the like. These polar solvents and hydrocarbon solvents can be used.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Examples include ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate. be able to.

Examples of the alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbuta Glycol ether solvents such as Lumpur can be mentioned.

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

Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to 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 ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

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

The organic developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the organic developer used in the present invention are the same as those in the basic compound that can be contained in the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.

When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.

By setting the discharge pressure of the discharged developer within the above range, it is possible to remarkably reduce pattern defects caused by resist residues after development.

The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.

The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.

Further, after the step of developing using a developer containing an organic solvent, a step of stopping development may be performed while substituting with another solvent.

In the pattern forming method of the present invention, a step of developing using a developer containing an organic solvent (organic solvent developing step) and a step of developing using an alkaline aqueous solution (alkali developing step) are used in combination. Also good. Thereby, a finer pattern can be formed.
In the present invention, a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 [0077]. ] And the same mechanism).
In the pattern forming method of the present invention, the order of the alkali development step and the organic solvent development step is not particularly limited.

It is preferable to include the process of wash | cleaning using a rinse liquid after the process developed using the developing solution containing an organic solvent.
The rinsing solution used in the rinsing step after the step of developing with a developer 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 rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.

More preferably, it contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents after the step of developing using a developer containing an organic solvent. A step of washing with a rinsing liquid is performed, more preferably, a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent is carried out, and particularly preferably, a rinsing liquid containing a monohydric alcohol is used. And, most preferably, the step of cleaning with a rinse solution containing a monohydric alcohol having 5 or more carbon atoms is performed.

Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 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 and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. Can.

A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

An appropriate amount of a surfactant can be added to the rinse solution.
In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among these, a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., 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 guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823).
The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method (preferably a negative type) of the present invention, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

Various materials used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention (for example, a developer, a rinsing liquid, a composition for forming an antireflection film, and for forming a top coat) The composition or the like preferably does not contain impurities such as metals. The content of the metal component contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less, and substantially not contained (the detection of the measuring device) with respect to the mass of each material. It is particularly preferred that it is below the limit.
Examples of a method for removing impurities such as metals from the various materials include filtration using a filter. The pore size of the filter is preferably 50 nm or less, more preferably 10 nm or less, and still more preferably 5 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
Moreover, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. And the like. The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
In addition to filter filtration, impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

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

<Synthesis of A1-2>
In a three-necked flask, 18 g (100 mmol) of A1-1 (adamantaneethanol) was dissolved in 160 g of methylene chloride, and 14.9 g (115 mmol) of diisopropylethylamine (iPr ₂ NEt) was added and cooled to −20 ° C. Subsequently, 30.8 g (110 mmol) of trifluoromethanesulfonic anhydride (Tf ₂ O) was dropped into the reaction solution using a dropping funnel. After further stirring at −20 ° C. for 1 hour, the reaction solution was added to a three-necked flask containing 400 g of saturated aqueous sodium bicarbonate and 300 g of hexane, and stirred at room temperature (25 ° C.) for 10 minutes. Subsequently, the organic phase was separated, washed with a saturated aqueous ammonium chloride solution, water and saturated brine, and concentrated to obtain 31 g of the desired compound A1-2.

<Synthesis of A1-4>
In a three-necked flask, 20 g (270 mmol) of A1-3 (2-methyl-1-propanol) was dissolved in 200 g of tetrahydrofuran (THF), and 38.4 g (297 mmol) of diisopropylethylamine was added and cooled to 0 ° C. Subsequently, 32.5 g (284 mmol) of methanesulfonic acid chloride (MsCl) was dropped into the reaction solution using a dropping funnel. After further stirring at 0 ° C. for 1 hour, the reaction solution was added to a three-necked flask containing 300 g of saturated aqueous sodium hydrogen carbonate, and stirred at room temperature (25 ° C.) for 10 minutes. Subsequently, after adding 300 g of ethyl acetate, the organic phase was separated, washed with water and saturated brine, and concentrated. The obtained crude product was purified by distillation (5 mmHG, external temperature 100 ° C.) to obtain 26 g of the target compound A1-4.

<Synthesis of A1-5>
In a three-necked flask, 20 g (134 mmol) of A1-4 was dissolved in 300 g of THF and 20 g of DMI (1,3-dimethyl-2-imidazolidinone) and cooled to −78 ° C. Subsequently, 50.6 ml (134 mmol) of n-BuLi (2.65 M / hexane solution) was added dropwise to the reaction solution with a syringe. After further stirring at −78 ° C. for 30 minutes, a solution prepared by dissolving 27.9 g (89.3 mmol) of A1-2 in 50 g of THF was dropped into the reaction solution using a dropping funnel. After raising the temperature to 0 ° C. and stirring for 1 hour, the reaction solution was added to a three-necked flask containing 1 L of hexane and 500 g of a saturated aqueous ammonium chloride solution, and stirred at room temperature (25 ° C.) for 30 minutes. Subsequently, the organic phase was separated, 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 target compound A1-5.

<Synthesis of A1-6>
In a three-necked flask, 11.6 g (37 mmol) of A1-5 was dissolved in 60 g of THF and cooled to −78 ° C. Subsequently, 58 ml (111 mmol) of sodium bis (trimethylsilyl) amide (NaHMDS) (1.9 M / hexane solution) was added dropwise to the reaction solution with a syringe. The mixture was further stirred at −78 ° C. for 30 minutes, and 35 g (111 mmol) of NFSi (N-fluorobenzenesulfonimide) was added to the reaction solution while being divided. After stirring at −78 ° C. for 2 hours, the reaction solution was added to a three-necked flask containing 500 g of hexane and 300 g of a saturated aqueous ammonium chloride solution, and stirred at room temperature (25 ° C.) for 30 minutes. Subsequently, the organic phase was separated, washed with water and saturated brine, and concentrated. The resulting crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 60/1) to obtain 5.0 g of the desired 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 solution, and the temperature was raised to 40 ° C. and stirred for 1 hour. Subsequently, after the internal temperature was brought to room temperature (25 ° C.), 50 g of methylene chloride and 50 g of water were added, and 1.96 g (5.7 mmol) of TPS-Br (triphenylsulfonium bromide) was added and stirred for 2 hours. The organic phase was separated and 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 following compounds A2 to A16 were synthesized by the same synthesis method as the above 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 this solution, 22.2 parts by mass of a monomer represented by the following structural formula M-1, 22.8 parts by mass of a monomer represented by the following structural formula M-2, and represented by the following structural formula M-3 A mixed solution of 6.6 parts by mass of monomer, 189.9 parts by mass of cyclohexanone, dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] over 5 hours It was dripped. After completion of dropping, the mixture was further stirred at 80 ° C. for 2 hours. The reaction solution was allowed to cool, then reprecipitated and filtered with a large amount of hexane / ethyl acetate (mass ratio 9: 1), and the obtained solid was vacuum-dried to obtain 41.1 parts by mass of Resin (1). .

The weight average molecular weight (Mw: converted to polystyrene) obtained from GPC (carrier: tetrahydrofuran (THF)) of the obtained resin (1) was Mw = 9500, and the dispersity was Mw / Mn = 1.62. ^The composition ratio measured by ¹³ C-NMR was 40/50/10 in molar ratio.
The same operations as in Synthesis Example 2 were performed to synthesize the following resins (2) to (12) as acid-decomposable resins.

<Resist preparation>
The components shown in Table 3 below are dissolved in a solvent, and a solution with a solid content of 4% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.05 μm. A functional resin composition was prepared. The actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in Table 3.
About each component in Table 3, the ratio at the time of using multiple is a mass ratio.

<Pattern formation method>
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto the silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. An actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was applied thereon and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.
The obtained wafer was used with an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) 1: Exposure was through a 6% halftone mask with a one line and space pattern. Ultra pure water was used as the immersion liquid. Then, it heated at 105 degreeC for 60 second (PEB: Post Exposure Bake). Subsequently, it was developed by paddling with butyl acetate for 30 seconds, and rinsed by padding with a rinsing solution [methyl isobutyl carbinol (MIBC)] for 30 seconds. Subsequently, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to form a 1: 1 line and space pattern having a line width of 50 nm.

<Evaluation>
(Focus tolerance (DOF: Depth of Focus))
Each pattern obtained by performing exposure and development by changing the exposure focus conditions in increments of 10 nm in the focus direction at the exposure amount for forming a line pattern having a line width of 50 nm under the exposure and development conditions of <Pattern Formation Method> Space line width (CD) was measured using a line width measurement scanning electron microscope SEM (Hitachi, Ltd. S-9380), and the minimum or maximum of the curve obtained by plotting each of the above CDs The focus corresponding to the value was the best focus. When the focus was changed around the best focus, a focus fluctuation range allowing a line width of 50 nm ± 10%, that is, a focus tolerance (nm) was calculated. A larger focus tolerance value is preferable.

(Sensitivity evaluation)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto the silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. A resist composition was applied thereon and baked at 90 ° C. for 60 seconds (PB: Prebake) to form a resist film having a thickness of 100 nm.
The obtained wafer was exposed with a liquid immersion exposure machine (manufactured by ASML; XT1700i) through a halftone mask with a pitch of 138 nm and a light shielding part of 50 nm. Ultra pure water was used as the immersion liquid. Thereafter, heating (PEB) was performed at a temperature of 85 ° C. for 60 seconds. The resulting wafer was developed with butyl acetate for 30 seconds to form a line and space pattern. By observing the obtained line and space pattern with a line width measurement scanning electron microscope SEM (Hitachi, Ltd. S-9380), the exposure amount at which the space width becomes 35 nm is defined as sensitivity (mJ / cm ² ). Asked. The sensitivity is preferably as the value is smaller.

The following abbreviations were used in the table.
<Compound (A) (Photoacid Generator (A))>

Also, the composition ratio (molar ratio; corresponding in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit are shown in Table 4 below. These were calculated | required by the method similar to resin (1) mentioned above.

<Acid diffusion controller (basic compound)>
The following compounds were used as acid diffusion control agents.

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

Table 5 shows the composition ratio (molar ratio; corresponding in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit. These were calculated | required by the method similar to resin (1) mentioned above.

<Surfactant>
W-1: Megafuck F176 (manufactured by DIC Corporation) (fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation) (fluorine and silicon)
W-3: PF6320 (manufactured by OMNOVA Solutions Inc.) (fluorine-based)
W-4: Troisol 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)

From the results shown in Table 3, the sensitivity of Examples 1 to 19 containing the compound (A) as compared with the actinic ray-sensitive or radiation-sensitive resin compositions of Comparative Examples 1 to 4 not containing the compound (A). It can be seen that the actinic ray-sensitive or radiation-sensitive resin composition has a large focus tolerance and high sensitivity.
Furthermore, T in the general formula (AI) is a single bond, Rx ₁ , Rx ₂ and Rx ₃ are alkyl groups, and the total number of carbon atoms of the alkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ And a resin having a group having a group that decomposes by the action of an acid and generates a polar group, wherein two or three of Rx ₁ , Rx ₂ , and Rx ₃ are not bonded to form a ring. 15 actinic ray-sensitive or radiation-sensitive resin composition, and resin having a group that decomposes by the action of an acid in which R ₃₂ in general formula (1) is an isopropyl group or a t-butyl group to generate a polar group It can be seen that the actinic ray-sensitive or radiation-sensitive resin compositions of Examples 2 and 9 to 15 that contain the compound further have a large focus tolerance and high sensitivity.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method using the same satisfy a large focus tolerance and a high sensitivity particularly in the formation of a very fine pattern (for example, a line width of 50 nm or less). be able to.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on July 1, 2014 (Japanese Patent Application No. 2014-136327), the contents of which are incorporated herein by reference.

Claims

An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (A) that generates a sulfonic acid represented by the following general formula (I) upon irradiation with actinic rays or radiation.

Where
Rf 1 and Rf 2 each independently represents a fluorine atom or a monovalent organic group containing at least one fluorine atom.
R 1 and R 2 each independently represents a monovalent organic group or hydrogen atom having no fluorine atom, and R 3 to R 5 each independently represents 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, the plurality of R 3 and the plurality of R 4 may be the same or different.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein R 1 and R 2 represent a hydrogen atom.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein R 5 represents a monovalent organic group having a cyclic structure.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3, wherein R 5 represents a monovalent organic group having a polycyclic ring structure.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein R 5 represents a polycyclic cycloalkyl group.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein Rf 1 and Rf 2 each represents a fluorine atom.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein R 3 and R 4 each represent a hydrogen atom.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein at least one of R 3 and R 4 represents an alkyl group.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8, wherein n represents 1.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9, wherein the compound (A) is an onium salt.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10, further comprising a resin having a group that decomposes by the action of an acid to generate a polar group.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 11, wherein the resin having a group that decomposes by the action of an acid to generate a polar group contains a repeating unit represented by the following general formula (AI). .

In 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 represents an alkyl group or a cycloalkyl group.
Two of Rx 1 to Rx 3 may combine to form a cycloalkyl group.
T in the general formula (AI) is a single bond, Rx 1 , Rx 2 and Rx 3 are alkyl groups, and the total number of carbon atoms of the alkyl group represented by Rx 1 , Rx 2 and Rx 3 is 4 or more. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 12, wherein two or three of Rx 1 , Rx 2 and Rx 3 are not bonded to form a ring.
The actinic ray-sensitive or resin according to claim 11, 12 or 13, wherein the resin having a group that decomposes by the action of an acid to generate a polar group is a resin having a repeating unit represented by the following general formula (1). Radiation sensitive resin composition.

In general formula (1),
R 31 represents a hydrogen atom, an alkyl group or a fluorinated alkyl group,
R 32 represents an alkyl group,
R 33 represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R 32 is bonded.
In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.
15. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 14, wherein R 32 is an isopropyl group or a t-butyl group.
Forming an actinic ray-sensitive or radiation-sensitive film from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 15;
A pattern forming method comprising: exposing the actinic ray sensitive or radiation sensitive film; and developing the exposed actinic ray sensitive 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.
An electronic device manufacturing method including the pattern forming method according to claim 16.
An electronic device manufactured by the electronic device manufacturing method according to claim 18.