JP6801115B2 - Sensitive light or radiation sensitive resin composition, resist film, pattern forming method, electronic device manufacturing method, mask blank with resist film, pattern forming method of mask blank with resist film - Google Patents

Description

The present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, a method for manufacturing an electronic device, a mask blank with a resist film, and a pattern forming method for a mask blank with a resist film.

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), microfabrication by lithography using a photoresist composition is performed.
In recent years, with the increasing integration of integrated circuits, the formation of ultrafine patterns in the submicron region or the quartermicron region has been required. Along with this, there is a tendency for the exposure wavelength to be shortened from g-ray to i-line and then to KrF excimer laser light, and now an exposure machine using an ArF excimer laser having a 193 nm wavelength as a light source has been developed. ing.
As a technique for further enhancing the resolving power, the development of the so-called "immersion method" in which the space between the projection lens and the sample is filled with a liquid having a high refractive index (hereinafter, also referred to as "immersion liquid") has progressed, and further, at present, In addition to excimer laser light, lithography using electron beam, X-ray, EUV (Extreme Ultra Violet) light, etc. is also being developed.
Along with this, chemically amplified resist compositions that are effectively sensitive to various active rays and radiation and have excellent sensitivity and resolution have been developed, and various compounds have also been developed for acid generators, which are the main constituents. ing.

For example, Patent Document 1 discloses a photoresist composition containing a specific acid generator.

Japanese Patent Publication No. 2011-511855

The present inventors have prepared an actinic cheilitis or radiation-sensitive resin composition using the acid generator described in Patent Document 1, and have a fine resist pattern having a narrow space width (for example, on the order of several tens of nm). Was prepared and examined with the above-mentioned actinic cheilitis or radiation-sensitive resin composition, and it was found that the shape of the pattern may not satisfy a predetermined requirement (that is, a shape other than a rectangle).
Further, the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition may have insufficient resolving power and exposure latitude.

Therefore, an object of the present invention is to provide a sensitive light-sensitive or radiation-sensitive resin composition having excellent resolution, exposure latitude, and pattern shape characteristics.
Further, the present invention relates to a resist film using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition, a pattern forming method, a method for manufacturing an electronic device, a mask blank with a resist film, and a pattern forming of a mask blank with a resist film. It also aims to provide a method.

As a result of diligent studies to achieve the above object, the present inventors have found that a desired effect can be obtained by using a compound that generates an acid having a specific structure, and have completed the present invention.
That is, the present inventors have found that the above object can be achieved by the following configuration.

[1] A sensitive light-sensitive or radiation-sensitive resin composition containing a resin and a compound that generates an acid represented by the following general formula (I) by irradiation with active light or radiation.

In the above general formula (I),
A represents a non-aromatic heterocycle having at least one linking group represented by X.
X is -O-, -S-, -S (= O)-, -S (= O) _2- , -O (C = O) O-, -O (C = O) NZ-, -S (= O) NZ-, -S (= O) ₂ NZ-, or a group combining these groups.
Z represents a monovalent organic group or a hydrogen atom.
R represents a monovalent organic group.
n represents an integer of 0 or more.
[2] The actinic light-sensitive or radiation-sensitive resin composition according to the above [1], wherein the compound is a compound represented by the following general formula (IA).

In the above general formula (IA),
M ⁺ represents a monovalent cation.
A represents a non-aromatic heterocycle having at least one linking group represented by X.
X is -O-, -S-, -S (= O)-, -S (= O) _2- , -O (C = O) O-, -O (C = O) NZ-, -S (= O) NZ-, -S (= O) ₂ NZ-, or a group combining these groups.
Z represents a monovalent organic group or a hydrogen atom.
R represents a monovalent organic group.
n represents an integer of 0 or more.
[3] The actinic or radiation-sensitive resin composition according to the above [1] or [2], wherein the resin is a resin having a group that decomposes by the action of an acid.
[4] The actinic light-sensitive or radiation-sensitive resin composition according to the above [1] or [2], which further contains a cross-linking agent and the resin is a resin having a phenolic hydroxyl group.
[5] The actinic cheilitis or radiation-sensitive property according to any one of the above [1] to [4], wherein a plurality of the above-mentioned Rs exist, and the plurality of the above-mentioned Rs may be connected to each other to form a ring. Resin composition.
[6] The actinic or radiation-sensitive resin composition according to any one of [1] to [5] above, wherein the volume of the acid generated by the compound is 240 Å ³ or more.
[7] The actinic light-sensitive or radiation-sensitive resin composition according to any one of the above [1] to [6], which further contains a basic compound.
[8] A resist film formed of the actinic or radiation-sensitive resin composition according to any one of the above [1] to [7].
[9] A resist film forming step of forming a resist film using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of the above [1] to [7], and an exposure step of exposing the resist film. A pattern forming method including a development step of developing the exposed resist film with a developing solution.
[10] The pattern forming method according to the above [9], wherein the exposure step is a step of exposing using an electron beam or extreme ultraviolet rays.
[11] A method for manufacturing an electronic device, which comprises the pattern forming method according to the above [9] or [10].
[12] A mask blank with a resist film, comprising the mask blank and the resist film according to the above [8] arranged on the mask blank.
[13] With a resist film, which comprises an exposure step of exposing the resist film in the mask blank with a resist film according to the above [12] and a developing step of developing the exposed resist film in the mask blank with a resist film. A method for forming a pattern of mask blanks.

According to the present invention, it is possible to provide a sensitive light-sensitive or radiation-sensitive resin composition having excellent resolution, exposure latitude, and pattern shape characteristics.
Further, according to the present invention, a resist film using the above-mentioned actinic cheilitis or radiation-sensitive resin composition, a pattern forming method, a method for manufacturing an electronic device, a mask blank with a resist film, and a mask blank with a resist film. A pattern forming method can be provided.

Hereinafter, the present invention will be described in detail.
Hereinafter, embodiments of the present invention will be described in detail.
In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substituent includes those having no substituent as well as those having 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).
The term "active light" or "radiation" as used herein refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), and the like. Means. In the present invention, "light" means active light rays or radiation.
Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), and exposure to X-rays, but also electron beams. , And drawing with particle beams such as ion beams is also included in the exposure.
In the specification of the present application, "~" is used in the meaning of including the numerical values described before and after the lower limit value and the upper limit value.

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are standard polystyrene-equivalent values obtained from GPC (gel permeation chromatography) under the following conditions.
Equipment: Tosoh HLC-8320GPC
Column: Tosoh TSK-GEL G3000PWXL
Developing solvent: THF (tetrahydrofuran)

[Actinic cheilitis or radiation-sensitive resin composition]
The actinic or radiation-sensitive resin composition of the present invention is a compound that generates an acid represented by the general formula (I) described later by irradiation with active light or radiation (hereinafter, also simply referred to as "acid generator". ) And a resin.

By adopting the above configuration, the sensitive light-sensitive or radiation-sensitive resin composition of the present invention is excellent in resolution and exposure latitude. Further, the resist pattern produced by the sensitive light-sensitive or radiation-sensitive resin composition of the present invention has a rectangular cross-sectional shape when cut in the direction perpendicular to the substrate which is the lower layer of the resist pattern. That is, the sensitive light-sensitive or radiation-sensitive resin composition of the present invention is also excellent in pattern shape characteristics.
The reason why the above characteristics are excellent is not clear, but it is presumed as follows.

The acid represented by the general formula (I) has a non-aromatic heterocycle, so that the interaction with the resin is increased. As a result, the diffusivity of the acid represented by the general formula (I) is suppressed, and the invasion into the non-exposed portion is reduced. As a result, it is presumed that the resolution and exposure latitude are excellent.
Further, since the acid represented by the general formula (I) has a high interaction with the resin, it is easy to disperse uniformly in the resist film (in other words, uneven distribution on the surface is suppressed). As a result, it is presumed that the pattern shape characteristics are excellent. For the same reason, it is presumed that the in-plane uniformity (CDU) of the line line width formed on the resist film is also excellent.

Hereinafter, the components contained in the sensitive light-sensitive or radiation-sensitive resin composition of the present invention will be described in detail.

<Acid generator>
The acid generator contained in the actinic or radiation-sensitive resin composition of the present invention generates an acid represented by the following general formula (I) by irradiation with active light or radiation.
The acid generator may be in the form of a low molecular weight compound or in the form of a polymer.
When the acid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.
When the acid generator is in the form of a polymer, its structure is not particularly limited, and for example, it may be incorporated as a part of <resin (A)> described later. When the acid generator is in the form of a polymer, its weight average molecular weight is preferably 1,000 to 200,000, more preferably 2,000 to 200,000 in terms of polystyrene by the GPC (Gel Permeation Chromatography) method. It is 20,000.

(Acid represented by general formula (I))
Hereinafter, the acid represented by the general formula (I) will be described.

In the above general formula (I),
A represents a non-aromatic heterocycle having at least one linking group represented by X.
X is -O-, -S-, -S (= O)-, -S (= O) _2- , -O (C = O) O-, -O (C = O) NZ-, -S (= O) NZ-, -S (= O) ₂ NZ-, or a group combining these groups.
Z represents a monovalent organic group or a hydrogen atom.
R represents a monovalent organic group.
n represents an integer of 0 or more.

In the general formula (I), the number of carbon atoms of the non-aromatic heterocycle represented by A (hereinafter, also referred to as “non-aromatic heterocycle A”) is not particularly limited, and is, for example, 3 to 20. 4 to 15 is preferable, and 4 to 10 is more preferable.

The non-aromatic heterocycle A has a linking group represented by X (hereinafter, also referred to as “linking group X”). The number of linking groups X in the non-aromatic heterocycle A is 1 or more, preferably 1 to 5, and more preferably 1 to 3.

The linking group X of the non-aromatic heterocycle A is -O-, -S-, -S (= O)-, -S (= O) _2- , -O (C = O) O-, -O. (C = O) NZ-, -S (= O) NZ-, -S (= O) ₂ NZ-, or a group combining these groups.
Here, Z represents a monovalent organic group or a hydrogen atom.
Examples of the monovalent organic group represented by Z include the same groups as the monovalent organic group represented by R in the general formula (I) described later, and among them, a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. Is preferable, and a linear alkyl group such as a methyl group or an ethyl group is more preferable.
As Z, a linear alkyl group or a hydrogen atom is preferable.

As the linking group X, −O− and −O (C = O) O− are preferable because the resolving power is more excellent.
On the other hand, the linking groups X are −S (= O) −, −S (= O) _2- , −O (C = O) NZ−, −S (= O) because the exposure latitude is superior. NZ-, -S (= O) ₂ NZ- is preferable, -S (= O) _2- , -O (C = O) NZ-, -S (= O) NZ-, -S (= O) ₂ NZ- is more preferred.

Specific examples of such a non-aromatic heterocycle A are shown below. However, the present invention is not limited to the following specific examples.

In the general formula (I), R represents a monovalent organic group.
The monovalent organic group represented by R is not particularly limited, and is, for example, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group and a tert-butoxy group; an aryl such as a phenoxy group and a p-tolyloxy group. Oxy group; Alkyltioxy group such as methylthioxy group, ethylthioxy group and tert-butyltioxy group; arylthiooxy group such as phenylthioxy group and p-tolyltioxy group; methoxycarbonyl group, butoxycarbonyl group and adamantylmethyloxycarbonyl group etc. Alkoxycarbonyl group; alkoxycarbonylalkylene group such as cyclohexyloxycarbonylmethylene group; aryloxycarbonyl group such as phenoxycarbonyl group; alkylcarbonyl group or cycloalkylcarbonyl group such as acetoxy group, cyclohexylcarbonyl group and adamantylcarbonyl group; methyl group , Ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group, 2-ethylhexyl group and other linear alkyl and branched alkyl groups; vinyl group, propenyl group and hexenyl group and other alkenyl groups; butazienyl group and the like. Alkadienyl group; Alcatrienyl group; Acetylene group; Alkinyl group such as propynyl group and hexynyl group; Cycloalkyl group; Aryl group such as phenyl group and tolyl group; benzyl group, 1-phenylethyl group, 2-phenylethyl group , 1-phenylpropyl group, 2-phenylpropyl group, 3-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and other aralkyl groups; monocyclic or polycyclic lactone group having 3 to 30 carbon atoms; Oxoalkyl group having 2 to 20 carbon atoms; oxocycloalkyl group having 6 to 10 carbon atoms; carbamoyl group; cyclic alkyl group such as cyclopentyl group and cyclohexyl group; carboxy group; heterocyclic group; cyano group; chlorine, fluorine atom, Halogen atoms such as iodine atom and bromine atom; a group combining these groups; and the like can be mentioned.
Of these, as the monovalent organic group represented by R, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxy group and an aryloxy group are preferable.

In the general formula (I), when a plurality of Rs exist (that is, when n is an integer of 2 or more), the plurality of Rs may be connected to each other to form a ring.

In the general formula (I), n represents an integer of 0 or more.
The integer represented by n is preferably 0 to 3, more preferably 0 to 2.

The reason that the effects of the present invention is more excellent, the volume of the acid represented by formula (I) is preferably 240 Å ³ or more, more preferably 300 Å ³ or more, more preferably 350 Å ³ or more, 400 Å ³ or more and particularly preferable. From the viewpoint of solubility or the like in a solvent, the volume is preferably 2000 Å ³ or less, more preferably 1500 Å ³ or less.
The volume of the acid is determined as follows using "WinMOPAC" manufactured by Fujitsu Limited. First, the chemical structure of each acid is input, then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure, and then these most stable conformations are determined. By calculating the molecular orbital of the conformation using the PM3 method, the "accessible volume" of each acid can be calculated.
1 Å is 0.1 nm.

Specific examples of the acid represented by the general formula (I) are shown below. However, the present invention is not limited to the following specific examples.

(Compound that generates an acid represented by the general formula (I) by irradiation with active light or radiation)
The structure of the compound that generates the acid represented by the general formula (I) by irradiation with active light or radiation is not particularly limited, and the compound has an ionic structure such as an onium salt such as a sulfonium salt and an iodonium salt, or , Oxim ester, imide ester and the like having a nonionic compound structure are preferable. The onium salt is more preferably a sulfonium salt.

-Compound having an ionic structure The compound that generates an acid represented by the general formula (I) by irradiation with active light or radiation is preferably a compound represented by the following general formula (IA).

In the above general formula (IA),
M ⁺ represents a monovalent cation.
A represents a non-aromatic heterocycle having at least one linking group represented by X.
X is -O-, -S-, -S (= O)-, -S (= O) _2- , -O (C = O) O-, -O (C = O) NZ-, -S (= O) NZ-, -S (= O) ₂ NZ-, or a group combining these groups.
Z represents a monovalent organic group or a hydrogen atom.
R represents a monovalent organic group.
n represents an integer of 0 or more.

A, R and n, and X and Z in the general formula (IA) are synonymous with A, R and n, and X and Z described in the general formula (I), respectively.

In the general formula (IA), examples of the monovalent cation represented by M ⁺ include cations represented by the following general formulas (ZI) and (ZII).

In the above general formula (ZI)
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
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 bonding two of R _{201 to} R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group).

The acid generator may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (ZI) is single-bonded or single-bonded to at least one of R _{201 to} R ₂₀₃ of another compound represented by the general formula (ZI). It may be a compound having a structure bonded via a linking group.

From the viewpoint of acid strength, it is preferable that the pKa of the generated acid is -1 or less in order to improve the sensitivity.

The organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include aryl groups (preferably 6 to 15 carbon atoms), linear or branched alkyl groups (preferably 1 to 10 carbon atoms), and cycloalkyl groups (carbons are preferable). Numbers 3 to 15 are preferable) and the like.
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , it is preferable that at least one is an aryl group, and it is more preferable that all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group and the like, a heteroaryl group such as an indole residue and a pyrrole residue can also be used.

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 a halogen atom such as a nitro group and a fluorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), and a cycloalkyl group (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), and an alkoxycarbonyloxy group (preferably carbon number 2 to 12). 2 to 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. Alkylene group as a linking group (preferably 1 to 3 carbon atoms), - O -, - S -, - CO-, and, -SO ₂ - and the like include, but are not limited to.
Preferred structures in the case where 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, USA. Compounds exemplified by formulas (I-1) to (I-70) in Japanese Patent Application Publication No. 2003/0224288A1 and formula (IA-1) in US Patent Application Publication No. 2003/0077540A1. -(IA-54), cation structures such as compounds exemplified by the formulas (IB-1) to (IB-24) can be mentioned.

Preferred examples of the cation represented by the general formula (ZI) include the cation represented by the general formula (ZI-3) or (ZI-4) described below.

First, the cation represented by the general formula (ZI-3) will be described.

In the above general formula (ZI-3),
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 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be linked to each other to form a ring.
R ₁ and R ₂ may be connected to each other to form a ring.
R _x and R _y each independently contain 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. Represented, R _x and R _y may be linked to each other to form a ring, and this ring structure contains an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond. May be good.

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, and n-octadecyl. Examples thereof include a linear alkyl group such as a group, and a branched alkyl group such as an isopropyl group, an isobutyl group, a t-butyl group, a neopentyl group, and a 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. And so on.

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

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

The aryl group as R ₁ is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a biphenyl group. The aryl group of R ₁ may have a substituent, and 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 group as the above-mentioned alkyl group as R ₁ , cycloalkyl group, alkoxy group and cycloalkoxy group can be mentioned.

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 linked to each other to form a ring. At least one of R ₂ and R ₃ preferably represents an alkyl group, a cycloalkyl group, and an aryl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group, and aryl group for R ₂ and R ₃ include the same specific examples and preferred examples as 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 contained in R ₂ and R ₃ that contribute to the formation of the ring is preferably 4 to 7, and 4 or 5 Is particularly preferable.

R ₁ and R ₂ may be connected to each other to form a ring. When R ₁ and R ₂ are linked 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. It is preferably an alkylene group (preferably a methylene group or an ethylene group), and examples of the preferred substituent include the same substituents that the above-mentioned 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, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group. , Pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, and , Eikosyl group and the like.

The cycloalkyl group represented by R _x and R _y preferably includes a cycloalkyl group having 3 to 20 carbon atoms, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like. it can.

The alkenyl group represented by R _x and R _y preferably includes 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, and specifically, a phenyl group, a naphthyl group, an azulenyl group, an acenaphthylenyl group, a phenanthrenyl group, a penalenyl group and a phenyl group Examples thereof include a nantrasenyl group, a fluorenyl group, an anthrasenyl group, a pyrenyl group, a benzopyrenyl group and the like. It is preferably a phenyl group or a naphthyl group, and more preferably 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.

The cation represented by the general formula (ZI-3) is preferably a cation represented by the following general formulas (ZI-3a) and (ZI-3b).

In formula (ZI-3a) and _{(ZI-3b), R 1} , R 2 and _{R 3} are as defined for the general formula (ZI-3).

Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and is preferably an oxygen atom or a nitrogen atom. m, n, p and q mean integers, preferably 0 to 3, more preferably 1 to 2, and even more preferably 1. The alkylene group connecting S ⁺ and Y 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 does not exist when Y is an oxygen atom or a sulfur atom. R ₅ is preferably a group containing an electron-attracting group, and more preferably a group represented by the following general formulas (ZI-3a-1) to (ZI-3a-4).

In the above (ZI-3a-1) to (ZI-3a-3), R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and is preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group, and aryl group for R include the same specific examples and preferred examples as described above for R ₁ in the above general formula (ZI-3).
In the above (ZI-3a-1) to (ZI-3a-4), * represents a bond that connects to a nitrogen atom as Y in the compound represented by the general formula (ZI-3a).

If Y is a nitrogen atom, _{R 5} is preferably a group represented by _-SO 2 -R _4. R ₄ represents an alkyl group, a cycloalkyl group or an aryl group, and is preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group, and aryl group for R ₄ include the same examples as those described above for R ₁ and preferred examples.

The cation represented by the general formula (ZI-3) is particularly preferably a cation represented by the following general formulas (ZI-3a') and (ZI-3b').

As in the general formula (ZI-3a ') and _{(ZI-3b'), R} 1, R 2, R 3, Y and _{R 5} are as defined above general formula (ZI-3a) and (ZI-3b) Is.

Specific examples of the cation represented by the general formula (ZI-3) are given below. In the following formula, Me represents a methyl group and ⁿ Bu represents an n-butyl group.

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

In the general formula (ZI-4),
R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have substituents.
When a plurality of R _14s are present, each of them independently has a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group. Represent. These groups may have substituents.
Each of R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. The two R _15s may be bonded to each other to form a ring, and the atoms constituting the ring may contain heteroatoms such as an oxygen atom, a sulfur atom and a nitrogen atom. These groups may have substituents.
l represents an integer from 0 to 2.
r represents an integer from 0 to 8.

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 of R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group.
The alkoxy groups of R ₁₃ and R ₁₄ are linear or branched, and preferably have 1 to 10 carbon atoms.
The alkoxycarbonyl groups of R ₁₃ and R ₁₄ are linear or branched, and preferably have 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.
Examples of the alkyl group of the alkylcarbonyl group of R ₁₄ include the same specific examples as those of the alkyl group as R _{13 to} R ₁₅ described above.
The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ are linear, branched, and cyclic, and preferably have 1 to 10 carbon atoms.

The substituents that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyl. Oxy groups and the like can be mentioned.

The two ring structure which may be R ₁₅ is formed by bonding two of R ₁₅ are of the general formula 5-membered or 6-membered to form with (ZI-4) a sulfur atom in the ring, particularly preferably Is a 5-membered ring (ie, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), which may be fused with an aryl group or a cycloalkyl group. This divalent R ₁₅ may have a substituent, and examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, and an alkoxycarbonyl. Examples include a group and an alkoxycarbonyloxy group. A plurality of substituents for the above ring structure may be present, or they may be bonded to each other to form a ring.

The R ₁₅ in the general formula (ZI-4) is preferably a divalent group in which a methyl group, an ethyl group, a naphthyl group, and two R _15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom. , a divalent group in which two R ₁₅ to form a tetrahydrothiophene ring structure bonded to together with the sulfur atom to each other are particularly preferred.

As the substituent that R ₁₃ and R ₁₄ can have, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, and a halogen atom (particularly, a fluorine atom) are preferable.
As l, 0 or 1 is preferable, and 1 is more preferable.
As r, an integer of 0 to 2 is preferable.

Specific examples of the cation structure represented by the general formula (ZI-3) or (ZI-4) described above include the above-mentioned JP-A-2004-233661, JP-A-2003-35948, and US patent application. In addition to the cationic structures of compounds and the like exemplified in Publication No. 2003/0224288A1 and US Patent Application Publication No. 2003/0077540A1, for example, paragraphs 0046, 0047, 0072 to JP-A-2011-533360. Examples thereof include a cation structure in a chemical structure exemplified in 0077, 0107 to 0110, a cation structure in a chemical structure or the like exemplified in paragraphs 0135 to 0137, 0151, 0196 to 0199 of JP2011-53430A. ..

Next, the general formula (ZII) will be described.
In the general formula (ZII), R ₂₀₄ and R ₂₀₅ each independently represent 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-mentioned compound (ZI).

Among them, the aryl group of 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.

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

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have a substituent. _{Examples of} the substituents that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have include the aryl group, alkyl group, and alkyl group of R _{201 to} R ₂₀₃ in the above-mentioned compound (ZI). Examples of the cycloalkyl group may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 15 carbon atoms). , Alkyl groups (for example, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.
A specific example of the cation represented by the general formula (ZII) is shown.

As a preferable example of the cation represented by the general formula (ZI), the cation represented by the general formula (7) described below can also be mentioned.

In the formula, A represents a sulfur atom.
m represents 1 or 2 and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3.
R represents an aryl group.
R _N represents an aryl group substituted with a proton acceptor functional group.
A proton-accepting functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, 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 having an unshared electron pair that does not contribute to. 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 shown in the following general formula.

Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza crown ether structure, a 1-3-grade amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.

A compound (PA) having a proton-accepting functional group is decomposed by irradiation with active light or radiation to generate a compound in which the proton-accepting property is lowered or eliminated, or the proton-accepting property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group. Specifically, it means that when a proton adduct is formed from a compound (PA) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
A specific example of the cation represented by the general formula (7) is shown. In the following general formula, Et represents an ethyl group.

-Compound having a non-ionic compound structure The compound that generates an acid represented by the general formula (I) by irradiation with active light or radiation may have a non-ionic compound structure, for example, the following. Examples thereof include compounds represented by the general formulas (ZV) and (ZVI).

In the general formula (ZV), (ZVI),
R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group, a cyano group or an aryl group. The aryl group, alkyl group, and cycloalkyl group of R ₂₀₉ and R ₂₁₀ are the same as those described as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the above-mentioned compound (ZI). is there. The aryl group, alkyl group, and cycloalkyl group of R ₂₀₉ and R ₂₁₀ may have a substituent. Examples of this substituent include the same substituents that the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the above-mentioned compound (ZI) may have.

A'represents an alkylene group, an alkenylene group or an arylene group.
The alkylene group as A'may have a substituent, and preferably has 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. be able to.
The alkenylene group as A'may have a substituent, and preferably has 2 to 6 carbon atoms, for example, an ethenylene group, a propenylene group, a butenylene group and the like.
The arylene group as A'may have a substituent, and preferably has 6 to 15 carbon atoms, for example, a phenylene group, a trilene group, a naphthylene group and the like.

Examples of the substituent that A'may have include those having an active hydrogen such as a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, and a carboxy group, and further. , Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (eg methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.) ), Acyloxy group (acetoxy group, propanoyloxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), cyano group, nitro group and the like. As the arylene group, an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.) can be further mentioned.

Rz represents a structure in which the H of the acid represented by the general formula (I) is dissociated, and is represented by the following general formula (IS).

In the general formula (IS),
* Represents a binding portion with a compound residue represented by the general formula (ZV) or (ZVI).
A represents a non-aromatic heterocycle having at least one linking group represented by X.
X is -O-, -S-, -S (= O)-, -S (= O) _2- , -O (C = O) O-, -O (C = O) NZ-, -S (= O) NZ-, -S (= O) ₂ NZ-, or a group combining these groups.
Z represents a monovalent organic group or a hydrogen atom.
R represents a monovalent organic group.
n represents an integer of 0 or more.

A, R and n, and X and Z in the general formula (IS) are synonymous with A, R and n, and X and Z described in the general formula (I), respectively.

Specific examples of compound residues represented by the general formula (ZV) or (ZVI) are shown below. * In the specific example represents a joint portion with * in the above general formula (IS). Me represents a methyl group.

Hereinafter, specific examples of compounds that generate an acid represented by the general formula (I) by irradiation with active light or radiation will be given. However, the present invention is not limited to the following specific examples.

Specific examples of the case where the compound that generates the acid represented by the general formula (I) by irradiation with active light or radiation is in the form of a polymer are given below. However, the present invention is not limited to the following specific examples.

The method for synthesizing the compound that generates the acid represented by the general formula (I) by irradiation with active light or radiation can be synthesized by a known synthesis method.

In the composition of the present invention, the above-mentioned compound that generates an acid represented by the general formula (I) (acid generator (I)) can be used alone or in combination of two or more.

The composition of the present invention may be used in combination with the acid generator (I) described above and an acid generator other than the acid generator (I).

As the acid generator other than the acid generator (I), it is used as a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent for pigments, a photodiscolorant, a microresist, or the like. Known compounds that generate acid by irradiation with active light or radiation, and mixtures thereof, can be appropriately selected and used.

For example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, or o-nitrobenzyl sulfonate can be mentioned.

A group in which an acid is generated by irradiation with these active rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of a polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407. Japanese Patent Application Laid-Open No. 63-26653, Japanese Patent Application Laid-Open No. 55-164824, Japanese Patent Application Laid-Open No. 62-69263, Japanese Patent Application Laid-Open No. 63-146038, Japanese Patent Application Laid-Open No. 63-163452, The compounds described in Japanese Patent Application Laid-Open No. 62-153853 or Japanese Patent Application Laid-Open No. 63-146029 can be used.

Further, compounds that generate acid by light as described in US Pat. No. 3,779,778 or European Patent No. 126,712 can also be used.

As the acid generator other than the acid generator (I), the description of paragraphs <0337> to <0400> of US2012 / 0076996A1 can be referred to, and these contents are incorporated in the present specification.

The content of the acid generator in the composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, based on the total solid content of the actinic or radiation-sensitive composition. It is 18% by mass, more preferably 5 to 18% by mass. When the composition of the present invention contains two or more photoacid generators, the total content of the photoacid generators is preferably within the above range.

<Resin (A)>
The resin (A) is, for example, a resin whose polarity changes due to the action of an acid. The actinic light-sensitive or radiation-sensitive resin composition of the present invention contains, as the resin (A), a resin having a group that decomposes by the action of an acid (hereinafter, also referred to as "resin (A1)"). Alternatively, it is preferable that the resin (A) contains a resin having a phenolic hydroxyl group (hereinafter, also referred to as “resin (A2)”).

(Resin (A1) having a group that decomposes by the action of acid)
The resin (A1) is a resin whose solubility in an alkaline developer is increased by the action of an acid, or its solubility in a developer containing an organic solvent as a main component is decreased by the action of an acid, and the main chain of the resin and the resin (A1) At least one of the side chains has a group (hereinafter, also referred to as "acid-degradable group") which is decomposed by the action of an acid to form an alkali-soluble group.
Examples of the alkali-soluble group include a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

The resin (A1) preferably has a repeating unit having the above-mentioned acid-degradable group. The repeating unit having an acid-degradable group is preferably a repeating unit represented by the following general formula (AI).

In the general formula (AI)
Xa ₁ represents a hydrogen atom and an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ independently represent an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
Two of Rx _{1 to} Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Represented by xa _1, as the alkyl group which may have a substituent group, include groups represented by methyl group or _-CH 2 _{-R 11.} R ₁₁ represents a halogen atom (fluorine atom or the like), a hydroxy group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. It is an alkyl group of, more preferably a methyl group. In one embodiment, Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.

Examples of the divalent linking group of T include an alkylene group, an -COO-Rt- group, an -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, a − (CH ₂ ) ₂ − group, or a − (CH ₂ ) ₃ − group.

Alkyl groups of Rx _{1 to} Rx ₃ include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. preferable.

Examples of the cycloalkyl group of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group and the like. The polycyclic cycloalkyl group of is preferred.
Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca. A polycyclic cycloalkyl group such as an Nyl group and an adamantyl group is preferable. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.

The cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced with.

As the repeating unit represented by the general formula (AI), for example, it is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), and a carboxy group. Examples thereof include a group, an alkoxycarbonyl group (2 to 6 carbon atoms), and a group having 8 or less carbon atoms is preferable.

The total content of the repeating units having an acid-degradable group is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, and more preferably 30 to all the repeating units in the resin (A1). It is more preferably ~ 80 mol%.

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

In the specific example, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and if there are a plurality of Z, they are independent of each other. p represents 0 or a positive integer. Examples of the substituent containing a polar group represented by Z include a linear or branched alkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, and a cycloalkyl group, which is preferable. Is an alkyl group having a hydroxyl group. The isopropyl group is particularly preferable as the branched alkyl group.

The resin (A1) preferably contains the repeating unit represented by the general formula (AI) as the repeating unit represented by the general formula (AI).

In general formula (3),
R ₃₁ represents a hydrogen atom or an alkyl group.
R ₃₂ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group.
R ₃₃ represents an atomic group required to form a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R ₃₂ is bonded. In the alicyclic hydrocarbon structure, a part of the carbon atoms constituting the ring may be substituted with a heteroatom or a group having a heteroatom.

The alkyl group of 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 a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl 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 a carbon atom, examples of the hetero atom that can form a ring include an oxygen atom and a sulfur atom, and examples of the group having the hetero atom include a carbonyl group and the like. Can be mentioned. 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 carbon atoms is preferably formed only of carbon atoms and hydrogen atoms.

Specific examples of the repeating unit having the structure represented by the general formula (3) are given below, but the present invention is not limited thereto.

The content of the repeating unit having the structure represented by the general formula (3) is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, and 30 to 30 to all the repeating units in the resin (A1). 70 mol% is more preferred.

The resin (A1) preferably contains a repeating unit having a lactone structure or a sultone (cyclic sulfonic acid ester) structure.

As the lactone group or sultone group, any one having a lactone structure or a sultone structure can be used, but it is preferably a 5- to 7-membered ring lactone structure or a sultone structure, and a 5- to 7-membered ring lactone. It is preferable that the structure or the sultone structure is fused with another ring structure so as to form a bicyclo structure or a spiro structure. 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). The lactone structure or sultone structure may be directly bonded to the main chain. The preferred lactone structure or sultone structure is (LC1-1), (LC1-4), (LC1-5), (LC1-8), and more preferably (LC1-4). By using a specific lactone structure or sultone structure, LWR (line width roughness) 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 an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group. , Halogen atom, hydroxyl group, cyano group, acid-degradable group and the like. More preferably, it is an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-degradable group. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, a plurality of existing substituents (Rb ₂ ) may be the same or different, and a plurality of existing substituents (Rb ₂ ) may be bonded to each other to form a ring.

The resin (A1) 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 _R0 , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
When there are a plurality of Z, they are independently single bond, ether bond, ester bond, amide bond, urethane bond.

Or urea bond

Represents. Here, R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
n is the number of repetitions of the structure represented by −R ₀ −Z−, and represents an integer of 0 to 2.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and cycloalkylene group of R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group of R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group of R ₇ may be substituted, respectively, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a mercapto group, and a hydroxy group. Examples thereof include an alkoxy group such as a group, a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group and a benzyloxy group, and an acetoxy group such as an acetyloxy group and a propionyloxy group. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

The preferred chain alkylene group in 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. Be done. Preferred cycloalkylene groups are cycloalkylene groups having 3 to 20 carbon atoms, and examples thereof include cyclohexylene group, cyclopentylene group, norbornene group, and adamantylene group. Of these, 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 as a specific example, the above-mentioned general formula (LC1-1) Examples thereof include a lactone structure or a sultone structure represented by (LC1-17), (SL1-1) and (SL1-2), and the structure represented by (LC1-4) is particularly preferable. It is more preferable that n ₂ in (LC1-1) to (LC1-17), (SL1-1) and (SL1-2) is 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or a sulton structure, or a monovalent organic group having a lactone structure or a sulton structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent, and cyano. A monovalent organic group having a lactone structure (cyanolactone) or a sulton structure (cyanosulton) having a group as a substituent is more preferable.

In the general formula (III), n is preferably 1 or 2.

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

In the following specific examples, R represents a hydrogen atom, an alkyl group or a halogen atom which may have a substituent, and preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group, or an acetoxymethyl group.
In the formula below, Me represents a methyl group.

When a plurality of types of repeating units are contained, the content of the repeating unit represented by the general formula (III) is preferably 15 to 60 mol%, more preferably 20 to 60 mol%, based on all the repeating units in the resin (A1). %, More preferably 30 to 50 mol%.

The resin (A1) may contain a repeating unit having the above-mentioned lactone structure or sultone structure in addition to the unit represented by the general formula (III).

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

Among the above specific examples, the following repeating units can be mentioned as particularly preferable repeating units. By selecting the optimum lactone structure or sultone structure, the pattern profile and sparse / density dependence are improved.

The repeating unit having a lactone group or a sultone group usually has an optical isomer, but any optical isomer may be used. One kind of 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.

When a plurality of types of repeating units having a lactone structure or sultone structure other than the repeating unit represented by the general formula (III) are contained, the total content of the repeating units is 15 to 60 mol% with respect to all the repeating units in the resin. It is preferable, more preferably 20 to 50 mol%, still more preferably 30 to 50 mol%.

It is also possible to use a repeating unit having two or more kinds of lactone structures or sultone structures selected from the general formula (III) in combination. When used in combination, it is preferable to select two or more of the repeating units having a lactone structure or a sultone structure in which n is 1 from the general formula (III) and use them in combination.

When the sensitive light-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure, the resin (A1) has substantially no aromatic group from the viewpoint of transparency to ArF light. Is preferable. More specifically, during the total repetition of the resin (A1), the repeating unit having an aromatic group is preferably 5 mol% or less, and more preferably 3 mol% or less.
The resin (A1) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

The resin (A1) has, for example, an alicyclic hydrocarbon structure having no polar group (for example, an alkali-soluble group, a hydroxyl group, a cyano group, etc.) as a repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure. However, it may contain non-acidolytic repeating units. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In the general formula (IV), R ₅ having at least one cyclic structure represents a hydrocarbon group having no polar group.
Ra represents a hydrogen atom, an alkyl group or _-CH 2 -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and more preferably a hydrogen atom or a methyl group.
The cyclic structure of 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 such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group, or a cyclohexenyl group having 3 to 12 carbon atoms. Cycloalkenyl groups can be mentioned. A preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferably a cyclopentyl group or a cyclohexyl group.
The polycyclic hydrocarbon group includes a ring-assembled hydrocarbon group or a cross-linked ring-type hydrocarbon group, and examples of the ring-assembled hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. Examples of the crosslinked cyclic hydrocarbon ring include 2 such as pinan, bornan, norpinan, norbornane, or bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredane, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, or tricyclo [4.3.1.1 ^2,5 ] undecane rings. Or, tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodecane, or a tetracyclic hydrocarbon ring such as a perhydro-1,4-methano-5,8-methanonaphthalene ring can be mentioned. The crosslinked cyclic hydrocarbon ring includes a fused cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, or perhydro. A fused ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenanthrene ring are condensed is also included.
As preferred crosslinked-ring hydrocarbon rings, a norbornyl group, an adamantyl group, a bicyclooctanyl group, or the like tricyclo [5,2,1,0 ^2,6] decanyl group. A more preferable crosslinked cyclic hydrocarbon ring includes a norbornyl group or an adamantyl group.
These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxy group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. Can be mentioned. As the halogen atom, a bromine atom, a chlorine atom or a fluorine atom is preferable. As the alkyl group, a methyl group, an ethyl group, a butyl group, or a t-butyl group is preferable. The above-mentioned alkyl group may further have a substituent, and the substituent which may further have is a halogen atom, an alkyl group, a hydroxy group substituted with a hydrogen atom, or a hydrogen atom substituted. Amino group can be mentioned.
Examples of the group in which the hydrogen atom is substituted 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. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and as a substituted methyl group, methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, or 2-methoxyethoxymethyl group is preferable, and a substituted ethyl group is used. 1-ethoxyethyl or 1-methyl-1-methoxyethyl is preferable, and the acyl group is an aliphatic having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl or pivaloyl group. An acyl group is preferable, and as the alkoxycarbonyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms is preferable.

When the resin (A1) has an alicyclic hydrocarbon structure having no polar group and contains a non-acid-decomposable repeating unit, the content of the repeating unit is the total repeating unit in the resin (A1). On the other hand, 1 to 40 mol% is preferable, and 2 to 20 mol% is more preferable.
Specific examples of the non-acid-decomposable repeating unit having an alicyclic hydrocarbon structure having no polar group include the repeating unit disclosed in paragraph 0354 of Japanese Patent Application Laid-Open No. 2012/0135348. , The present invention is not limited to these.

On the other hand, when the resist film is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light (EUV light or the like) having a wavelength of 50 nm or less, the resin (A1) has an aromatic hydrocarbon group. It preferably contains a repeating unit, and more preferably contains a repeating unit having a phenolic hydroxyl group. As the repeating unit having a phenolic hydroxyl group, the repeating unit shown below is particularly preferable.

Specific examples of the resin containing a repeating unit having such an aromatic hydrocarbon group include a resin having a repeating unit represented by the following general formula (A).

In the formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Ar ₁ represents, for example, an aromatic ring group. R ₀₃ and Ar ₁ may be alkylene groups, and both may be bonded to each other to form a 5-membered or 6-membered ring together with the -CC- chain.

The n Ys each independently represent a group that is eliminated by the action of a hydrogen atom or an acid. However, at least one of Y represents a group that is eliminated by the action of an acid.
n represents an integer of 1 to 4, preferably 1 to 2, and more preferably 1.

The alkyl groups as R _{01 to} R ₀₃ are, for example, alkyl groups having 20 or less carbon atoms, preferably methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, and hexyl groups. , 2-Ethylhexyl group, octyl group or dodecyl group. More preferably, these alkyl groups are alkyl groups having 8 or less carbon atoms. These alkyl groups may have a substituent.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R _{01 to} R ₀₃ .

The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Preferably, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group can be mentioned. These cycloalkyl groups may have a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is more preferable.

When R ₀₃ represents an alkylene group, the alkylene group preferably includes an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.

The aromatic ring group as Ar ₁ is preferably an aromatic ring group having 6 to 14 carbon atoms, and examples thereof include a benzene ring, a toluene ring and a naphthalene ring. These aromatic ring groups may have a substituent.

Examples of the group Y desorbed by the action of an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (= O) -OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ). ), -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ) -C (= O) -OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) and Examples include groups represented by −CH (R ₃₆ ) (Ar).

In the formula, R _{36 to} R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be coupled to each other to form a ring structure.
R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
Ar represents an aryl group.

The alkyl group as R _{36 to} R ₃₉ , R ₀₁ , or R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, or sec-. Examples include a butyl group, a hexyl group and an octyl group.

The cycloalkyl group as R _{36 to} R ₃₉ , R ₀₁ , or R ₀₂ may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. As the polycyclic cycloalkyl group, a cycloalkyl group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinanyl group, a tricyclodecanyl group, and the like. Examples thereof include a tetracyclododecyl group and an androstanyl group. Some of the carbon atoms in the cycloalkyl group may be replaced by heteroatoms such as oxygen atoms.

The aryl group as R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ , or Ar is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

The aralkyl group as R _{36 to} R ₃₉ , R ₀₁ , or R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and for example, a benzyl group, a phenethyl group, and a naphthylmethyl group are preferable.

The alkenyl group as R _{36 to} R ₃₉ , R ₀₁ , or R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group. ..

The ring that can be formed by combining R ₃₆ and R ₃₇ with each other may be a monocyclic type or a polycyclic type. The monocyclic type is preferably a cycloalkane structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. As the polycyclic type, a cycloalkane structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. A part of the carbon atom in the ring structure may be replaced by a hetero atom such as an oxygen atom.

Each of the above groups may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group, a thioether group, an acyl group and an acyloxy group. , Halkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.

As the group Y desorbed by the action of an acid, a structure represented by the following general formula (B) is more preferable.

In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group, a cyclic aliphatic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. These cyclic aliphatic groups and aromatic ring groups may contain heteroatoms.
Q, M, at least two of L ₁ may be bonded to each other to form a 5-membered or 6-membered ring.

The alkyl groups as L ₁ and L ₂ are, for example, alkyl groups having 1 to 8 carbon atoms, and specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group and An octyl group can be mentioned.

The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

The aryl group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group and an anthryl group.

The aralkyl group as L ₁ and L ₂ is, for example, an aralkyl group having 6 to 20 carbon atoms, and specific examples thereof include a benzyl group and a phenethyl group.

The divalent linking group as M is, for example, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group), a cycloalkylene group (for example, a cyclopentylene group or a cyclohexylene group). ), Alkenylene group (eg, ethylene group, propenylene group or butenylene group), arylene group (eg, phenylene group, tolylen group or naphthylene group), -S-, -O-, -CO-, -SO ₂ -,- N (R ₀ )-or a combination of two or more of these. Here, R ₀ is a hydrogen atom or an alkyl group. The alkyl group as R ₀ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group and an octyl group. Can be mentioned.

The alkyl group and cycloalkyl group as Q are the same as the above-mentioned groups as L ₁ and L ₂ .
Examples of the cyclic aliphatic group or aromatic ring group as Q include the cycloalkyl group and aryl group as L ₁ and L ₂ described above. These cycloalkyl groups and aryl groups are preferably groups having 3 to 15 carbon atoms.

Examples of the cyclic aliphatic group or aromatic ring group containing a heteroatom as Q include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazol, and the like. Examples thereof include groups having a heterocyclic structure such as thiazole and pyrrolidone. However, the ring is not limited to these as long as it is a ring formed by carbon and a hetero atom or a ring formed only by a hetero atom.

Examples of the ring structure in which at least two of Q, M and L ₁ can be formed by bonding with each other include a 5-membered or 6-membered ring structure formed by forming a propylene group or a butylene group. This 5- or 6-membered ring structure contains oxygen atoms.

Each group represented by L ₁ , L ₂ , M and Q in the general formula (B) may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group, a thioether group, an acyl group and an acyloxy group. , Halkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.

As the group represented by − (MQ), a group having 1 to 20 carbon atoms is preferable, a group having 1 to 10 carbon atoms is more preferable, and a group having 1 to 8 carbon atoms is further preferable.
Specific examples of the resin (A1) having a hydroxystyrene repeating unit are shown below, but the present invention is not limited thereto. In the specific examples below, tBu represents a t-butyl group and Et represents an ethyl group.

The resin (A1) in the present invention can be synthesized according to a conventional method (for example, radical polymerization).

The weight average molecular weight of the resin (A1) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and further preferably 3 as a polystyrene conversion value by the GPC (Gel Permeation Chromatography) method. It is 000 to 15,000, particularly preferably 3,000 to 11,000.

The dispersity (molecular weight distribution) of the resin (A1) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1. It is 1 to 2.0. The smaller the molecular weight distribution, the more preferable.

The content of the resin (A1) in the composition is preferably 30 to 99% by mass, more preferably 50 to 95% by mass, based on the total solid content.
The resin (A1) may be used alone or in combination of two or more.

(Resin having a phenolic hydroxyl group (A2))
The actinic light-sensitive or radiation-sensitive resin composition of the present invention may contain a resin (A2) having a phenolic hydroxyl group as the resin (A).
The phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic ring group with a hydroxy group. The aromatic ring is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

When the sensitive light-sensitive or radiation-sensitive resin composition of the present invention contains a resin (A2), it is generated from an acid generator by irradiation with active light or radiation in an exposed portion formed by using this composition. By the action of the acid (general formula (I) described above), the cross-linking reaction between the resin (A2) having a phenolic hydroxyl group and the acid cross-linking agent (C) described later proceeds, and a negative pattern is formed.

The resin (A2) having a phenolic hydroxyl group preferably contains a repeating unit having at least one kind of phenolic hydroxyl group. The repeating unit having a phenolic hydroxyl group is not particularly limited, and is preferably a repeating unit represented by the following general formula (1).

In the general formula (1), R ₁₁ represents a hydrogen atom, a methyl group which may have a substituent, or a halogen atom.
B ₁ represents a single bond or a divalent linking group.
Ar represents an aromatic ring.
m1 represents an integer of 1 or more.

Examples of the methyl group that may have a substituent in R ₁₁ include a trifluoromethyl group and a hydroxymethyl group.

R ₁₁ is preferably a hydrogen atom or a methyl group, and preferably a hydrogen atom for the reason of developability.

The divalent linking group of B ₁ includes a carbonyl group, an alkylene group (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group (−S (= O) ₂ −), and −O. -, -NH- or a divalent linking group combining these is preferable.

B ₁ preferably represents a single bond, a carbonyloxy group (-C (= O) -O-) or -C (= O) -NH-, and is a single bond or a carbonyloxy group (-C (= O)). -O-) is more preferable, and a single bond is more preferable from the viewpoint of improving dry etching resistance.

The aromatic ring of Ar is a monocyclic or polycyclic aromatic ring, and has a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring. Aromatic hydrocarbon rings, or, for example, thiophene rings, furan rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrol rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, thiadiazol rings, and Examples include aromatic heterocycles including heterocycles such as thiazole rings. Among them, the benzene ring and the naphthalene ring are preferable from the viewpoint of resolution, and the benzene ring is more preferable from the viewpoint of sensitivity.

m1 is preferably an integer of 1-5, more preferably 1. When m1 is 1 and Ar is a benzene ring, the substitution position of -OH is the meta position even at the para position with respect to the bond position with B ₁ (polymer main chain when B ₁ is a single bond) of the benzene ring. However, the ortho position may be used, but from the viewpoint of cross-linking reactivity, the para position and the meta position are preferable, and the para position is more preferable.

The aromatic ring of Ar may have a substituent other than the group represented by −OH, and examples of the substituent include an alkyl group, a cycloalkyl group, a halogen atom, a hydroxyl group, an alkoxy group and a carboxy group. Examples thereof include a group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, and an arylcarbonyl group.

The repeating unit having a phenolic hydroxyl group is more preferably a repeating unit represented by the following general formula (2) for the reasons of cross-linking reactivity, developability, and dry etching resistance.

In general formula (2),
R ₁₂ represents a hydrogen atom or a methyl group.
Ar represents an aromatic ring.
R ₁₂ represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable for the reason of developability.

Ar in the general formula (2) is synonymous with Ar in the general formula (1), and the preferable range is also the same. The repeating unit represented by the general formula (2) is a repeating unit derived from hydroxystyrene (that is, in the general formula (2), R ₁₂ is a hydrogen atom and Ar is a benzene ring). Is preferable from the viewpoint of sensitivity.

Further, the resin (A2) preferably has a repeating unit represented by the following general formula (3).

In the general formula (3), R ₁₃ represents a hydrogen atom or a methyl group.
X represents a group having a non-acidolytic polycyclic alicyclic hydrocarbon structure.
Ar ₁ represents an aromatic ring.
m2 is an integer of 1 or more.

R ₁₃ in the general formula (3) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.

The aromatic ring of Ar ₁ of the general formula (3) may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring. Aromatic hydrocarbon ring, or, for example, thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrol ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring. Aromatic heterocycles containing such heterocycles can be mentioned. Among them, the benzene ring and the naphthalene ring are preferable from the viewpoint of resolution, and the benzene ring is the most preferable.

The aromatic ring of Ar ₁ may have a substituent other than the group represented by -OX, and examples of the substituent include an alkyl group (preferably 1 to 6 carbon atoms) and a cycloalkyl group. (Preferably 3 to 10 carbon atoms), aryl group (preferably 6 to 15 carbon atoms), halogen atom, hydroxyl group, alkoxy group (preferably 1 to 6 carbon atoms), carboxy group, alkoxycarbonyl group (preferably carbon number of carbons) 2 to 7) are mentioned, an alkyl group, an alkoxy group, or an alkoxycarbonyl group is preferable, and an alkoxy group is more preferable.

X represents a group having a non-acidolytic polycyclic alicyclic hydrocarbon structure.
Preferred non-acidolytic polycyclic alicyclic hydrocarbon structures include adamantane structure, decalin structure, norbornane structure, norbornene structure, sedrol structure, structure having multiple cyclohexyl groups, structure having multiple cycloheptyl groups, and cyclooctyl. Examples thereof include a structure having a plurality of groups, a structure having a plurality of cyclodecanyl groups, a structure having a plurality of cyclododecanyl groups, and a tricyclodecane structure, and the adamantane structure is particularly preferable.

m2 is preferably an integer of 1-5, most preferably 1. When m2 is 1 and Ar ₁ is a benzene ring, the substitution position of -OX may be the para-position, the meta-position, or the ortho-position with respect to the bonding position of the benzene ring with the polymer main chain, but the para-position or the meta-position is Preferably, the para position is more preferable.

Specific examples of the repeating unit represented by the general formula (3) include the following.

When the resin (A2) has a repeating unit represented by the above general formula (3), the content thereof is preferably 1 to 40 mol%, more preferably 1 to 40 mol%, based on all the repeating units of the resin (A2). It is 2 to 30 mol%.

It is also preferable that the resin (A2) used in the present invention further has the following repeating unit (hereinafter, also referred to as “another repeating unit”) as a repeating unit other than the above repeating unit.

Examples of polymerizable monomers for forming these other repeating units are styrene, alkyl-substituted styrene, alkoxy-substituted styrene, halogen-substituted styrene, O-alkylated styrene, O-acylated styrene, hydrohydroxystyrene, and malean anhydride. Acids, acrylic acid derivatives (acrylic acid, acrylic acid esters, etc.), methacrylic acid derivatives (methacrylic acid, methacrylic acid esters, etc.), N-substituted maleimide, acrylonitrile, methacrylonitrile, vinylnaphthalene, vinylanthracene, and substituents. Examples thereof include indens and the like which may be possessed.

The resin (A2) may or may not contain these other repeating units, but when they are contained, the content of these other repeating units in the resin (A2) is all that constitutes the resin (A2). It is generally 1 to 30 mol%, preferably 1 to 20 mol%, and more preferably 2 to 10 mol% with respect to the repeating unit.

The resin (A2) can be synthesized by a known radical polymerization method, anion polymerization method or living radical polymerization method (iniferer method or the like).

The weight average molecular weight of the resin (A2) is preferably 1000 to 200,000, more preferably 2000 to 50000, and even more preferably 2000 to 15000.

The dispersity (molecular weight distribution) (Mw / Mn) of the resin (A2) is preferably 2.0 or less, more preferably 1.0 to 1.80 from the viewpoint of further improving sensitivity and resolution. 0 to 1.60 is more preferable, and 1.0 to 1.20 is particularly preferable. By using living polymerization such as living anionic polymerization, the dispersity (molecular weight distribution) of the obtained polymer compound becomes uniform, which is preferable. The weight average molecular weight and dispersity of the resin (A2) are defined as polystyrene-equivalent values measured by GPC.

When the above-mentioned resin (A2) is contained in the sensitive light-sensitive or radiation-sensitive resin composition of the present invention, the content thereof is preferably 30 to 95% by mass, preferably 40 to 90% by mass, based on the total solid content. Is more preferable, and 50 to 85% by mass is further preferable.
The resin (A2) may be used alone or in combination of two or more.

<Crosslinking agent (C)>
When the sensitive light-sensitive or radiation-sensitive resin composition of the present invention is used for forming a negative pattern, and when a resin (A2) having a phenolic hydroxyl group is used as the resin (A), a cross-linking agent is used. It is preferable to use. The cross-linking agent preferably contains a compound having two or more methylol groups in the molecule (hereinafter referred to as "compound (C)" or "cross-linking agent").

Of these, hydroxymethylated or alkoxymethylated phenol compounds, alkoxymethylated melamine compounds, alkoxymethyl glycol urelyl compounds and alkoxymethylated urea compounds are preferable, and these may have arbitrary substituents. A particularly preferable compound (C) as a cross-linking agent is a phenol derivative having 3 to 5 benzene rings in the molecule, 2 or more hydroxymethyl groups or alkoxymethyl groups in total, and a molecular weight of 1200 or less, or Examples thereof include alkoxymethylglycol uryl derivatives.
As the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable.

Among the above-mentioned cross-linking agents, a phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound having no corresponding hydroxymethyl group with formaldehyde under a base catalyst. A phenol derivative having an alkoxymethyl group can be obtained by reacting a phenol derivative having a corresponding hydroxymethyl group with an alcohol under an acid catalyst.

As another example of a preferable cross-linking agent, a compound having an N-hydroxymethyl group or an N-alkoxymethyl group, such as an alkoxymethylated melamine compound, an alkoxymethyl glycol ureyl compound and an alkoxymethylated urea compound. Can be mentioned.

Examples of such a compound include hexamethoxymethylmelamine, hexaethoxymethylmelamine, tetramethoxymethylglycoluryl, 1,3-bismethoxymethyl-4,5-bismethoxyethyleneurea, bismethoxymethylurea and the like, and EP0. , 133,216A, Western German Patent No. 3,634,671, No. 3,711,264, EP0,212,482A.
Among these cross-linking agents, particularly preferable ones are listed below.

In the formula, L _{1 to} L ₈ independently represent a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or an alkyl group having 1 to 6 carbon atoms.

When the actinic light-sensitive or radiation-sensitive resin composition of the present invention contains a cross-linking agent, the content of the cross-linking agent is preferably 3 to 65% by mass with respect to the total solid content in the composition. ~ 50% by mass is more preferable.
The cross-linking agent (C) may be used alone or in combination of two or more.

<Low molecular weight compound (D) having a nitrogen atom and having a group eliminated by the action of an acid>
The composition of the present invention may contain a compound having a nitrogen atom and having a group desorbed by the action of an acid (hereinafter, also referred to as “compound (D)”).
The group desorbed by the action of an acid is not particularly limited, and an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminol ether group is preferable, and a carbamate group or a hemiami. A nal ether group is more preferred.
The molecular weight of the compound (D) having a group eliminated by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
As the compound (D), an amine derivative having a group eliminated by the action of an acid on a nitrogen atom is preferable.
Compound (D) 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 the general formula (d-1)
R _b is independently 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), and an aralkyl group. It represents (preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 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 indicated by _Rb are substituted with functional groups such as hydroxy group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group and oxo group, alkoxy group and halogen atom. It may have been done. The same applies to the alkoxyalkyl group indicated by R _b .

The alkyl group, cycloalkyl group, aryl group, and aralkyl group of R _b (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the functional group, alkoxy group, or halogen atom. Good) include, for example, groups derived from linear or branched alcans such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane, these alcans Groups derived from, for example, a group substituted with one or more or one or more cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornan, adamantan. , And groups derived from cycloalkanes such as noradamantan, and groups derived from these cycloalcans, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methyl. Groups substituted with one or more or one or more linear or branched alkyl groups such as propyl group, 1-methylpropyl group and t-butyl group, aromatics such as benzene, naphthalene and anthracene. Groups derived from compounds, groups derived from these aromatic compounds, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl Groups and groups substituted with one or more or one or more linear or branched alkyl groups such as t-butyl groups, pyrrolidine, piperidine, morpholin, tetrahydrofuran, tetrahydropyran, indol, indolin, quinoline, per One or more groups derived from heterocyclic compounds such as hydroquinolin, indazole, and benzimidazole, and groups derived from these heterocyclic compounds as linear or branched alkyl groups or groups derived from aromatic compounds. Alternatively, one of a group substituted with one or more, a group derived from a linear or branched alkane, a group derived from a cycloalcan, a group derived from an aromatic compound such as a phenyl group, a naphthyl group, and an anthracenyl group. A group substituted with one or more species or one or more, or a group in which the above-mentioned substituent is substituted with a functional group such as a hydroxy group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo group, etc. Can be mentioned.

The 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 a cycloalkyl group.

Examples of the ring formed by connecting the two R _bs to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
Specific structures of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph 0466 of US2012 / 0135348A1.

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

In the general formula (6), _Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two _Ras may be the same or different, and the two _Ras may be interconnected to form a heterocycle with the nitrogen atom in the equation. 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 as R _a, a cycloalkyl group, an aryl group and, the aralkyl group, the alkyl group represented by R _b, cycloalkyl, aryl, and aralkyl groups are substituted As a good group, 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 _Ra (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above group) include. , R _b , the same group as the above-mentioned specific example can be mentioned.
Above for _{heterocycles R a} is formed by the interconnected, preferably not more than 20 carbon atoms, for example, pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1, 2, 3, 4-Tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazin, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7- Triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazole [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] heptane , 1,5,7-Triazabicyclo [4.4.0] Deck-5-ene, Indol, Indoline, 1,2,3,4-Tetrahydroquinoxalin, Perhydroquinolin, and 1,5,9- Groups derived from heterocyclic compounds such as triazacyclododecane, groups derived from these heterocyclic compounds to linear and branched alcan-derived groups, cycloalcan-derived groups, aromatic compounds Derived group, group derived from heterocyclic compound, hydroxy group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, and group substituted with one or more functional groups such as oxo group. And so on.

Specific examples of the compound (D) include, but are not limited to, the compound disclosed in US2012 / 0135348A1 paragraph 0475.
The compound represented by the general formula (6) can be synthesized based on JP-A-2007-298569, JP-A-2009-199021 and the like.
In the present invention, the low molecular weight compound (D) having a group eliminated by the action of an acid on a nitrogen atom can be used alone or in combination of two or more.
When the actinic light-sensitive or radiation-sensitive resin composition of the present invention contains compound (D), the content thereof is preferably 0.001 to 20% by mass, more preferably, based on the total solid content of the composition. Is 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

<Basic compound (E)>
The actinic light-sensitive or radiation-sensitive resin composition of the present invention preferably contains the basic compound (E) in order to reduce the change in performance with time from exposure to heating.
As the basic compound, preferably, a compound having a structure represented by the following formulas (A) to (E) can be mentioned.

In the general formulas (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and may be the same or different, and may be a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), or a cycloalkyl group (preferably carbon). It represents a number 3 to 20) or an aryl group (preferably 6 to 20 carbon atoms), where R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

Regarding the above alkyl group, as the alkyl group having a substituent, 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 is preferable.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.
It is more preferable that the alkyl groups in these general formulas (A) and (E) are unsubstituted.

Preferred compounds include guanidine, aminopyrrolidin, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholin, piperidin and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure and onium. Examples thereof include compounds having a carboxylate 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.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Compounds having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, and 1,8-diazabicyclo [5,4. 0] Undeca-7-en and the like can be mentioned. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, and tris (t-butylphenyl). Examples thereof include sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of the compound having an onium carboxylate structure include those in which the anion portion of the compound having an onium hydroxide structure is carboxylated, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine and the like. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.

Preferred basic compounds include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy 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. The amine compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group (preferably 3 to 20 carbon atoms) in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom. 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 has an oxyalkylene group formed therein. The number of oxyalkylene groups is one or more, preferably 3 to 9, and more preferably 4 to 6 in the molecule. 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 It is an 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. The ammonium salt compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably 6 to 12 carbon atoms) may be bonded to the 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, preferably 3 to 9, and more preferably 4 to 6 in the molecule. 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 It is an ethylene group.
Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate, and among them, a halogen atom and a sulfonate are preferable. Chloride, bromide, or iodide is preferable as the halogen atom, and organic sulfonate having 1 to 20 carbon atoms is preferable as the sulfonate. Examples of the organic sulfonate include an alkyl sulfonate having 1 to 20 carbon atoms and an aryl sulfonate. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkyl sulphonate include methane sulphonate, ethane sulphonate, butane sulphonate, hexane sulphonate, octane sulphonate, benzyl sulphonate, trifluoromethane sulphonate, pentafluoroethane sulphonate, and nonafluorobutane sulphonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring, and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. As a linear or branched alkyl group or cycloalkyl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, or an n-hexyl group. , And a cyclohexyl group and the like. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group and the like.

The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or the ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryl. Examples include oxy groups. The substituent of the substituent may be any of 2 to 6 positions. The number of substituents may be in the range of 1 to 5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more, preferably 3 to 9, and more preferably 4 to 6 in the molecule. 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 oxyethylene. It is a group.

The amine compound having a phenoxy group is prepared by heating and reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium. , Ethyl acetate, chloroform and the like can be obtained by extraction with an organic solvent. Alternatively, the amine compound having a phenoxy group is an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium after heating and reacting a primary or secondary amine with a haloalkyl ether having a phenoxy group at the terminal. Can also be obtained by extracting with an organic solvent such as ethyl acetate or chloroform after adding the above.

(A compound (PA) that has a proton-accepting functional group and decomposes by irradiation with active light or radiation to reduce or eliminate the proton-accepting property, or to generate a compound that has changed from proton-accepting property to acidic. )
The sensitive light-sensitive or radiation-sensitive resin composition of the present invention has a proton-accepting functional group as a basic compound, and is decomposed by irradiation with active light or radiation to reduce the proton accepting property. It may further contain a compound [hereinafter, also referred to as compound (PA)] that generates a compound that has disappeared or changed from proton acceptor to acidic.

A proton-accepting functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, 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 having an unshared electron pair that does not contribute to. 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 shown in the following general formula.

Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza crown ether structure, a 1-3-grade amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.

The compound (PA) is decomposed by irradiation with active light or radiation to generate a compound whose proton acceptor property is reduced or eliminated, or whose proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group. Specifically, it means that when a proton adduct is formed from a compound (PA) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.

Specific examples of the compound (PA) include the following compounds.
Further, as a specific example of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP2014-413328A and paragraphs 0108 to 0116 of JP2014-134686 can be incorporated. , These contents are incorporated herein by reference. In the following formula, Bu represents a butyl group.

As the compound (PA), in addition to those listed above, those described in paragraphs 0249 to 0433 of JP2014-413328A can be incorporated, and these contents are incorporated in the present specification.

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

The amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content in the composition.

The ratio of the acid generator and the basic compound used in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to the thickening of the resist pattern over time from exposure to heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

As the basic compound, for example, the compounds described in paragraphs 0140 to 0144 of JP2013-11833A can be used (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.).

<Surfactant (F)>
The sensitive light-sensitive or radiation-sensitive resin composition of the present invention can further contain a surfactant (F), and is a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based). It may contain any one of a surfactant (a surfactant having both a fluorine atom and a silicon atom), or two or more kinds.

Examples of the fluorine-based and / or silicon-based surfactant include Japanese Patent Application Laid-Open No. 62-36663, Japanese Patent Application Laid-Open No. 61-226746, Japanese Patent Application Laid-Open No. 61-226745, and Japanese Patent Application Laid-Open No. 62-170950. JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2002-277862, USA 5405720, 5360692, 5528881, 5296330, 5436098, 5576143, 5294511, 5824451. Surfactants can be mentioned, and the following commercially available surfactants can be used as they are.

As commercially available surfactants that can be used, for example, Ftop EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Asahi Glass Co., Ltd.) Troy Chemical Co., Ltd.), GF-300, GF-150 (Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), Ftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351,352, EF801, EF802, EF601 (manufactured by Gemco Co., Ltd.), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, Fluorine-based surfactants such as 222D (manufactured by Neos Co., Ltd.) or silicon-based surfactants can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

As the surfactant, in addition to the known ones as shown above, it was derived from a fluoroaliphatic compound produced by a telomerization method (also called a telomer method) or an oligomerization method (also called an 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-2002-090991.
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 the polymer is irregularly distributed. It may be a block copolymerized product. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and poly (a block conjugate of oxyethylene, oxypropylene, and oxyethylene). , Or a unit having alkylenes having different chain lengths within the same chain length, such as poly (block conjugate of oxyethylene and oxypropylene). Further, the copolymer of the monomer having a fluoroaliphatic group and the (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer, but also a monomer having two or more different fluoroaliphatic groups. Alternatively, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

For example, as a commercially available surfactant, Megafvck F-178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) can be mentioned. .. Further, a copolymer of an acrylate (or methacrylate) having ₁₃ C ₆ F groups and a (poly (oxyalkylene)) acrylate (or methacrylate), and an acrylate (or methacrylate) having ₇ C ₃ F groups and (poly (oxyalkylene)). Examples thereof include a copolymer of (ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate).

In the present invention, surfactants other than fluorine-based and / or silicon-based surfactants can also be used. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol ether. Etc., Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristeer. Polysorbate fatty acid esters such as rates, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Examples thereof include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters and the like.

These surfactants may be used alone or in combination of several.

The content of the surfactant in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total amount of the composition (excluding the solvent).

<Hydrophobic resin (H)>
The sensitive light-sensitive or radiation-sensitive resin composition of the present invention may contain a hydrophobic resin (hereinafter, also referred to as “hydrophobic resin (H)” or simply “resin (H)”). The hydrophobic resin (H) is preferably different from the resin (A).
The hydrophobic resin (H) is preferably designed to be unevenly distributed at the interface, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and polar / non-polar substances are uniformly mixed. It does not have to contribute to doing so.
The effects of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with water, improvement of immersion liquid followability, suppression of outgas, and the like.

The hydrophobic resin (H) is 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 on the film surface layer. It is preferable to have the above, and it is more preferable to have two or more kinds.
When the hydrophobic resin (H) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin (H) may be contained in the main chain of the resin. , May be contained in the side chain.

When the hydrophobic resin (H) contains a fluorine atom, it is 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. It is preferable to have.
The alkyl group having a fluorine atom (preferably 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, and further, a fluorine atom. It may have a substituent other than.
The cycloalkyl group having a fluorine atom and the aryl group having a fluorine atom are a cycloalkyl group in which one hydrogen atom is substituted with a fluorine atom and an aryl group having a fluorine atom, respectively, and further have a substituent other than the fluorine atom. You may have.

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

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

The hydrophobic resin (H) may contain silicon atoms. As the partial structure having a silicon atom, a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure is preferable.
Examples of repeating units having a fluorine atom or a silicon atom include those exemplified in US2012 / 0251948A1 [0519].

As described above, it is also preferable that the hydrophobic resin (H) contains a CH _3- part structure in the side chain portion.
Here, CH ₃ partial structure contained in the side chain portion in the hydrophobic resin (H) (hereinafter, simply referred to as "side chain CH ₃ partial structure") The, CH ₃ partial structure an ethyl group, and a propyl group having It includes.
On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (H) (for example, the α-methyl group of a repeating unit having a methacrylic acid structure) is on the surface of the hydrophobic resin (H) due to the influence of the main chain. for contribution to uneven distribution is small, and shall not be included in the CH ₃ partial structures in the present invention.

More specifically, the hydrophobic resin (H) is 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). When R _{11 to} R ₁₄ are CH ₃ “itself”, the CH ₃ is not included in the CH ₃ partial structure of the side chain portion in the present invention.
Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed to have "one" CH ₃ partial structure in the present invention.

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

The hydrophobic resin (H) is preferably a resin having a repeating unit having a CH _3- part structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II) and a repeating unit. , It is more preferable to have at least one repeating unit (x) among the repeating units represented by the following general 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, the organic group that is stable to an acid is more preferably an organic group that does not have an acid-degradable group.

The alkyl group of X _b1 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, but a methyl group is preferable.
X _b1 is preferably a hydrogen atom or a methyl group.
The R _2, has one or more CH ₃ moiety, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and, aralkyl groups. The cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group described above may further have an alkyl group as a substituent.
R ₂ has one or more CH ₃ moiety, the alkyl group or alkyl-substituted cycloalkyl groups are preferred.
Acid stable organic group having one or more CH ₃ partial structure as R ₂ preferably has a CH ₃ partial structure more than 10 or less, and more preferably has 8 or less 2 or more.
Preferred specific examples of the repeating unit represented by the general formula (II) are given below. 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 is decomposed by the action of an acid to produce a polar group. It is preferable that the repeating unit does not have.

Hereinafter, the repeating unit represented by the general 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, and R ₃ represents an acid-stable organic group having one or more CH ₃ partial structures. n represents an integer from 1 to 5.
The alkyl group of X _b2 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, but a hydrogen atom is preferable.
X _b2 is preferably a hydrogen atom.
Since R ₃ is an organic group stable to an acid, more specifically, it is preferably an organic group having no acid-degradable group.

Examples of R ₃ include alkyl groups 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, and more preferably 1 or more and 8 or less. It is more preferable to have 1 or more and 4 or less.
n represents an integer from 1 to 5, more preferably an integer from 1 to 3, and even more preferably 1 or 2.

A preferable specific example of the repeating unit represented by the general formula (III) is given below. 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 is decomposed by the action of an acid to produce a polar group. It is preferable that the repeating unit does not have.

When the hydrophobic resin (H) contains a CH _3- part structure in the side chain portion, and further does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II) and the repeating unit and The content of at least one repeating unit (x) among the repeating units represented by the general formula (III) is preferably 90 mol% or more with respect to all the repeating units of the hydrophobic resin (H). More preferably, it is 95 mol% or more. The content is usually 100 mol% or less with respect to all the repeating units of the hydrophobic resin (H).

The hydrophobic resin (H) uses at least one of the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III) (x) as the hydrophobic resin (H). ) Is contained in an amount of 90 mol% or more based on all the repeating units, so that the surface free energy of the hydrophobic resin (H) is increased. As a result, the hydrophobic resin (H) is less likely to be unevenly distributed on the surface of the resist membrane, the static / dynamic contact angle of the resist membrane with respect to water is surely improved, and the immersion liquid followability is improved. it can.

The hydrophobic resin (H) has the following (x) to (z) regardless of whether (i) a fluorine atom and / or a silicon atom is contained, or (ii) a CH _3- part structure is contained in the side chain portion. It may have at least one group selected from the group.
(X) Acid group,
(Y) A group having a lactone structure, an acid anhydride group, or an acidimide group,
(Z) A group that decomposes 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, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (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, and tris (alkyl) Sulfonyl) Methylene group and the like can be 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) is a repeating unit in which an acid group is directly bonded to the main chain of a resin such as a repeating unit made of acrylic acid or methacrylic acid, or a repeating unit of a resin via a linking group. A repeating unit in which an acid group is bonded to the main chain can be mentioned, and a polymerization initiator or a chain transfer agent having an acid group can be used at the time of polymerization to be introduced into the end of the polymer chain. In either case. 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 1 to 50 mol%, more preferably 3 to 35 mol%, still more preferably 5 to 5 mol% with respect to all the repeating units in the hydrophobic resin (H). It is 20 mol%.
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, the acid anhydride group, or the acidimide group (y), a group having a lactone 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, for example, a repeating unit made of an acrylic acid ester and a methacrylic acid ester. Alternatively, the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced into the end of the resin by using a polymerization initiator or chain transfer agent having this group at the time of polymerization.
Examples of the repeating unit having a group having a lactone structure include the same as the repeating unit having a lactone structure described above in the section of resin (A).

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

The repeating unit having a group (z) that decomposes by the action of an acid in the hydrophobic resin (H) is, for example, a repeating unit having a group that decomposes by the action of an acid mentioned in the resin (A) to generate a carboxy group. Similar, but not limited to, the same. The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin (H) is preferably 1 to 80 mol%, more preferably 1 to 80 mol%, based on all the repeating units in the resin (H). It is 10 to 80 mol%, more preferably 20 to 60 mol%.
The hydrophobic resin (H) may further have a repeating unit different from the repeating unit described above.

The repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all the repeating units contained in the hydrophobic resin (H).
The repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on all the repeating units contained in the hydrophobic resin (H).

On the other hand, especially if the hydrophobic resin (H) comprises a CH ₃ partial structure side chain moiety, a hydrophobic resin (H) is a form that does not contain a fluorine atom and a silicon atom substantially also preferred.
It is preferable that the hydrophobic resin (H) is substantially composed of only repeating units composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

The weight average molecular weight of the hydrophobic resin (H) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
The hydrophobic resin (H) may be used alone or in combination of two or more.
The content of the hydrophobic resin (H) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition.

The hydrophobic resin (H) preferably contains a residual monomer and an oligomer component in an amount of 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. The molecular weight distribution (Mw / Mn, also referred to as the degree of dispersion) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.

As the hydrophobic resin (H), various commercially available products can be used, or the hydrophobic resin (H) can be synthesized according to a conventional method (for example, radical polymerization).

<Solvent (G)>
The sensitive light-sensitive or radiation-sensitive resin composition of the present invention usually further contains a solvent.
The solvent may contain, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, alkyl alkoxypropionate, cyclic lactone (preferably 4 to 10 carbon atoms), and a ring monoketone. Examples thereof include organic solvents such as compounds (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate. , Propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate are preferable.

Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and the like. , Ethylene glycol monoethyl ether is preferably mentioned.

Preferable examples of the lactate alkyl ester 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. Iclactone and α-hydroxy-γ-butyrolactone are preferable.

Examples of the monoketone compound that may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, and 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,5-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-Nanonone, 3-Nanonanone, 5-Nanonanone, 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, and 3-methylcycloheptanone are preferred.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.

Examples of the alkoxyalkyl acetate include -2-methoxyethyl acetate, -2-ethoxyethyl acetate, -2- (2-ethoxyethoxy) ethyl acetate, -3-methoxy-3-methylbutyl acetate, and -1-acetic acid. Preference is given to methoxy-2-propyl.

Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

Examples of the solvent that can be preferably used include a solvent having a boiling point of 130 ° C. or higher at normal temperature and pressure. 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 -2- (2-ethoxyethoxy) ethyl and propylene carbonate can be mentioned.

In the present invention, the above-mentioned solvent may be used alone or in combination of two or more.

In the present invention, a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group are mixed may be used as the organic solvent.

As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplified compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether, Ethyl lactate is more preferred.
As the solvent containing no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether acetate, Ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, ethylethoxypropionate and 2-heptanone are even more preferred.

The mixing ratio (mass ratio) of the hydroxyl group-containing solvent and the hydroxyl group-free solvent is, for example, 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60. / 40. A mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferable in terms of coating uniformity.

The solvent is preferably a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

<Other ingredients>
In addition to the components described above, the sensitive light-sensitive or radiation-sensitive composition of the present invention may appropriately contain an onium carboxylic acid salt, a dye, a plasticizer, a photosensitizer, a light absorber, and the like.

The sensitive light-sensitive or radiation-sensitive resin composition of the present invention, and various materials (for example, resist solvent, developing solution, rinsing solution, antireflection film forming composition) used in the pattern forming method of the present invention described later. , Topcoat forming composition, etc.) preferably does not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 10 pppb or less, further preferably 100 ppt or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. Here, as metal impurities, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, And Zn and the like can be mentioned.

As a method for removing impurities such as metals from the various materials, for example, filtration using a filter can be mentioned. The filter pore size is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter may be a composite material in which these materials and an ion exchange medium are combined. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step.
In the production of an actinic light-sensitive or radiation-sensitive resin composition, after each component such as a resin and a photoacid generator is dissolved in a resist solvent, circulation filtration may be performed using a plurality of filters made of different materials. preferable. For example, it is preferable to connect a polyethylene filter having a pore diameter of 50 nm, a nylon filter having a pore diameter of 10 nm, and a polyethylene filter having a pore diameter of 3 nm in a permutation, and perform circulation filtration 10 times or more. The smaller the pressure difference between the filters, the more preferable, and generally, it is 0.1 MPa or less, preferably 0.05 MPa or less, and further preferably 0.01 MPa or less. The smaller the pressure difference between the filter and the filling nozzle, the more preferable, and generally, it is 0.5 MPa or less, preferably 0.2 MPa or less, and further preferably 0.1 MPa or less.
It is preferable to replace the inside of the apparatus for producing the actinic light-sensitive or radiation-sensitive resin composition with an inert gas such as nitrogen. Thereby, it is possible to suppress the dissolution of the active gas such as oxygen in the composition.
The sensitive light-sensitive or radiation-sensitive resin composition is filtered by a filter and then filled in a clean container. The composition filled in the container is preferably stored refrigerated. As a result, performance deterioration over time is suppressed. The shorter the time from the completion of filling the composition into the container to the start of refrigerated storage is preferably, generally within 24 hours, preferably within 16 hours, more preferably within 12 hours, and 10 Within hours is even more preferred. The storage temperature is preferably 0 to 15 ° C, more preferably 0 to 10 ° C, still more preferably 0 to 5 ° C.

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, a filter filtering is performed on the raw material constituting the various materials, and the raw material is filtered. Examples thereof include a method of lining the inside of the apparatus with Teflon (registered trademark) and performing distillation under conditions in which contamination is suppressed as much as possible. The preferred 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 by an adsorbent, or filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel and zeolite, and an organic adsorbent such as activated carbon can be used. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the mixing of metal impurities in the manufacturing process. Whether or not the metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal components contained in the cleaning liquid used for cleaning the manufacturing equipment. The content of the metal component contained in the cleaning liquid after use is preferably 100 ppt (parts per trillion) or less, more preferably 10 ppt or less, still more preferably 1 ppt or less.

Organic treatment liquids such as developer and rinse liquid are made of conductive compounds in order to prevent damage to chemical liquid piping and various parts (filters, O-rings, tubes, etc.) due to static electricity charging and subsequent electrostatic discharge. It may be added. The conductive compound is not particularly limited, and examples thereof include methanol. The amount to be added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable development characteristics and rinsing characteristics. As for the members of the chemical solution piping, SUS (stainless steel) or various piping coated with antistatic treated polyethylene, polypropylene or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) may be used. it can. Similarly, for the filter and the O-ring, antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used.
The inner wall surface of the container for storing the various materials is preferably treated so that impurities such as metals do not elute. As the inner wall surface of the container, a surface made of electropolished stainless steel, a glass-lined surface, and a surface coated with a fluororesin are more preferable.

A method for improving the surface roughness of the pattern may be applied to the pattern formed by the method of the present invention. Examples of the method for improving the surface roughness of the pattern include a method of treating the resist pattern with a plasma of a hydrogen-containing gas disclosed in International Publication No. 2014/002808. In addition, JP-A-2004-235468, US Patent Application Publication No. 2010/0020297, JP-A-2008-83384, and Proc. of SPIE Vol. A known method as described in 8328 83280N-1 "EUV Resist Curing Technology for LWR Reduction and Etch Sensitivity Enhancement" may be applied.

The pattern forming method of the present invention can also be used for guide pattern forming in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Page 4815-4823).

The resist pattern formed by the above method can be used as, for example, the core material of the spacer process disclosed in JP-A-3-270227 and JP2013-164509.

[Resist film]
The present invention also relates to a resist film formed of the above-mentioned actinic or radiation-sensitive resin composition. Such a resist film is formed by using the above-mentioned actinic light-sensitive or radiation-sensitive resin composition and applying it on a substrate at a solid content concentration as described later, for example. The above-mentioned sensitive light-sensitive or radiation-sensitive resin composition is applied onto a substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., and at 60 to 150 ° C. A resist film is formed by prebaking for 1 to 20 minutes, preferably 80 to 120 ° C. for 1 to 10 minutes. The film thickness of the formed resist film is preferably 10 to 200 nm, more preferably 10 to 150 nm, and even more preferably 20 to 150 nm.

Examples of the substrate include a silicon substrate, a metal vapor deposition film, or a substrate provided with a film containing a metal, and a vapor deposition film made of Cr, MoSi, TaSi, or an oxide or nitride thereof is provided on the surface. Substrates are preferred.

[Pattern formation method]
The present invention also relates to a pattern forming method using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.
The pattern forming method of the present invention includes a resist film forming step of forming a resist film using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition, an exposure step of exposing the resist film, and the exposed resist. It includes a developing step of developing the film with a developing solution. The pattern forming method of the present invention may further include a rinsing step of rinsing with a rinsing solution, if necessary.

The total solid content concentration in the actinic light-sensitive or radiation-sensitive resin composition is generally 1.0 to 10% by mass, preferably 1.0 to 8.0% by mass, and more preferably 1.0 to 1.0. It is 6.0% by mass.

The actinic light-sensitive or radiation-sensitive resin composition of the present invention is preferably used by dissolving the above-mentioned components in a solvent, filtering the mixture, and then applying the composition to a support. As the filter, those made of polytetrafluoroethylene, polyethylene, and nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less are preferable. A plurality of types of filters may be connected in series or in parallel. The composition may be filtered multiple times. Further, the composition may be degassed before and after the filter filtration.

The composition is applied onto a substrate (eg, silicon / silicon dioxide coating) such as that used in the manufacture of integrated circuit devices by a suitable coating method such as a spinner. After that, it is dried to form a sensitive light-sensitive or radiation-sensitive resin film (resist film).

The resist film is irradiated with active light or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. This makes it possible to obtain a good pattern. In the irradiation of the electron beam, drawing (direct drawing) without using a mask is common.
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 developing step.
The heating temperature is preferably 70 to 120 ° C., more preferably 80 to 110 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, still more preferably 30 to 90 seconds.

The heating can be performed by means provided in a normal exposure developing machine, or may be performed using a hot plate or the like.
Baking accelerates the reaction of the exposed area and improves sensitivity and pattern profile.

The active light beam or radiation is not particularly limited, and examples thereof include KrF excimer laser, ArF excimer laser, electron beam, EUV light and the like. From the viewpoint of better resolution and exposure latitude, electron beam or EUV light (extreme ultraviolet light) is preferable.

The developing solution used in the step of developing the resist film formed by using the sensitive light-sensitive or radiation-sensitive composition of the present invention is not particularly limited, and for example, an alkaline developing solution or a developing solution containing an organic solvent ( Hereinafter, it is also referred to as an organic developer). From the viewpoint of better resolution and exposure latitude, it is preferable to use an organic developer.

Examples of the alkaline developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, and primary amines such as ethylamine and n-propylamine. , Diethylamine, and secondary amines such as di-n-butylamine, triethylamine, tertiary amines such as methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxy Alkaline aqueous solutions such as quaternary ammonium salts such as tetraethylammonium hydroxide and cyclic amines such as pyrrole and piperidine can be used. Further, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution for use. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass.
The pH of the alkaline developer is usually 10.0 to 15.0.

As the organic developer, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent can be used.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone (methylamylketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutylketone. Examples thereof include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

Examples of the ester solvent 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, and diethylene glycol monoethyl. 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, propyl lactate, etc. Can be mentioned.

Examples of the alcohol-based solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, and n-heptyl alcohol. n-octyl alcohol, alcohols such as n-decanol, glycol-based 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 Examples thereof include ethers, diethylene glycol monomethyl ethers, triethylene glycol monoethyl ethers, and glycol ether-based solvents such as methoxymethylbutanol.

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

Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone. Etc. 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 a solvent other than the above or water may be mixed and used. The content of water contained in the organic developer is preferably less than 10% by mass, and more preferably substantially free of water.

That is, the amount of the organic solvent used with respect to the organic developer is preferably 90% by mass or more and 100% by mass or less, and preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developing solution.

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

An appropriate amount of surfactant can be added to the organic developer, if necessary. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based surfactant and / or a silicon-based surfactant can be used. Examples of these fluorine and / or silicon-based surfactants include Japanese Patent Application Laid-Open No. 62-36663, Japanese Patent Application Laid-Open No. 61-226746, Japanese Patent Application Laid-Open No. 61-226745, and Japanese Patent Application Laid-Open No. 62-170950. Japanese Patent Application Laid-Open No. 63-34540, Japanese Patent Application Laid-Open No. 7-230165, Japanese Patent Application Laid-Open No. 8-62834, Japanese Patent Application Laid-Open No. 9-54432, Japanese Patent Application Laid-Open No. 9-5988, US Pat. No. 5,405720, the same. The surfactants described in the specification of 5360692, 5529881, 5296330, 5436098, 5576143, 5294511, and 5824451 can be mentioned. , Preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, and it is more preferable to use a fluorine-based surfactant or a silicon-based 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 developing solution.

Pure water may be used as the rinsing liquid, and an appropriate amount of a surfactant may be added before use.

As a developing method, for example, a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), or a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle). Method), a method of spraying the developer on the surface of the substrate (spray method), a method of continuously ejecting the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic discharge method). Etc. can be applied.

After the developing step or the rinsing step, a process of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid can be performed.

An antireflection film may be applied on the substrate in advance before forming the sensitive light-sensitive or radiation-sensitive film (resist film).
As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type composed of a light absorber and a polymer material can be used. As the organic antireflection film, commercially available organic antireflection films such as DUV30 series and DUV-40 series manufactured by Brewer Science, AR-2, AR-3 and AR-5 manufactured by Shipley can also be used.

When irradiating with active light or radiation, the film and the lens may be filled with a liquid (immersion medium) having a refractive index higher than that of air for exposure (immersion exposure). This makes it possible to improve the resolution. Water is preferably used as the immersion medium. Water is also suitable in terms of low temperature coefficient of refractive index, easy availability, and ease of handling.
A medium having a refractive index of 1.5 or more can also be used in that the refractive index can be improved. This medium may be an aqueous solution or an organic solvent.

When water is used as the immersion liquid, an additive for the purpose of improving the refractive index may be added in a small proportion. Examples of additives are described in detail in Chapter 12 of CMC Publishing, "Processes and Materials for Immersion Lithography". On the other hand, the presence of a substance opaque to 193 nm light and impurities having a refractive index significantly different from that of water causes distortion of the optical image projected on the film, and therefore distilled water is preferable as the water to be used. Further, pure water purified by an ion exchange filter or the like may be used. The electrical resistance of pure water is preferably 18.3 MΩcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and degassing treatment is preferable.

<Upper layer film (top coat) and composition for forming upper layer film (top coat composition)>
Between the membrane (resist membrane) formed of the sensitive light-sensitive or radiation-sensitive composition and the immersion liquid, an immersion liquid sparingly soluble membrane (in order to avoid contact between the resist membrane and the immersion liquid) Hereinafter, a "superlayer film" or "top coat") may be provided. Functions required for the top coat include suitability for coating on a resist film, transparency to radiation, particularly radiation having a wavelength of 193 nm, and poor solubility in immersion liquid. As the composition for forming the top coat (“composition for forming an upper layer film” or “top coat composition”), the resist is not mixed with the actinic light-sensitive or radiation-sensitive composition constituting the resist film. It is preferable to use one that can be uniformly applied on the film.

As the material contained in the top coat, an aromatic-free polymer is preferable from the viewpoint of transparency at 193 nm. Examples of such polymers include hydrocarbon polymers, acrylic acid ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers and fluorine-containing polymers. The above-mentioned hydrophobic resin is also suitable as a top coat. When impurities are eluted from the top coat to the immersion liquid, the optical lens is contaminated. Therefore, it is preferable that the amount of residual monomer component of the polymer contained in the top coat is small.

The top coat is preferably formed by coating on a resist film using, for example, a top coat composition containing the above-mentioned hydrophobic resin and solvent.

The solvent that can be used is not particularly limited as long as the resin described later is not dissolved and the resist film is not dissolved. For example, an alcohol solvent, an ether solvent, an ester solvent, a fluorine solvent, or a hydrocarbon solvent is used. Etc. are preferably mentioned, and it is more preferable to use a non-fluorine-based alcohol solvent. As a result, the insolubility in the resist film is further improved, and when the top coat composition is applied onto the resist film, the top coat can be formed more uniformly without dissolving the resist film. The viscosity of the solvent is preferably 5 cP (centipores) or less, more preferably 3 cP or less, further preferably 2 cP or less, and particularly preferably 1 cP or less. From centipores to pascal seconds, it can be converted by the following formula: 1000 cP = 1 Pa · s.

These solvents may be used alone or in combination of two or more.

The topcoat composition preferably further contains at least one compound selected from the group consisting of the following (A1) to (A3).
(A1) Acid diffusion control agent (A2) Compound containing a bond or group selected from the group consisting of ether bond, thioether bond, hydroxy group, thiol group, carbonyl bond and ester bond (A3) Compound having radical trap group Hereinafter, (A1) to (A3) will be described respectively.

(A1) Acid Diffusion Control Agent The topcoat composition preferably further contains an acid diffusion control agent. As the acid diffusion control agent that can be contained in the topcoat composition, for example, the same as the basic compound (E) that can be contained in the actinic cheilitis or radiation-sensitive resin composition can be used.

The content of the acid diffusion control agent in the topcoat composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and 1 to 5% by mass, based on the solid content of the topcoat composition. % Is more preferable.

(A2) Compounds containing bonds or groups selected from the group consisting of ether bonds, thioether bonds, hydroxy groups, thiol groups, carbonyl bonds and ester bonds Ether bonds, thioether bonds, hydroxy groups, thiol groups, carbonyl bonds and A compound containing at least one group or bond selected from the group consisting of ester bonds (hereinafter, also referred to as compound (A2)) will be described below.

As described above, the compound (A2) is a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxy group, a thiol group, a carbonyl bond and an ester bond. Since the oxygen atom or sulfur atom contained in these groups or bonds has an unshared electron pair, the acid can be trapped by the interaction with the acid diffused from the resist film.

In one form of the topcoat composition, compound (A2) preferably has two or more groups or bonds selected from the above group, more preferably three or more, and even more preferably four or more. .. In this case, the group or bond selected from a plurality of ether bonds, thioether bonds, hydroxy groups, thiol groups, carbonyl bonds and ester bonds contained in the compound (A2) may be the same or different from each other. Good.

The molecular weight of the compound (A2) is preferably 3,000 or less, more preferably 2,500 or less, further preferably 2,000 or less, and particularly preferably 1,500 or less.

The number of carbon atoms contained in the compound (A2) is preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more.
The number of carbon atoms contained in the compound (A2) is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.

The boiling point of compound (A2) is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and even more preferably 240 ° C. or higher.

The compound (A2) is preferably a compound having an ether bond, preferably has two or more ether bonds, more preferably three or more, and further preferably four or more.
In the topcoat composition, the compound (A2) preferably contains a repeating unit containing an oxyalkylene structure represented by the following general formula (1).

During the ceremony
R ₁₁ represents an alkylene group which may have a substituent and represents
n represents an integer of 2 or more
* Represents a bond.

The carbon number of the alkylene group represented by R ₁₁ in the general formula (1) is not particularly limited, and is preferably 1 to 15, more preferably 1 to 5, further preferably 2 or 3, and particularly preferably 2. When this alkylene group has a substituent, the substituent is not particularly limited, and for example, an alkyl group (preferably 1 to 10 carbon atoms) is preferable.
n is preferably an integer of 2 to 20, and more preferably 10 or less because the DOF (Depth of field) becomes larger.
The average value of n is preferably 20 or less, more preferably 2 to 10, further preferably 2 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. preferable. Here, the "average value of n" means a value of n determined by measuring the weight average molecular weight of the compound (A2) by GPC and making the obtained weight average molecular weight consistent with the general formula. If n is not an integer, it shall be rounded off.
The plurality of R _11s may be the same or different.

The compound having a partial structure represented by the general formula (1) is preferably a compound represented by the following general formula (1-1) because the DOF becomes larger.

During the ceremony
Definition of R _11, specific examples and preferred embodiments are the same as R ₁₁ in general formula (1).
R ₁₂ and R ₁₃ each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, and is preferably 1 to 15. R ₁₂ and R ₁₃ may be combined with each other to form a ring.
m represents an integer of 1 or more. m is preferably an integer of 1 to 20, and more preferably 10 or less because of the larger DOF.
The average value of m is preferably 20 or less, more preferably 1 to 10, further preferably 1 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. preferable. Here, the "mean value of m" is synonymous with the above-mentioned "mean value of n".
When m is 2 or more, a plurality of R _11s may be the same or different.

In the topcoat composition, the compound having the partial structure represented by the general formula (1) is preferably an alkylene glycol containing at least two ether bonds.

The compound (A2) may be a commercially available product or may be synthesized by a known method.

Specific examples of the compound (A2) will be given below, but the present invention is not limited thereto.

The content of the compound (A2) is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and further 2 to 20% by mass, based on the total solid content in the upper layer film (top coat). It is preferable, and 3 to 18% by mass is particularly preferable.

-(A3) Compound having radical trap group (A3) Compound having radical trap group is also referred to as compound (A3).
A radical trap group is a group that captures active radicals and terminates the radical reaction. Examples of such a radical trap group include a group that reacts with an active radical and is converted into a stable free radical, and a group having a stable free radical.
Examples of the compound having such a radical trap group include hydroquinone, catechol, benzoquinone, nitroxyl radical compound, aromatic nitro compound, N-nitroso compound, benzothiazole, dimethylaniline, phenothiazine, vinylpyrene, and derivatives thereof. And so on.
As the non-basic radical trap group, specifically, at least one selected from the group consisting of, for example, a hindered phenol group, a hydroquinone group, an N-oxyl-free radical group, a nitroso group, and a nitrone group. The base of is preferably mentioned.

The number of radical trap groups contained in the compound (A3) is not particularly limited, and when the compound (A3) is a compound other than a polymer compound, the number of radical trap groups is preferably 1 to 10 in one molecule, and 1 to 5 More preferably, 1 to 3 are even more preferable.

On the other hand, when the compound (A3) is a polymer compound having a repeating unit, the repeating unit having a radical trap group preferably has 1 to 5 radical trap groups, and preferably has 1 to 3 radical trap groups. Is more preferable. The composition ratio of the repeating unit having a radical trap group in the polymer compound is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, still more preferably 30 to 100 mol%.

As the compound (A3) having a radical trap group, a compound having a nitrogen-oxygen bond is preferable, and a compound represented by any of the following general formulas (1) to (3) is more preferable.

The compound represented by the following general formula (1) corresponds to a compound having an N-oxyl-free radical group, the compound represented by the following general formula (2) corresponds to a compound having a nitroso group, and the following general The compound represented by the formula (3) corresponds to a compound having a nitrone group.

In the general formulas (1) to (3), R _{1 to} R ₆ independently represent an alkyl group, a cycloalkyl group, or an aryl group, respectively. In formula (1), R ₁ and R ₂ may be bonded to form a ring, and in formula (3), at least two of R _{4 to} R ₆ may be bonded to form a ring.
An alkyl group represented by R _{1 to} R ₆ , a cycloalkyl group, a ring which may be formed by bonding an aryl group, R ₁ and R _2, and at least two of R _{4 to} R ₆ are bonded. The ring that may be formed may have a substituent.

Examples of the alkyl group represented by R _{1 to} R ₆ include a linear or branched alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, and an n-propyl group. , I-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group and the like. A methyl group, an ethyl group, an n-butyl group, or a t-butyl group is preferable.

Examples of the cycloalkyl group represented by R _{1 to} R ₆ include a cycloalkyl group having 3 to 15 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl. Preferred examples thereof include a group, a cyclooctyl group, a norbornyl group, and an adamantyl group.

Examples of the aryl group represented by R _{1 to} R ₆ include an aryl group having 6 to 14 carbon atoms, and specific examples thereof preferably include a phenyl group, a tolyl group, a naphthyl group and the like.

The rings that R ₁ and R ₂ may form and the rings that R _{4 to} R ₆ may form are preferably 5 to 10-membered rings, and more preferably 5 or 6-membered rings. Is.

An alkyl group represented by R _{1 to} R ₆ , a cycloalkyl group, a ring which may be formed by bonding an aryl group, R ₁ and R _2, and at least two of R _{4 to} R ₆ are bonded. Examples of the substituent that the ring that may be formed may have include a halogen atom (for example, a fluorine atom), a hydroxy group, a carboxy group, a cyano group, a nitro group, an amino group, an oxy group, and an alkoxy group. , Alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group, acylamide group (RCONH-: R is a substituted or unsubstituted alkyl group or phenyl group), -SO ₂ Na, and -P (= O) (OC). ₂ H ₅ ) ₂ etc. can be mentioned.
Further, examples of the cycloalkyl group represented by R _{1 to} R ₆ and the substituent that the aryl group may have include an alkyl group.

The compound represented by any of the general formulas (1) to (3) may be in the form of a resin, in which case at least one of R _{1 to} R ₆ is bonded to the main chain or side chain of the resin. You may be doing it.

Specific examples of the compound (A3) having a radical trap group are shown below, but the present invention is not limited thereto.

When the compound (A3) having a radical trap group is a low molecular weight compound, its molecular weight is not particularly limited, and the molecular weight is preferably 100 to 5,000, more preferably 100 to 2,000, and further 100 to 1,000. preferable.
When the compound (A3) having a radical trap group is a polymer compound having a repeating unit, the weight average molecular weight thereof is preferably 5,000 to 20,000, more preferably 5,000 to 10,000.

As the compound (A3) having a radical trap group, a commercially available compound may be used, or a compound synthesized by a known method may be used. Compound (A3) is synthesized by reacting a commercially available low molecular weight compound having a radical trap group with a high molecular compound having a reactive group such as an epoxy group, an alkyl halide group, an acid halide group, a carboxy group and an isocyanate group. You may.

The content of the compound (A3) having a radical trap group is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the topcoat composition.

The topcoat composition may contain a plurality of one compound selected from the group consisting of (A1) to (A3). For example, it may contain two or more compounds (A1) that are distinguished from each other.
The topcoat composition may contain two or more compounds selected from the group consisting of (A1) to (A3). For example, it may contain both compound (A1) and compound (A2).
When the topcoat composition contains a plurality of compounds selected from the group consisting of (A1) to (A3), the total content of these compounds is usually 0 based on the total solid content of the topcoat composition. It is .001 to 20% by mass, preferably 0.01 to 10% by mass, and more preferably 1 to 8% by mass.
The compound (A3) having a radical trap group can be used alone or in combination of two or more.

When peeling off the top coat, a developing solution may be used, or a peeling agent may be used separately. As the release agent, a solvent having a small penetration into the actinic cheilitis or radiation-sensitive film is preferable. It is preferable that the peeling step can be performed with an alkaline developer in that the peeling step can be performed at the same time as the resist developing process. From the viewpoint of peeling with an alkaline developer, the top coat is preferably acidic, but from the viewpoint of non-intermixability with the resist, it may be neutral or alkaline.

It is preferable that there is no or small difference in refractive index between the top coat and the immersion liquid. In this case, the resolving power can be improved. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water as the immersion liquid, so that the top coat for ArF immersion exposure is close to the refractive index of water (1.44). preferable.

From the viewpoint of transparency and refractive index, the top coat is preferably a thin film. The topcoat is preferably not mixed with the actinic or radiation sensitive membrane and is not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is sparingly soluble in the solvent used for the sensitive light-sensitive or radiation-sensitive resin composition of the present invention and is water-insoluble. It is preferably a sexual medium. When the immersion liquid is an organic solvent, the top coat may be water-soluble or water-insoluble.
A top coat may be formed on the resin film even when the exposure is performed by a method other than the immersion exposure treatment.

[Manufacturing method of electronic devices]
The present invention also relates to a method for manufacturing an electronic device including the above-described method for forming a pattern of the present invention. The electronic device obtained by the above manufacturing method is suitably mounted on electrical and electronic equipment (home appliances, OA (office automation) / media-related equipment, optical equipment, communication equipment, etc.).

[Mask blanks with resist film]
The present invention also relates to a mask blank with a resist film provided with the resist film obtained as described above. The mask blank with a resist film of the present invention includes a mask blank and the above-mentioned resist film arranged on the mask blank. The mask blanks have, for example, a transparent substrate, and further have a light-shielding film or the like arranged on the transparent substrate.
Examples of the transparent substrate used include transparent substrates such as quartz and calcium fluoride. Generally, necessary functional films such as a light-shielding film, an antireflection film, a phase shift film, an etching stopper film, and an etching mask film are laminated on this substrate. Examples of the material of the functional film include silicon, chromium, molybdenum, zirconium, tantalum, tungsten, titanium, and transition metals such as niobium. As the material used for the outermost layer, a material whose main constituent material is silicon or a material containing silicon and oxygen and / or nitrogen; and a silicon compound material whose main constituent material is a material containing a transition metal thereof; Mainly materials containing one or more selected from transition metals, especially chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium, etc., or one or more elements selected from oxygen, nitrogen, and carbon. Examples include transition metal compound materials used as constituent materials; and the like.
The light-shielding film may have a single-layer structure, but is preferably a multi-layer structure in which a plurality of materials are coated. In the case of a multi-layer structure, the thickness of the film per layer is not particularly limited, and is preferably 5 nm to 100 nm, more preferably 10 nm to 80 nm. The thickness of the entire light-shielding film is not particularly limited, and is preferably 5 nm to 200 nm, more preferably 10 nm to 150 nm.

[Pattern forming method for mask blanks with resist film]
The present invention also relates to a method for forming a pattern of a mask blank with a resist film provided with the resist film obtained as described above.
The method for forming a pattern of a mask blank with a resist film of the present invention includes an exposure step of exposing the resist film in the mask blank with a resist film described above, a developing step of developing the exposed resist film in the mask blank with a resist film, and a developing step. including.

The exposure step is the same as the exposure step described as the method for forming a pattern of the sensitive light-sensitive or radiation-sensitive resin composition described above, and the preferred embodiment is also the same.
The developing step is the same as the developing step described as the method for forming a pattern of the sensitive light-sensitive or radiation-sensitive resin composition described above, and the preferred embodiment is also the same.
After forming a pattern on the mask blank with a resist film, this pattern is used as a mask and appropriately etched and ion-implanted to prepare a semiconductor microcircuit, a mold structure for imprinting, and the like.
The process for producing an imprint mold using the actinic light-sensitive or radiation-sensitive resin composition of the present invention is described in, for example, Japanese Patent No. 4190805 and Japanese Patent Application Laid-Open No. 2008-162101. There is.

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not construed as limiting by the examples shown below.

The various components contained in the actinic light-sensitive or radiation-sensitive resin composition are shown below.

<Acid generator>
The following compounds were synthesized and used as acid generators.

<Resin (A1)>
The following resin was used as the resin (A1).

<Resin (A2)>
The following resin was used as the resin (A2).

<Basic compound>
The following were used as the basic compounds.

Tetrabutylammonium hydroxide (E-15)

<Crosslinking agent>
The following substances were used as the cross-linking agent.

<Hydrophobic resin>
The following hydrophobic resins were used.

<Surfactant>
The following surfactants were used as the surfactants.
W-1: Mega Fvck F176 (manufactured by DIC Corporation) (fluorine type)
W-2: Megafuck R08 (manufactured by DIC Corporation) (fluorine-based and silicon-based)
W-3: PF6320 (manufactured by OMNOVA Solutions Inc.) (fluorine type)
W-4: Troysol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon type)

<Solvent>
The following solvents were used as the solvent.
S1: Propylene glycol monomethyl ether acetate (PGMEA)
S2: Cyclohexanone S3: γ-Butyrolactone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate

The components shown in each table below were dissolved in a solvent to prepare a solution having a solid content concentration of 4% by mass for each. Then, each active light-sensitive or radiation-sensitive resin composition (resist composition) was prepared by filtering the obtained solution using a polytetrafluoroethylene filter having a pore size of 0.05 μm.
For each component in each table, the ratio when a plurality of components are used is the "mass ratio".
The content of each component in the actinic light-sensitive or radiation-sensitive resin composition (resist composition) is as described in the table.
The content of the solvent (* 1 in the table) was set to the amount at which the composition had the above solid content concentration.
The performance of the obtained actinic cheilitis or radiation-sensitive resin composition was evaluated by various methods shown below, and the results are shown in each table.

<Examples 1A to 18A, Comparative Examples 1A to 4A>
(Exposure condition 1: ArF immersion exposure, alkaline development)
The organic antireflection film forming composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 98 nm. Next, the prepared anti-reflective or radiation-sensitive resin composition was applied onto the obtained antireflection film, and baking (PB: Prebake) was performed at 130 ° C. for 60 seconds to form a resist film having a film thickness of 120 nm. Formed.
When a top coat is used, a 3% by mass solution in which the top coat resin is further dissolved in decane / octanol (mass ratio 9/1) is applied onto the resist film obtained above, and at 85 ° C., 60. Baking was performed for 2 seconds to form a top coat layer having a thickness of 50 nm. An ArF excimer laser immersion scanner (ASML XT1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection) was used for this, and a 1: 1 line and space with a line width of 48 nm. Exposure was made through a 6% halftone mask of the pattern. Ultrapure water was used as the immersion liquid. Then, it was heated at 100 ° C. for 60 seconds (PEB: Post Exposure Bake). Then, it was developed by paddling with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, paddled with pure water and rinsed. Then, it was spin-dried to form a positive resist pattern.

(Evaluation test)
-Sensitivity evaluation The line pattern (ArF immersion exposure: line width 48 nm) obtained above with line / space = 1/1 was observed with a scanning electron microscope (S9380 manufactured by Hitachi, Ltd.). The minimum irradiation energy when resolving a line-and-space pattern (line: space = 1: 1) with a line width of 48 nm was defined as the sensitivity.

-Resolution power evaluation The resolution power was defined as the limit resolution power (the minimum line width at which lines and spaces are separated and resolved) at the irradiation dose showing the above sensitivity. The smaller this value, the better the resolving power.

-Exposure latitude evaluation The optimum exposure amount is the exposure amount that reproduces a 1: 1 line-and-space pattern with a line width of 48 nm, and the exposure amount width that allows the pattern size to be 48 nm ± 10% when the exposure amount is changed is obtained. It was. This value was divided by the optimum exposure and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

-Evaluation of in-plane uniformity (CDU) of line width 100 line widths in each line pattern in the 1: 1 line and space pattern formed by the above optimum exposure amount were measured. The in-plane uniformity (CDU) (nm) of the line width was evaluated by obtaining a triple value (3σ) of the standard deviation (σ) of the average value calculated from the measurement results. The smaller the value of 3σ obtained from the above, the higher the in-plane uniformity (CDU) of each line CD formed on the resist film.

-Pattern shape evaluation A scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.) was used to determine the cross-sectional shape of a line-and-space pattern (line: space = 1: 1) with a line width of 48 nm at an irradiation dose showing the above sensitivity. I observed it.
In the cross-sectional shape of the line pattern, the ratio represented by [line width at the bottom (bottom) of the line pattern / line width at the middle of the line pattern (half the height of the line pattern)] is 1.05. The above was defined as "taper", and the one having the above ratio of less than 1.05 was designated as "rectangle", and the evaluation was performed in two stages.

The results of these evaluations are shown in Table 4.

<Examples 1B to 18B, Comparative Examples 1B to 4B>
(Exposure condition 2: ArF immersion exposure, organic solvent-based development)
The organic antireflection film forming composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 95 nm. Next, the prepared actinic light-sensitive or radiation-sensitive resin composition was applied onto the obtained antireflection film, and baking (PB: Prebake) was performed at 100 ° C. for 60 seconds to obtain a film thickness of 100 nm. A resist film was formed.

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) at a line width of 48 nm 1: Exposure was performed through a 6% halftone mask with a 1-line and space pattern. Ultrapure water was used as the immersion liquid. Then, it was heated at 105 ° C. for 60 seconds (PEB: Post Exposure Bake). Then, it was developed by paddling with a negative developer (butyl acetate) for 30 seconds, and then paddled with a rinsing solution [methylisobutylcarbinol (MIBC)] for 30 seconds for rinsing. Subsequently, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds to form a 1: 1 line-and-space negative resist pattern having a line width of 48 nm.

Sensitivity evaluation, resolution evaluation, exposure latitude evaluation, and in-plane uniformity (CDU) evaluation of line width were performed on the obtained negative resist pattern. These evaluation methods are the same as the evaluation methods in Examples 1A to 18A. The pattern shape evaluation was performed by the following method. The results are shown in Table 5.

-Pattern shape evaluation A scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.) was used to determine the cross-sectional shape of a line-and-space pattern (line: space = 1: 1) with a line width of 48 nm at an irradiation dose showing the above sensitivity. I observed it.
In the cross-sectional shape of the line pattern, the ratio represented by [line width at the top (surface) of the line pattern / line width at the middle of the line pattern (half the height of the line pattern)] is 1. Those having a ratio of 05 or more were regarded as "reverse taper", and those having the above ratio of less than 1.05 were regarded as "rectangular" and evaluated in two stages.

<Examples 1C to 18C, Comparative Examples 1C to 4C>
(Exposure condition 3: EB (electron beam) exposure, alkaline development, positive pattern)
The prepared actinic light-sensitive or radiation-sensitive resin composition was uniformly applied onto a silicon substrate treated with hexamethyldisilazane using a spin coater. Next, it was heated and dried on a hot plate at 120 ° C. for 90 seconds to form an actinic or radiation-sensitive film (resist film) having a film thickness of 60 nm. An electron beam irradiation device (HL750 manufactured by Hitachi, Ltd., accelerating voltage 50 keV) was used to irradiate the obtained sensitive light-sensitive or radiation-sensitive film with an electron beam. Immediately after the irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds. Further, it was developed at 23 ° C. for 60 seconds using an aqueous solution of tetramethylammonium hydrooxide having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then spin-dried to form a positive resist pattern.

(Evaluation test)
-Sensitivity evaluation The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.). The exposure amount (electron beam irradiation amount) when resolving a 1: 1 line-and-space resist pattern having a line width of 50 nm was used as the sensitivity. The smaller this value, the higher the sensitivity.

-Resolution power evaluation The limit resolution power (minimum line width at which lines and spaces are separated and resolved) at the exposure amount (electron beam irradiation amount) indicating the above sensitivity was defined as the LS resolution power. The smaller this value, the better the resolving power.

-Exposure latitude evaluation The optimum exposure amount is the exposure amount that reproduces the line-and-space pattern (line: space = 1: 1) with a line width of 50 nm, and the pattern size allows 50 nm ± 20% when the exposure amount is changed. The exposure amount width was calculated. This value was divided by the optimum exposure and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

-Pattern shape evaluation Scanning electron microscope (S-Made by Hitachi, Ltd.) shows the cross-sectional shape of a 1: 1 line-and-space resist pattern with a line width of 50 nm at the exposure amount (electron beam irradiation amount) showing the above sensitivity. It was observed using 4300).
In the cross-sectional shape of the line pattern, the ratio represented by [line width at the bottom (bottom) of the line pattern / line width at the middle of the line pattern (half the height of the line pattern)] is 1.05. The above was defined as "taper", and the one having the above ratio of less than 1.05 was designated as "rectangle", and the evaluation was performed in two stages.
The results of these evaluation methods are shown in Table 6.

<Examples 1D to 18D, Comparative Examples 1D to 4D>
(Exposure condition 4: EB (electron beam) exposure, alkaline development, negative pattern)
The prepared actinic light-sensitive or radiation-sensitive resin composition was uniformly applied onto a silicon substrate treated with hexamethyldisilazane using a spin coater. Next, it was heated and dried on a hot plate at 120 ° C. for 90 seconds to form an actinic or radiation-sensitive film (resist film) having a film thickness of 60 nm. An electron beam irradiation device (HL750 manufactured by Hitachi, Ltd., accelerating voltage 50 keV) was used to irradiate the obtained sensitive light-sensitive or radiation-sensitive film with an electron beam. Immediately after irradiation, it was heated on a hot plate at 110 ° C. for 60 seconds. Further, it was developed at 23 ° C. for 60 seconds using an aqueous solution of tetramethylammonium hydrooxide having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then spin-dried to obtain a negative resist pattern.

Sensitivity evaluation, resolution evaluation, and exposure latitude evaluation were performed on the obtained negative resist pattern. These evaluation methods are the same as the evaluation methods in Examples 1C to 18C. The pattern shape evaluation was performed by the following method. The results are shown in Table 7.
-Pattern shape evaluation Scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.) scans the cross-sectional shape of a 1: 1 line-and-space resist pattern with a line width of 50 nm at the exposure amount (electron beam irradiation amount) showing the above sensitivity. Was observed using.
In the cross-sectional shape of the line pattern, the ratio represented by [line width at the top (surface) of the line pattern / line width at the middle of the line pattern (half the height of the line pattern)] is 1. Those having a ratio of 05 or more were regarded as "reverse taper", and those having the above ratio of less than 1.05 were regarded as "rectangular" and evaluated in two stages.

<Examples 1E to 18E, Comparative Examples 1E to 4E>
(Exposure condition 5: EUV (extreme ultraviolet) exposure, alkaline development)
-Applying the resist composition and baking after application (PB)
DUV44 (Brewer), which is a composition for forming an organic film, is placed on a 12-inch silicon wafer.
(Manufactured by Science) was applied and baked at 200 ° C. for 60 seconds to form an organic film having a film thickness of 60 nm. The prepared sensitive light-sensitive or radiation-sensitive resin composition is applied onto the formed organic film, baked for 60 seconds under the condition of 120 ° C., and the sensitive light-sensitive or radiation-sensitive film (resist) having a film thickness of 40 nm is obtained. Membrane) was formed.

・ Exposure (L / S pattern evaluation)
The wafer produced above was subjected to EUV exposure with NA (numerical aperture number, Natural Aperture) 0.25 and dipole illumination (Dipole 60x, outer sigma 0.81, inner sigma 0.43). Specifically, EUV exposure was performed by changing the exposure amount through a mask containing a pattern for forming a line-and-space pattern (L / S pattern) having a wafer dimension of 40 nm in pitch and 20 nm in width. ..

・ Post Exposure Bake (PEB)
After irradiation, it was taken out from the EUV exposure apparatus and immediately baked (PEB) at a temperature of 120 ° C. for 60 seconds.

-Development Developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution.

(Evaluation test)
-Sensitivity The irradiation energy when resolving a line-and-space pattern (L / S pattern) having a pitch of 40 nm and a width of 20 nm was defined as sensitivity (Eop). The smaller this value is, the better the performance is.

-Resolution power evaluation In the above Eop, the minimum line width of the separated (1: 1) line and space patterns was defined as the resolution power. The smaller this value is, the better the performance is.

-Exposure latitude evaluation The optimum exposure amount is the exposure amount that reproduces a line-and-space pattern (L / S pattern) with a pitch of 40 nm and a width of 20 nm, and an exposure that allows a pattern size of 50 nm ± 20% when the exposure amount is changed. The quantity range was calculated. This value was divided by the optimum exposure and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

-Pattern shape evaluation Scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.) shows the cross-sectional shape of the resist pattern of the line and space pattern (L / S pattern) with a line pitch of 40 nm and a width of 20 nm at the exposure amount showing the above sensitivity. ) Was used for observation.
In the cross-sectional shape of the line pattern, the ratio represented by [line width at the bottom (bottom) of the line pattern / line width at the middle of the line pattern (half the height of the line pattern)] is 1.05. The above was defined as "taper", and the one having the above ratio of less than 1.05 was designated as "rectangle", and the evaluation was performed in two stages.

<Examples 1F to 18F, Comparative Examples 1F to 4F>
(Exposure condition 6: EUV (extreme ultraviolet) exposure, organic solvent-based development)
-Preparation of composition for forming upper layer film Each component shown in Table 9 below was dissolved in the solvent shown in the same table. This was filtered using a polyethylene filter having a pore size of 0.03 μm to obtain a composition for forming an upper layer film (solid content concentration: 5% by mass). In Table 9 below, "MIBC" represents methylisobutylcarbinol.

The resins V-1 to V-3 and the additive X1 used in obtaining the composition for forming the upper layer film are shown below. Additives other than these are the same as those described above.
The composition ratio, weight average molecular weight and dispersity of the resins V-1 to V-3 are shown in Table 10 below.

Using the actinic or radiation-sensitive resin composition (resist composition) shown in Table 13 below, a resist pattern was formed by the following operation.

-Applying the resist composition and baking after application (PB)
DUV44 (manufactured by Brewer Science), which is a composition for forming an organic film, was applied onto a 12-inch silicon wafer and baked at 200 ° C. for 60 seconds to form an organic film having a film thickness of 60 nm. The prepared sensitive light-sensitive or radiation-sensitive resin composition is applied onto the formed organic film, baked for 60 seconds under the condition of 120 ° C., and the sensitive light-sensitive or radiation-sensitive film (resist) having a film thickness of 40 nm is obtained. Membrane) was formed.

-Applying the composition for forming the upper layer film and baking after application (PB)
For Examples 3F, 5F, 6F, 10F, 12F, and 15F, the upper layer film forming composition (top coat composition) shown in Table 9 above was applied onto the resist film after baking. Then, it was baked at the PB temperature (unit: ° C.) of the upper layer film shown in Table 13 below for 60 seconds to form an upper layer film (top coat) having a film thickness of 40 nm.

・ Exposure (L / S pattern evaluation)
The wafer produced above was subjected to EUV exposure with NA (numerical aperture number, Natural Aperture) 0.25 and dipole illumination (Dipole 60x, outer sigma 0.81, inner sigma 0.43). Specifically, EUV exposure was performed by changing the exposure amount through a mask containing a pattern for forming a line-and-space pattern (L / S pattern) having a wafer dimension of 40 nm in pitch and 20 nm in width. ..

・ Post Exposure Bake (PEB)
Immediately after being taken out from the EUV exposure apparatus after irradiation, it was baked (PEB) for 60 seconds at the temperature shown in Table 13 below.

-Development After that, using a shower-type developing device (ADE3000S manufactured by ACTES Co., Ltd.), while rotating the wafer at 50 rotations (rpm), the developer (23 ° C.) is spray-discharged at a flow rate of 200 mL / min for 30 seconds. By doing so, development was performed. As the developing solution, the developing solution shown in Table 13 below was used. Table 11 below also shows the developers used in each example.

-Rinse After that, the rinsing treatment was performed by spraying and discharging the rinsing solution (23 ° C.) at a flow rate of 200 mL / min for 15 seconds while rotating the wafer at 50 rpm.
Finally, the wafer was dried at a high speed of 2500 rpm for 60 seconds. As the rinsing solution, the rinsing solution shown in Table 13 below was used. Table 12 below also shows the rinse solutions used in each example.

(Evaluation test)
The following items were evaluated. Details of the results are shown in Table 13 below.

-Sensitivity evaluation The irradiation energy when resolving a line-and-space pattern (L / S pattern) having a wafer dimension of 40 nm in pitch and 20 nm in width was defined as sensitivity (Eop). The smaller this value is, the better the performance is.

-Resolution power evaluation In the above Eop, the minimum line width of the separated (1: 1) line and space patterns was defined as the resolution power. The smaller this value is, the better the performance is.

-Exposure latitude evaluation The optimum exposure amount is the exposure amount that reproduces the line-and-space pattern (L / S pattern) with a pitch of 40 nm and a width of 20 nm on the wafer, and the pattern size is 50 nm ± 20% when the exposure amount is changed. The exposure amount range that allows the above was determined. This value was divided by the optimum exposure and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

-Pattern shape evaluation A scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.) was used to determine the cross-sectional shape of the resist pattern of a line-and-space pattern (L / S pattern) with a width of 40 nm and a width of 20 nm at an exposure amount showing the above sensitivity. Observed using.
In the cross-sectional shape of the line pattern, the ratio represented by [line width at the top (surface) of the line pattern / line width at the middle of the line pattern (half the height of the line pattern)] is 1. Those having a ratio of 05 or more were regarded as "reverse taper", and those having the above ratio of less than 1.05 were regarded as "rectangular" and evaluated in two stages.

<Results of comparison between Examples and Comparative Examples>
From the results of Tables 4 to 8 and 13, the sensitive actinic or radiation-sensitive resin compositions of the examples containing the compounds that generate the acid represented by the general formula (I) have resolution, exposure latitude, and exposure latitude. , It was confirmed that all of the pattern shape characteristics were excellent.
Further, from the results of Tables 4 to 5, it was confirmed that the actinic light-sensitive or radiation-sensitive resin composition of the example containing the compound that generates the acid represented by the general formula (I) is also excellent in CDU. Was done.
On the other hand, the sensitive light-sensitive or radiation-sensitive resin composition of the comparative example containing no compound that generates an acid represented by the general formula (I) has poor resolution, exposure latitude, and pattern shape characteristics. It was enough.

Claims (13)

A sensitive light-sensitive or radiation-sensitive resin composition containing a resin and a compound that generates an acid represented by the following general formula (I) by irradiation with active light or radiation .
The resin is a sensitive photosensitive or radiation-sensitive resin composition having a phenolic hydroxyl group or a repeating unit having a lactone structure or a sultone structure.

In the general formula (I),
A represents a non-aromatic heterocycle having at least one linking group represented by X, or a non-aromatic heterocycle represented by the following formula (A) or formula (B) .

X _{is, - S -, - S (} = O) -, - S (= O) 2 -, - O (C = O) O -, - O (C = O) NZ -, - S (= O) Represents NZ-, -S (= O) ₂ NZ-, or a group combining these groups.
Z represents a monovalent organic group or a hydrogen atom.
R represents a monovalent organic group.
n represents an integer of 0 or more. The actinic or radiation-sensitive resin composition according to claim 1, wherein the compound is a compound represented by the following general formula (IA).

In the general formula (IA),
M ⁺ represents a monovalent cation.
A represents a non-aromatic heterocycle having at least one linking group represented by X.
X is -O-, -S-, -S (= O)-, -S (= O) _2- , -O (C = O) O-, -O (C = O) NZ-, -S (= O) NZ-, -S (= O) ₂ NZ-, or a group combining these groups.
Z represents a monovalent organic group or a hydrogen atom.
R represents a monovalent organic group.
n represents an integer of 0 or more. The actinic or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin is a resin having a group that decomposes by the action of an acid. In addition, it contains a cross-linking agent
The actinic or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin is a resin having a phenolic hydroxyl group. The actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein a plurality of the R's are present, and the plurality of the R's may be connected to each other to form a ring. The actinic or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the volume of the acid generated by the compound is 240 Å ³ or more. The actinic or radiation-sensitive resin composition according to any one of claims 1 to 6, further comprising a basic compound. A resist film formed of the actinic or radiation-sensitive resin composition according to any one of claims 1 to 7. A resist film forming step of forming a resist film using the actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7.
An exposure step for exposing the resist film and
A pattern forming method including a developing step of developing the exposed resist film with a developing solution. The pattern forming method according to claim 9, wherein the exposure step is a step of exposing using an electron beam or extreme ultraviolet rays. A method for manufacturing an electronic device, which comprises the pattern forming method according to claim 9 or 10. A mask blank with a resist film, comprising a mask blank and the resist film according to claim 8 arranged on the mask blank. The exposure step of exposing the resist film in the mask blank with the resist film according to claim 12.
A method for forming a pattern of a mask blank with a resist film, which comprises a developing step of developing the exposed resist film in the mask blank with a resist film.