JP5401371B2 - Actinic ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the composition - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon reaction with irradiation of actinic rays or radiation, and a pattern forming method using the composition. More specifically, the present invention relates to semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, creation of nanoimprint mold structures, and other photofabrication processes, planographic printing plates, acid curable compositions. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for a product, and a pattern forming method using the composition.

  Here, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, soft X-rays, and electron beams. Here, “light” means actinic rays or radiation.

  In addition, “exposure” means not only light irradiation with a mercury lamp, far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. .

  The chemically amplified resist composition generates an acid in the exposed area by irradiation with radiation such as far ultraviolet light, and dissolves in the developing solution of the actinic ray or radiation irradiated part and the non-irradiated part by a reaction using this acid as a catalyst. It is a pattern forming material that changes the properties and forms the pattern on the substrate.

  When a KrF excimer laser is used as an exposure light source, a resin having a basic skeleton of poly (hydroxystyrene) having a small absorption mainly in the 248 nm region is used as a main component. A pattern is formed, which is a better system than the conventional naphthoquinone diazide / novolak resin system.

On the other hand, when a further short wavelength light source, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group exhibits a large absorption in the 193 nm region. It wasn't.
For this reason, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed.

A triphenylsulfonium salt is generally known as an acid generator that is a main constituent of a chemically amplified resist (see, for example, Patent Document 1).
However, since the acid generator still has many inadequate points, the development of a photosensitive composition with improved sensitivity, pattern shape, roughness characteristics, stability over time, etc. can be achieved by improving the acid generator. It is desired.
In particular, the roughness characteristic becomes more serious as the pattern dimension is smaller. For example, in lithography using X-rays, electron beams, or EUV, since a target is to form a fine pattern of several tens of nanometers, particularly excellent roughness characteristics are required.

  Further, in the formation of a fine pattern, there is a problem that the line width varies depending on the temperature of heating after irradiation (post exposure bake: PEB). Therefore, there is also a need for such an improvement in PEB temperature dependence.

US Pat. No. 6,548,221

  The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition having excellent sensitivity, roughness characteristics, stability over time, and capable of forming a pattern having a good shape, and further having a suppressed PEB temperature dependency. It is an object of the present invention to provide a resist film formed using an object and a pattern forming method using the composition.

  For example, the present invention is as follows.

  [1] An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (A) having an amine oxide group and a photoacid generating site.

[2] The composition according to [1], wherein the compound (A) is a compound represented by the general formula (I) or (II).

In general formulas (I) and (II),
A ^- _is, ^-SO 3 ^_-, -CO ₂ - or _R 4 -Z-N ^{- -} represents a.
Y represents a divalent linking group, and Y ′ represents a single bond or a divalent linking group.
R ₁ , R ₂ , R ₃ and R ₄ represent a monovalent organic group.
Z is, -SO ₂ - represents or -CO- group.
X ⁺ represents an onium ion.
n represents 0 or 1.

Represents a heterocycle containing an N atom.

[3] The composition according to [1] or [2], further comprising a resin (C) that is decomposed by the action of an acid to increase the solubility in an alkali developer.

[4] The composition according to [3], wherein the resin (C) includes a repeating unit represented by the following general formula (VI).

Where
R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Ar ₁ represents an aromatic ring group.

Alternatively, R ₀₃ represents an alkylene group, and may be bonded to Ar ₁ as an aromatic ring group to form a ring together with the —C—C— chain. Alternatively, R ₀₃ and Ar ₁ may represent an alkylene group, and both may be bonded to each other to form a ring together with the —C—C— chain.

  n represents an integer of 1 to 4.

  [5] The composition according to [1] or [2], further comprising a resin soluble in an alkali developer and an acid crosslinking agent that crosslinks the resin soluble in the alkali developer by the action of an acid. object.

  [6] The composition according to any one of [1] to [5], further comprising a compound (B) that decomposes upon irradiation with actinic rays or radiation to generate an acid.

  [7] The composition according to any one of [1] to [6], which is exposed to an electron beam, an X-ray or EUV light.

[8] A resist film formed using the composition according to any one of [1] to [6].
[9] forming a film using the composition according to any one of [1] to [7];
Exposing the film;
Developing a pattern of the exposed film.
[10] The pattern forming method according to [9], wherein the pattern is exposed to an electron beam, an X-ray or EUV light.

  According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition having excellent sensitivity, roughness characteristics and stability over time and capable of forming a pattern having a good shape and having a suppressed PEB temperature dependency, It is possible to provide a resist film formed using the composition and a pattern forming method using the composition.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the groups and atomic groups that do not explicitly indicate substitution or non-substitution include both those that do not have a substituent and those that have a substituent. For example, an “alkyl group” that does not clearly indicate substitution or unsubstituted is not only an alkyl group that does not have a substituent (unsubstituted alkyl group) but also an alkyl group that has a substituent (substituted alkyl group) Is also included.

  The composition according to the present invention contains a compound (A) having an amine oxide group and a photoacid generating site. The composition according to the present invention may further contain a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “photoacid generator”).

In addition, the composition of the present invention may be used as a positive composition or a negative composition.
In the former case, the composition according to the present invention typically comprises [A1] a resin that decomposes under the action of an acid and increases the solubility in an alkaline developer (hereinafter also referred to as “acid-decomposable resin”). In addition. The composition may further contain a compound having a molecular weight of 3000 or less (hereinafter also referred to as a dissolution inhibiting compound) that decomposes by the action of [A3] acid to increase the solubility in an alkaline developer.
In the latter case, the composition according to the present invention typically comprises [A2] an alkali developer-soluble resin (hereinafter also referred to as “alkali-soluble resin”) and [A4] an acid by the action of an acid. It further contains a soluble resin and an acid crosslinking agent that crosslinks.
[1] Compound having amine oxide group and photoacid generating site (A)
The amine oxide group possessed by the compound (A) is a group of compounds having a structure represented by any of the following structural formulas that are chemically equivalent, and has a polarity comparable to that of a quaternary ammonium ion (R ₄ N ⁺ ). It is a structure with In addition, amine oxide has weak basicity, an acid dissociation constant pKa value of about 4.5, and it is known to take a cationic hydroxylamine structure R ₃ N ⁺ —OH by addition of a proton. Moreover, since polarity is high and volatility can be suppressed, the temperature dependence in PEB can be improved.

  The photoacid generation site is a structure that efficiently generates an acid upon irradiation with actinic rays or radiation, for example, a diazonium salt structure, an iodonium salt structure, a sulfonium salt structure, a sulfonic acid ester structure, an oxathiazole derivative, and an s-triazine derivative. , Disulfone derivatives, imide sulfonate structures, and oxime sulfonate structures.

As the compound (A) having an amine oxide group and a photoacid generating site, a compound represented by the general formula (I) or (II) is preferable.

In general formulas (I) and (II),
A ^- _is, ^-SO 3 ^_-, -CO ₂ - or _R 4 -Z-N ^{- -} represents a.
Y represents a divalent linking group, and Y ′ represents a single bond or a divalent linking group.
R ₁ , R ₂ , R ₃ and R ₄ represent a monovalent organic group.
Z is, -SO ₂ - represents or -CO- group.
X ⁺ represents an onium ion.
n represents 0 or 1.

Represents a heterocycle containing an N atom.

The general formula (I) or (II) will be described in detail.
Y represents a divalent linking group, and Y ′ represents a single bond or a divalent linking group. Examples of the divalent linking group represented by Y and Y ′ include an alkylene group, a cycloalkylene group, an arylene group, —COO—, —OCO—, —CO—, —O—, —S—, —S (= O) —, —S (═O) ₂ —, —OS (═O) ₂ —, —NH— and any one or more selected from divalent nitrogen-containing non-aromatic heterocyclic groups Groups.

The alkylene group and cycloalkylene group are preferably linear, branched or cyclic alkylene groups having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms (for example, methylene, ethylene, propylene, 1,4-cyclohexylene). And part or all of the hydrogen atoms bonded to carbon may have a substituent.
The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms (for example, phenylene or naphthylene), and a part or all of the hydrogen atoms bonded to carbon are substituted. You may have.

  Examples of the substituent that the alkylene group, cycloalkylene group and arylene group may have include, for example, a halogen group such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, tert-butoxy group and the like An alkoxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group and a p-tolyloxycarbonyl group; an acetoxy group; Acyloxy groups such as propionyloxy group and benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; alkylsulfuric groups such as methylsulfanyl group and tert-butylsulfanyl group Aryl group; arylsulfanyl group such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl or cycloalkylamino group such as methylamino group and cyclohexylamino group; dialkylamino such as dimethylamino group, diethylamino group, morpholino group and piperidino group Group, phenylamino group, arylamino group such as p-tolylamino group, alkyl group such as methyl group, ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group In addition to aryl groups such as anthryl group and phenanthryl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, perfluoroalkyl Group, trialkylsilyl group, etc. And the like.

In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means a non-aromatic heterocyclic group having at least one nitrogen atom, preferably 3 to 8 members, specifically, for example, Examples thereof include a divalent linking group having a structure.

Represents a heterocycle containing an N atom. Here, the N atom is bonded to the O atom in the general formula (II) and the R ₃ group when n = 1, and the Y ′ group (or the A ^- group when the Y ′ group is a single bond) May or may not be bonded.

  The hetero ring may be an aromatic ring or a non-aromatic ring, and may further contain a hetero atom in addition to the N atom in the formula. Such heterocycles include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, isoindole ring, purine ring, quinolidine ring, isoquinolidine. Ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, phenothiazine ring, morpholine ring, piperidine ring, triazine ring, pyrazole ring, iso Examples include a thiazole ring, an isoxazole ring, a phenazine ring, a pyrrolidine ring, a julolidine ring, a piperazine ring, and a pyrazoline ring. Of these, morpholine ring, piperidine ring, pyridine ring, quinoline ring and isoquinoline ring are preferred.

R ₁ -R ₄ represents a monovalent organic group, an optionally substituted alkyl group, which may have a substituent cycloalkyl group, an optionally substituted aryl group, a substituted An alkenyl group which may have a group, an alkynyl group which may have a substituent, and the like.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group Group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl Group, 3-trifluoromethylphenacyl group, 3-nitrophenacyl group and the like.

  The cycloalkyl group which may have a substituent is preferably a cycloalkyl group having 6 to 30 carbon atoms, and may be monocyclic or polycyclic, and examples thereof include a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group. Can be mentioned.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthraceni Group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexa Examples thereof include a phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  Examples of the substituent that can be introduced into these groups include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Aryloxy groups such as tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, aryloxycarbonyl groups such as phenoxycarbonyl group, p-tolyloxycarbonyl group, acetoxy group, propionyloxy group, benzoyloxy group, etc. Acyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group and other acyl groups, methylsulfanyl group, alkylsulfanyl groups such as tert-butylsulfanyl group, phenylsulfanyl group, p-tolyl Arylsulfanyl groups such as sulfanyl groups, alkyl or cycloalkylamino groups such as methylamino groups, cyclohexylamino groups, dialkylamino groups such as dimethylamino groups, diethylamino groups, morpholino groups, piperidino groups, phenylamino groups, p-tolylamino groups Aryl groups such as methyl group, ethyl group, tert-butyl group, dodecyl group, etc., aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group Etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico Group, phosphono group, Methyl ammonium Niu mill group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

Specific examples of the anion moiety of the compound (A) include the following.

  The amine oxide structure is usually synthesized by oxidizing a heterocyclic compound such as amine or pyridine. As the oxidizing agent, percarboxylic acids such as hydrogen peroxide, persulfuric acid and metachloroperbenzoic acid are used.

R ₃ N + (oxidant) → R ₃ N ⁺ —O ⁻
For example, in the oxidation of pyridine, peracetic acid generated from hydrogen peroxide and acetic acid can act on pyridine to synthesize pyridine oxide.

In the general formulas (I) and (II), the onium ion represented by M ⁺ is an onium ion represented by the following general formulas (ZI) and (ZII) in one embodiment.

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group. The carbon number of the organic group as R _201, R ₂₀₂ and R ₂₀₃ is, for example, 1 to 30, preferably 1 to 20.

Two of R _{201 to} R ₂₀₃ may be bonded to each other via a single bond or a linking group to form a ring structure. Examples of the linking group in this case include an ether bond, a thioether bond, an ester bond, an amide bond, a carbonyl group, a methylene group, and an ethylene group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include alkylene groups such as a butylene group and a pentylene group.

Specific examples of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compound (ZI-1), (ZI-2) or (ZI-3) described later.

As the compound (A), a compound having a plurality of structures represented by the general formula (ZI) may be used. For example, a cation represented by the general formula (ZI) of R ₂₀₁ to R _203, at least one, but at least one coupling structure of the general formula R Another cation represented by (ZI) ₂₀₁ to R ₂₀₃ It may be a compound.

  More preferable (ZI) components include cations (ZI-1) to (ZI-3) described below.

The cation (ZI-1) is an arylsulfonium cation in which at least one of R _{201 to} R _{203 in} the general formula (ZI) is an aryl group.

Cations (ZI-1) is all R ₂₀₁ to R ₂₀₃ is may be an aryl group or a part of R ₂₀₁ to R ₂₀₃ is an aryl group, except they may be an alkyl group. In addition, when compound (ZI-1) has a plurality of aryl groups, these aryl groups may be the same as or different from each other.

  Examples of the cation (ZI-1) include a triarylsulfonium ion, a diarylalkylsulfonium ion, and an aryldialkylsulfonium ion.

  The aryl group in the cation (ZI-1) is preferably a phenyl group, a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, and particularly preferably a phenyl group, a naphthyl group, or an indole residue.

  The alkyl group which the cation (ZI-1) has as necessary is preferably a linear, branched or cycloalkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, n -Butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group and cyclohexyl group are mentioned.

  These aryl groups and alkyl groups may have a substituent. Examples of the substituent include an alkyl group (preferably 1 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxy group (preferably 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and phenylthio. Groups.

Preferable substituents include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms. Particularly preferred substituents include alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms. The substituent may be substituted to any one of the three R ₂₀₁ to R _203, or may be substituted on all three. When R _{201 to} R ₂₀₃ are a phenyl group, the substituent is preferably substituted at the p-position of the aryl group.

In another embodiment, one or two of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is an aryl group which may have a substituent, and the remaining group is a linear, branched or cyclic alkyl group. preferable. Specific examples of this structure include the structures described in paragraphs 0141 to 0153 of JP-A-2004-210670.

At this time, as the aryl group, specifically, the same as the aryl group of R _201, R ₂₀₂ and R _203, a phenyl group or a naphthyl group is preferable. The aryl group preferably has any one of a hydroxyl group, an alkoxy group, and an alkyl group as a substituent. More preferably, it is a C1-C12 alkoxy group as a substituent, More preferably, it is a C1-C6 alkoxy group.

  The linear, branched or cyclic alkyl group as the remaining group is preferably an alkyl group having 1 to 6 carbon atoms. These groups may further have a substituent. In addition, when two of the remaining groups are present, these two may be bonded to each other to form a ring structure.

As one aspect | mode of a cation (ZI-1), what is represented by the following general formula (ZI-1A) is mentioned.

In general formula (ZI-1A),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.
R ₁₄ is each independently an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, a cycloalkylsulfonyl group, or a monocyclic or polycyclic cycloalkyl skeleton when there are a plurality of R14 Represents a group having These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring structure.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
The alkyl group for R ₁₃ , R ₁₄ or R ₁₅ may be a linear alkyl group or a branched alkyl group. The alkyl group is preferably one having 1 to 10 carbon atoms, for example, methyl group, ethyl group, 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, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group. Of these, a methyl group, an ethyl group, an n-butyl group, and a t-butyl group are particularly preferable.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ or R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclobenenyl, cyclohexenyl, norbornyl, and tricyclodecanyl. , Tetracyclodecanyl, adamantyl and cyclooctadienyl groups. Of these, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl groups are particularly preferred.

Examples of the alkyl group moiety of the alkoxy group of R ₁₃ or R ₁₄ include those enumerated above as the alkyl group of R ₁₃ , R ₁₄ or R ₁₅ . As the alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group are particularly preferable.

The cycloalkyl moiety of the cycloalkyl group of R _13, for example, those previously listed as the cycloalkyl group of _{R 13, R 14} or _{R 15.} As this cycloalkyloxy group, a cyclopentyloxy group and a cyclohexyloxy group are particularly preferable.

The alkoxy group moiety of the alkoxycarbonyl group R _13, for example, those previously listed as alkoxy groups R ₁₃ or R _14. As the alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and an n-butoxycarbonyl group are particularly preferable.

The alkyl group moiety of the alkylsulfonyl group R _14, for example, those previously listed as alkyl group _{R 13, R 14} or _{R 15. Further,} the cycloalkyl group moiety cycloalkylsulfonyl group _{R 14,} for example, those previously listed as the cycloalkyl group of _{R 13, R 14} or _{R 15.} As these alkylsulfonyl groups or cycloalkylsulfonyl groups, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, and a cyclohexanesulfonyl group are particularly preferable.

Examples of the group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. Can be mentioned. These groups may further have a substituent.

  l is preferably 0 or 1, more preferably 1. r is preferably 0-2.

Each group of R ₁₃ , R ₁₄ and R ₁₅ may further have a substituent. Examples of this substituent include halogen atoms such as fluorine atoms, hydroxy groups, carboxy groups, cyano groups, nitro groups, alkoxy groups, cycloalkyloxy groups, alkoxyalkyl groups, cycloalkyloxyalkyl groups, alkoxycarbonyl groups, cyclocarbonyls, Examples include an alkyloxycarbonyl group, an alkoxycarbonyloxy group, and a cycloalkyloxycarbonyloxy group.

The alkoxy group may be linear or branched. Examples of the alkoxy group include carbon number 1 such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, and t-butoxy group. -20.
Examples of the cycloalkyloxy group include those having 3 to 20 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group.

The alkoxyalkyl group may be linear or branched. Examples of the alkoxyalkyl group include those having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group and 2-ethoxyethyl group. Can be mentioned.
Examples of the cycloalkyloxyalkyl group include those having 4 to 21 carbon atoms such as a cyclohexyloxymethyl group, a cyclopentyloxymethyl group, and a cyclohexyloxyethyl group.

The alkoxycarbonyl group may be linear or branched. Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group and t. -A C2-C21 thing, such as a butoxycarbonyl group, is mentioned.
Examples of the cycloalkyloxycarbonyl group include those having 4 to 21 carbon atoms such as a cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl.

The alkoxycarbonyloxy group may be linear or branched. Examples of the alkoxycarbonyloxy group include carbon such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group and t-butoxycarbonyloxy group. The thing of number 2-21 is mentioned.
Examples of the cycloalkyloxycarbonyloxy group include those having 4 to 21 carbon atoms such as a cyclopentyloxycarbonyloxy group and a cyclohexyloxycarbonyloxy group.

The ring structure that can be formed by bonding two R ₁₅ to each other includes a 5-membered ring or a 6-membered ring, particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring) together with the S atom in the general formula (ZI-1A). ) Is preferred.
This ring structure may further have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group.

As R ₁₅ , a methyl group, an ethyl group, and a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom are particularly preferable.

Alkyl groups R _13, cycloalkyl group, alkoxy group and alkoxycarbonyl group, alkyl group of R _14, cycloalkyl group, alkoxy group, alkylsulfonyl group and cycloalkylsulfonyl group may further have a substituent . As this substituent, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, and a halogen atom (particularly a fluorine atom) are preferable.
Specific examples of preferable cations represented by general formula (ZI-1A) are shown below.

Moreover, what is represented by the following general formula (ZI-1B) is mentioned as another aspect of a cation (ZI-1). The cation represented by the general formula (ZI-1B) is effective in suppressing outgas.

In general formula (ZI-1B),
R ^{1 to} R ¹³ each independently represents a hydrogen atom or a substituent. At least one of R ^{1 to} R ¹³ is preferably a substituent containing an alcoholic hydroxyl group. Here, “alcoholic hydroxyl group” means a hydroxyl group bonded to a carbon atom of an alkyl group.
X is a single bond or a divalent linking group.

When R ^{1 to} R ¹³ are substituents containing an alcoholic hydroxyl group, R ^{1 to} R ¹³ are preferably groups represented by — (W—Y). Here, Y is an alkyl group substituted with a hydroxyl group, and W is a single bond or a divalent linking group.

Preferable examples of the alkyl group represented by Y include an ethyl group, a propyl group, and an isopropyl group. Y particularly preferably includes a structure represented by —CH ₂ CH ₂ OH.

  The divalent linking group represented by W is not particularly limited, but preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, A divalent group in which an arbitrary hydrogen atom in an alkoxycarbonyl group or a carbamoyl group is replaced by a single bond, and more preferably an arbitrary hydrogen atom in a single bond, an acyloxy group, an alkylsulfonyl group, an acyl group or an alkoxycarbonyl group. It is a divalent group replaced by a single bond.

When R ^{1 to} R ¹³ are substituents containing an alcoholic hydroxyl group, the number of carbon atoms contained is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.

The substituent containing an alcoholic hydroxyl group as R ^{1 to} R ¹³ may have two or more alcoholic hydroxyl groups. The number of the alcoholic hydroxyl group which the substituent containing the alcoholic hydroxyl group as R < ¹ > -R < ¹³ > has is 1-6, Preferably it is 1-3, More preferably, it is 1.

The number of alcoholic hydroxyl groups contained in the compound represented by the general formula (ZI-1B) is 1 to 10, preferably 1 to 6, more preferably 1 to 3 in total for R ^{1 to} R ^13. is there.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, examples of the substituent as R ^{1 to} R ¹³ include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an aryl group. , Heterocyclic group, cyano group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group ( Anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, Duplicate Ring thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, Phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group [—B (OH) ₂ ], phosphato group [—OPO (OH) ₂ ], Examples thereof include a sulfato group (—OSO ₃ H) and other known substituents.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are preferably a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, Cyano group, carboxy group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino Group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfonyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, silyl group or ureido group.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are more preferably a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a cyano group, an alkoxy group, an acyloxy group, an acylamino group, An aminocarbonylamino group, an alkoxycarbonylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, a sulfamoyl group, an alkyl and arylsulfonyl group, an alkoxycarbonyl group or a carbamoyl group.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are particularly preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or an alkoxy group.

Two adjacent ones of R ^{1 to} R ¹³ may be bonded to each other to form a ring structure. This ring structure includes aromatic and non-aromatic hydrocarbon rings and heterocycles. These ring structures may be further combined to form a condensed ring.

In the general formula (ZI-1B), preferably at least one of R ^{1 to} R ¹³ has a structure containing an alcoholic hydroxyl group, and more preferably at least one of R ^{9 to} R ¹³ is an alcohol. It has a structure containing a functional hydroxyl group.

  X represents a single bond or a divalent linking group as described above. Examples of the divalent linking group include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, a thioether group, an amino group, a disulfide group, an acyl group, Examples thereof include an alkylsulfonyl group, -CH = CH-, an aminocarbonylamino group, and an aminosulfonylamino group.

This divalent linking group may have a substituent. As these substituents, for example, those similar to those listed above for R ^{1 to} R ¹³ can be mentioned.

  X is preferably a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, a bond having no electron withdrawing property such as —CH═CH—, an aminocarbonylamino group, and an aminosulfonylamino group, or It is a group. Z is more preferably a single bond, an ether group or a thioether group, and particularly preferably a single bond.

  Next, the cation (ZI-2) will be described.

The cation (ZI-2) is a cation when R _{201 to} R ₂₀₃ in the formula (ZI) each independently represents an organic group not containing an aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ is a 1 to 30 carbon atoms for example, preferably 1 to 20.

R _{201 to} R ₂₀₃ are preferably each independently an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group. A linear, branched or cyclic 2-oxoalkyl group or an alkoxycarbonylmethyl group is more preferable, and a linear or branched 2-oxoalkyl group is particularly preferable.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be linear, branched chain and may be any of circular, preferred examples are straight chain or branched chain alkyl group (e.g., methyl group having 1 to 10 carbon atoms, An ethyl group, a propyl group, a butyl group or a pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group or a norbornyl group).

The 2-oxoalkyl group as R _{201 to} R ₂₀₃ may be linear, branched or cyclic, and preferably includes a group having> C═O at the 2-position of the above alkyl group. .

Preferred examples of the alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R ₂₀₃ is an alkoxy group having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with, for example, a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and / or a nitro group.

Two of R ₂₀₁ to R ₂₀₃ is bonded to each other, they may form a ring structure. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond and / or a carbonyl group in the ring. The two of the group formed by bonding of the R ₂₀₁ to R _203, for example, an alkylene group (e.g., butylene or pentylene group).

Next, the cation (ZI-3) will be described.
The cation (ZI-3) is a cation represented by the following general formula (ZI-3), and is a cation having a phenacylsulfonium salt structure.

In the formula, R _{1c to} R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a phenylthio group, or a halogen atom. As for carbon number of an alkyl group and an alkoxy group, 1-6 are preferable, and, as for carbon number of a cycloalkyl machine, 5-12 are preferable.

R _6c and R _7c represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. As for carbon number of an alkyl group, 1-6 are preferable. The aryl group preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. As for carbon number of these atomic groups, 1-6 are preferable.

Any two or more of R _{1c to} R _7c may be bonded to each other to form a ring structure. Further, R _x and R _y may be bonded to form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond and / or an amide bond.
In particular, when R _6c and R _7c are combined to form a ring, the group formed by combining R _6c and R _7c is preferably an alkylene group having 2 to 10 carbon atoms.

  Specific examples of the cation (ZI-3) are described in the compounds exemplified in paragraphs 0046 and 0047 of JP-A No. 2004-233661 or paragraphs 0040 to 0046 of JP-A No. 2003-35948. And cations.

Next, general formula (ZII) will be described.
In formula (ZII), R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group or a cycloalkyl group. These aryl group, alkyl group and cycloalkyl group may have a substituent.
Preferable examples of the aryl group as R ₂₀₄ and R ₂₀₅ include the same groups as those enumerated above for R _{201 to} R ₂₀₃ in the compound (ZI-1).
Preferable examples of the alkyl group and cycloalkyl group as R ₂₀₄ and R ₂₀₅ include the straight chain, branched chain, or cycloalkyl group listed above for R _{201 to} R ₂₀₃ in compound (ZI-2).
Specific examples of the compound (A) according to the present invention include the following.

Compound (A) may be used alone or in combination of two or more.
The content of the compound (A) is preferably 0.1 to 40% by mass, more preferably 0.3 to 30% by mass, and still more preferably 0. 0% by mass based on the total solid content of the composition of the present invention. 5 to 20% by mass.

[2] Photoacid generator (B)
The photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation. Here, the “photoacid generator” does not include the above-mentioned compound (A), and does not include a basic compound that generates an acid upon irradiation with actinic rays or radiation other than the compound (A).

Examples of the photoacid generator include a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, an actinic ray or radiation used for a microresist, etc. Known compounds that generate an acid upon irradiation and mixtures thereof can be appropriately selected and used. Examples of these include onium salts such as sulfonium salts and iodonium salts, and diazodisulfone compounds such as bis (alkylsulfonyldiazomethane).
Preferable examples of the photoacid generator include compounds represented by the following general formulas (ZX), (ZXI) and (ZXII).

In the general formula (ZX), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group. The carbon number of the organic group as R _201, R ₂₀₂ and R ₂₀₃ is, for example, 1 to 30, preferably 1 to 20.
Two of R _{201 to} R ₂₀₃ may be bonded to each other via a single bond or a linking group to form a ring structure. Examples of the linking group in this case include an ether bond, a thioether bond, an ester bond, an amide bond, a carbonyl group, a methylene group, and an ethylene group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include alkylene groups such as a butylene group and a pentylene group.

Specific examples of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the cation (ZI-1), (ZI-2) or (ZI-3) described above.

X ⁻ represents a non-nucleophilic anion. Examples of X ⁻ include a sulfonate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ^—, and SbF ₆ ^— . X ⁻ is preferably an organic anion containing a carbon atom. As a preferable organic anion, the organic anion shown to following AN1-AN3 is mentioned, for example.

In the formula _AN1~AN3, Rc 1 ~Rc ₃ independently represents an organic group. Examples of the organic group include those having 1 to 30 carbon atoms, preferably an alkyl group, an aryl group, or a group in which a plurality of these groups are linked through a linking group. Examples of this linking group include a single bond, —O—, —CO ₂ —, —S—, —SO ₃ —, and —SO ₂ N (Rd ₁ ) —. Here, Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with a bonded alkyl group or aryl group.

The organic group of Rc _{1 to} Rc ₃ may be an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By containing a fluorine atom or a fluoroalkyl group, it becomes possible to increase the acidity of the acid generated by light irradiation. Thereby, the sensitivity of the actinic ray-sensitive or radiation-sensitive resin composition can be improved. Rc _{1 to} Rc ₃ may be bonded to other alkyl groups and aryl groups to form a ring structure.

Further, as preferred X ⁻ , a sulfonate anion represented by the following general formula (SA1) or (SA2) can be mentioned.

In formula (SA1),
Ar represents an aryl group and may further have a substituent other than a-(D-B) group.
n represents an integer of 1 or more. n is preferably 1 to 4, more preferably 2 to 3, and most preferably 3.
D represents a single bond or a divalent linking group. The divalent linking group is an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, or an ester group.
B represents a hydrocarbon group.

In formula (SA2),
Xf each independently represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.

R ₁ and R ₂ are each independently a hydrogen atom, a fluorine atom, an alkyl group and represents a group in which at least one hydrogen atom is selected from alkyl group substituted with a fluorine atom, R ₁ in the case where there are multiple And each of R ₂ may be the same as or different from each other.
L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same as or different from each other.
E represents a group having a cyclic structure.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

First, the sulfonate anion represented by the formula (SA1) will be described in detail.
In formula (SA1), Ar is preferably an aromatic ring having 6 to 30 carbon atoms. Specifically, Ar represents, for example, a benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene Ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring Benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, Antoren ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. Of these, a benzene ring, a naphthalene ring or an anthracene ring is preferable, and a benzene ring is more preferable, from the viewpoint of achieving both roughness improvement and high sensitivity.

  When Ar further has a substituent other than a-(D-B) group, examples of this substituent include the following. That is, as this substituent, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group Alkylthioxy groups such as methylthioxy, ethylthioxy and tert-butylthioxy groups; arylthioxy groups such as phenylthioxy and p-tolylthioxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl Acetoxy group; straight chain alkyl group such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; branched chain alkyl group; vinyl group, propenyl group and hexenyl group An alkenyl group of Styrene group; hydroxy group; a carboxy group; an aryl group such as a phenyl group and tolyl group; an alkynyl group such as propynyl group and hexynyl group and a sulfonic acid group. Of these, straight chain alkyl groups and branched chain alkyl groups are preferred from the viewpoint of improving roughness.

  In formula (SA1), D is preferably a single bond, or an ether group or an ester group. More preferably, D is a single bond.

  In formula (SA1), B is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a cycloalkyl group. B is preferably an alkyl group or a cycloalkyl group. The alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B may have a substituent.

  The alkyl group as B is preferably a branched alkyl group. Examples of the branched chain alkyl group include isopropyl group, tert-butyl group, tert-pentyl group, neopentyl group, sec-butyl group, isobutyl group, isohexyl group, 3,3-dimethylpentyl group and 2-ethylhexyl group. Can be mentioned.

  The cycloalkyl group as B may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. Can be mentioned.

  When the alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B has a substituent, examples of the substituent include the following. That is, as this substituent, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group Alkylthioxy groups such as methylthioxy, ethylthioxy and tert-butylthioxy groups; arylthioxy groups such as phenylthioxy and p-tolylthioxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl Acetoxy group; straight chain alkyl group such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group and dodecyl group; branched chain alkyl group such as 2-ethylhexyl group; cycloalkyl group such as cyclohexyl group; Vinyl group, propeni Alkenyl groups such as and hexenyl; include and carbonyl group; acetylene group; hydroxy group; a carboxy group; a sulfonic acid group an aryl group such as a phenyl group and tolyl group; an alkynyl group such as propynyl group and hexynyl group. Among these, a straight chain alkyl group and a branched chain alkyl group are preferable from the viewpoint of achieving both improved roughness and high sensitivity.

Next, the sulfonate anion represented by the formula (SA2) will be described in detail.
In formula (SA2), Xf represents a fluorine atom or an alkyl group in which at least one hydrogen atom has been substituted with a fluorine atom. As this alkyl group, a C1-C10 thing is preferable and a C1-C4 thing is more preferable. The alkyl group substituted with a fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, Xf is preferably a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F _{17, CH 2 CF 3, CH} 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F ₉ or CH ₂ CH ₂ C ₄ F ₉ . Among these, a fluorine atom or CF ₃ is preferable, and a fluorine atom is most preferable.

In formula (SA2), each of R ₁ and R ₂ is a group selected from a hydrogen atom, a fluorine atom, an alkyl group, and an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group which may be substituted with a fluorine atom is preferably an alkyl group having 1 to 4 carbon atoms. Moreover, as an alkyl group substituted by the fluorine atom, a C1-C4 perfluoroalkyl group is especially preferable. Specifically, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH _{2 CH 2 CF 3, CH 2 C} 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 and _CH 2 _CH 2 _{C 4} F ₉ is mentioned, and among them, CF ₃ is preferable.

  In the formula (SA2), x is preferably 1 to 8, and more preferably 1 to 4. y is preferably 0 to 4, and more preferably 0. z is preferably from 0 to 8, and more preferably from 0 to 4.

In formula (SA2), L represents a single bond or a divalent linking group. Examples of the divalent linking group include —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, and an alkenylene group. It is done. Among these, —COO—, —OCO—, —CO—, —O—, —S—, —SO— or —SO ₂ — is preferable, and —COO—, —OCO— or —SO ₂ — is more preferable.

  In formula (SA2), E represents a group having a cyclic structure. Examples of the group having a cyclic structure include a cyclic aliphatic group, an aryl group, and a group having a heterocyclic structure.

  The cycloaliphatic group as E may have a monocyclic structure or a polycyclic structure. As the cyclic aliphatic group having a monocyclic structure, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are preferable. The cycloaliphatic group having a polycyclic structure is preferably a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. In particular, when a cycloaliphatic group having a bulky structure of 6-membered ring or more is adopted as E, diffusibility in the film in the PEB (post-exposure heating) step is suppressed, and the resolution and EL (exposure latitude) are further improved. It becomes possible to improve.

The aryl group as E is, for example, a phenyl group, a naphthyl group, a phenanthryl group, or an anthryl group.
The group having a heterocyclic structure as E may have aromaticity or may not have aromaticity. The heteroatom contained in this group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, a piperidine ring, and a morpholine ring. Among these, a furan ring, a thiophene ring, a pyridine ring, a piperidine ring, and a morpholine ring are preferable.

  E may have a substituent. Examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably 1 to 12 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), a hydroxy group, Examples include an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group.

As the photoacid generator, a compound having a plurality of structures represented by the general formula (ZX) may be used. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZX), at least one coupling structure of R ₂₀₁ to R ₂₀₃ of another compound represented by the general formula (ZX) It may be a compound.
More preferable examples of the cation structure of the (ZX) component include the general formulas (ZI-1) to (ZI-3) described above.

Hereinafter, general formulas (ZXI) and (ZXII) will be described.
In the general formula (ZXI) and (ZXII), R ₂₀₄ ~R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group. These aryl group, alkyl group and cycloalkyl group may have a substituent.

Preferable examples of the aryl group as R _{204 to} R ₂₀₇ include the same groups as those enumerated above for R _{201 to} R ₂₀₃ in the compound (ZI-1).
Preferable examples of the alkyl group and cycloalkyl group as R _{204 to} R ₂₀₇ include the straight chain, branched chain, or cycloalkyl group listed above for R _{201 to} R ₂₀₃ in compound (ZI-2).

Incidentally, X in the general formula (ZXI) ^- is, X in the general formula (ZX) ^- is synonymous.
Other preferred examples of the photoacid generator include compounds represented by the following general formula (ZIV), (ZV) or (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents a substituted or unsubstituted aryl group.
R ₂₀₈ represents an alkyl group, a cycloalkyl group, or an aryl group independently in the general formulas (ZV) and (ZVI). These alkyl group, cycloalkyl group and aryl group may be substituted or unsubstituted.
These groups are preferably substituted with a fluorine atom. If it carries out like this, it will become possible to raise the intensity | strength of the acid which a photo-acid generator generate | occur | produces.

R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an electron-withdrawing group. These alkyl group, cycloalkyl group, aryl group and electron-withdrawing group may be substituted or unsubstituted.
Preferable R ₂₀₉ includes a substituted or unsubstituted aryl group.
Preferable R ₂₁₀ includes an electron withdrawing group. As this electron attractive group, Preferably, a cyano group and a fluoroalkyl group are mentioned.

  A represents an alkylene group, an alkenylene group or an arylene group. These alkylene group, alkenylene group and arylene group may have a substituent.

A compound having a plurality of structures represented by the general formula (ZVI) is also preferable as the photoacid generator. Such compounds, for example, binding to _{R 209} or _{R 210} of the compound represented by the general formula (ZVI), and the _{R 209} or _{R 210} of another compound represented by the general formula (ZVI) together And a compound having the above structure.

As a photo-acid generator, the compound represented by general formula (ZX)-(ZXII) is more preferable, the compound represented by general formula (ZX) is still more preferable, and the compound represented by general formula (ZX) What a cation structure is represented with general formula (ZI-1)-(ZI-3) is especially preferable.
Below, the specific example of a photo-acid generator is shown.

  In addition, a photo-acid generator may be used individually by 1 type, and may be used in combination of 2 or more type. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.

  The content of the photoacid generator is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 on the basis of the total solid content of the composition. ˜20 mass%.

[3] Acid-decomposable resin The acid-decomposable resin typically includes a group (hereinafter also referred to as an acid-decomposable group) that is decomposed by the action of an acid to generate an alkali-soluble group. This resin may have an acid-decomposable group in one of the main chain and side chain of the resin, or in both of them. This resin preferably has an acid-decomposable group in the side chain.

  As the acid-decomposable group, a group in which a hydrogen atom of an alkali-soluble group such as a —COOH group and a —OH group is substituted with a group capable of leaving by the action of an acid is preferable. As the group capable of leaving by the action of an acid, an acetal group or a tertiary ester group is particularly preferable.

  Examples of the base resin in the case where these acid-decomposable groups are bonded as side chains include alkali-soluble resins having —OH or —COOH groups in the side chains. Examples of such alkali-soluble resins include those described later.

  The alkali dissolution rate of these alkali-soluble resins is preferably 17 nm / second or more as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). This speed is particularly preferably 33 nm / second or more.

  From this point of view, particularly preferable alkali-soluble resins include o-, m- and p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene). ), Partially O-alkylated or O-acylated product of poly (hydroxystyrene), styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, and hydrogenated novolac resin. And a resin containing a repeating unit having a carboxy group such as (meth) acrylic acid and norbornenecarboxylic acid.

  Examples of the preferred repeating unit having an acid-decomposable group include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, and (meth) acrylic acid tertiary alkyl ester. As this repeating unit, 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate is more preferable.

  Resins that are decomposed by the action of an acid and have increased solubility in an alkaline developer are disclosed in European Patent 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. As disclosed, for example, a resin is reacted with a precursor of a group capable of leaving by the action of an acid, or an alkali-soluble resin monomer having a group capable of leaving by the action of an acid is combined with various monomers. It is obtained by polymerizing.

  In the case where the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray or high energy light having a wavelength of 50 nm or less (for example, EUV), this resin preferably has a hydroxystyrene repeating unit. . More preferably, the resin is a copolymer of hydroxystyrene and hydroxystyrene protected with a group capable of leaving by the action of an acid, or a copolymer of hydroxystyrene and a (meth) acrylic acid tertiary alkyl ester. It is.

Specific examples of such a resin 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 an aromatic ring group, for example. Note that R ₀₃ is an alkylene group, and may combine with the Ar ₁ as an aromatic ring group to form a ring together with the —C—C— chain. R ₀₃ and Ar ₁ are alkylene groups, and they may be bonded to each other to form, for example, a 5-membered or 6-membered ring together with the —C—C— chain.

n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4, preferably 1 to 2, and more preferably 1.

The alkyl group as R _{01 to} R ₀₃ is, for example, an alkyl group having 20 or less carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a hexyl group. , 2-ethylhexyl group, octyl group or dodecyl group. More preferably, these alkyl groups are alkyl groups having 8 or less carbon atoms. In addition, 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 described above.

  The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Preferably, a C3-C8 monocyclic cycloalkyl group, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is mentioned. In addition, 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 is preferably 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 preferably has 6 to 14 carbon atoms, and examples thereof include a benzene ring, a toluene ring and a naphthalene ring. In addition, these aromatic ring groups may have a substituent.

Examples of the group Y leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ). ), -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ) -C (= O) -O-C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) and And a group represented by —CH (R ₃₆ ) (Ar).

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring structure.
R ₀₁ and R ₀₂ each independently represents 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, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl. Groups, hexyl groups and octyl groups.

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. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, such as an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, A tetracyclododecyl group and an androstanyl group are mentioned. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

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 formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. 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. Note that some of the carbon atoms in the ring structure may be substituted with a heteroatom 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 hydroxyl group, a carboxy group, a halogen atom, an alkoxy group, a thioether group, an acyl group, and an acyloxy group. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.

As the group Y leaving 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 cycloaliphatic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. In addition, these cycloaliphatic groups and aromatic ring groups may contain a hetero atom.
In addition, at least two of Q, M, and L ₁ may be bonded to each other to form a 5-membered or 6-membered ring.

The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and An octyl group is 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 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 specifically includes 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 include a benzyl group and a phenethyl group.

The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group), cycloalkylene group (for example, cyclopentylene group or cyclohexylene group). ), an alkenylene group (e.g., an ethylene group, a propenylene group or a butenylene group), an arylene group (e.g., phenylene, tolylene or naphthylene group), - S -, - O -, - CO -, - SO 2 -, - N (R ₀ ) — or a combination of two or more thereof. 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 includes 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-described groups as L ₁ and L ₂ .

Examples of the cycloaliphatic group or aromatic ring group represented by Q include the above-described cycloalkyl groups and aryl groups as L ₁ and L ₂ . These cycloalkyl group and aryl group are preferably groups having 3 to 15 carbon atoms.

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

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

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 hydroxyl group, a carboxy group, a halogen atom, an alkoxy group, a thioether group, an acyl group, and an acyloxy group. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.

  The group represented by-(MQ) is preferably a group having 1 to 30 carbon atoms, and more preferably a group having 5 to 20 carbon atoms. In particular, a group having 6 or more carbon atoms is preferable from the viewpoint of outgas suppression.

Other preferred resins include resins having a repeating unit represented by the following general formula (X).

In general formula (X),
Xa ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. T represents a single bond or a divalent linking group.
Rx ₁ to Rx ₃ are each independently a linear or branched alkyl group, or a cycloalkyl group of monocyclic or polycyclic ring. In addition, at least two of Rx _{1 to} Rx ₃ may be bonded to each other to form a monocyclic or polycyclic cycloalkyl group.

  Examples of the divalent linking group as T include an alkylene group, a-(COO-Rt)-group, and a-(O-Rt)-group. Here, Rt represents an alkylene group or a cycloalkylene group.

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

The alkyl group as Rx _{1 to} Rx ₃ is preferably an alkyl group 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. It is.

The cycloalkyl group as Rx _{1 to} Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. It is a polycyclic cycloalkyl group.

Examples of the cycloalkyl group that can be formed by combining at least two of Rx _{1 to} Rx ₃ with each other include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecane group, and the like. Polycyclic cycloalkyl groups such as nyl group and adamantyl group are preferred.

In particular, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to each other to form the above-described cycloalkyl group is preferable.

Specific examples of the repeating unit represented by the general formula (X) are shown below, but the present invention is not limited thereto.

  The content of the repeating unit represented by the general formula (X) in the acid-decomposable resin is preferably in the range of 3 to 90 mol%, more preferably 5 to 80 mol%, based on all repeating units. And particularly preferably within the range of 7 to 70 mol%.

In addition, when the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray or high energy light beam having a wavelength of 50 nm or less (for example, EUV), this resin is a compound represented by the general formula (VI). It is preferable to have a unit. Since the repeating unit of the general formula (VI) has an alkali-soluble group, it can assist the alkali solubility of the resin. Further, the pattern strength can be improved, and further, a function of controlling the Tg of a film formed using the composition of the present invention can be imparted.

Where
R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
Ar ₁ represents an aromatic ring group.
Alternatively, R ₀₃ represents an alkylene group, and may be bonded to Ar ₁ as an aromatic ring group to form a ring together with the —C—C— chain. Alternatively, R ₀₃ and Ar ₁ may represent an alkylene group, and both may be bonded to each other to form a ring together with the —C—C— chain.

  n represents an integer of 1 to 4. n is preferably 1 to 2, and more preferably 1.

The alkyl group as R _{01 to} R ₀₃ is, for example, an alkyl group having 20 or less carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a hexyl group. , 2-ethylhexyl group, octyl group or dodecyl group. More preferably, these alkyl groups are alkyl groups having 8 or less carbon atoms. In addition, 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 described above.
The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Preferably, a C3-C8 monocyclic cycloalkyl group, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is mentioned. In addition, 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 is preferably 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 preferably has 6 to 14 carbon atoms, and examples thereof include a benzene ring, a toluene ring and a naphthalene ring. In addition, these aromatic ring groups may have a substituent.
Specific examples of the repeating unit represented by the general formula (VI) are shown below. However, it is not limited to these.

  The content of the repeating unit represented by the general formula (VI) in the acid-decomposable resin is preferably in the range of 20 to 90 mol%, more preferably 30 to 80 mol%, based on all repeating units. Is within the range.

Although the specific example of resin demonstrated above is shown below, this invention is not limited to these.

In the above specific example, tBu represents a t-butyl group.
The content of the group capable of decomposing with an acid is determined by the formula B according to the number of groups (B) capable of decomposing with an acid in the resin and the number of alkali-soluble groups not protected by a group capable of leaving with an acid (S). / (B + S). This content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

  When the composition of the present invention is irradiated with ArF excimer laser light, the resin preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure. Hereinafter, such a resin is referred to as “alicyclic hydrocarbon-based acid-decomposable resin”.

Examples of the alicyclic hydrocarbon-based acid-decomposable resin include a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following general formulas (pI) to (pV), and the following general formula (II- A resin containing at least one selected from the group consisting of repeating units represented by AB) is preferred.

In general formulas (pI) to (pV),
R ₁₁ 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, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group. However, at least one of R _{12 to} R ₁₄ represents a cycloalkyl group. Moreover, any of R ₁₅ and R ₁₆ represents a cycloalkyl group.

R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{17 to} R ₂₁ represents a cycloalkyl group. Further, any one of R ₁₉ and R ₂₁ represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{22 to} R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring structure.

In general formula (II-AB),
R ₁₁ ′ and R ₁₂ ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Z ′ represents an atomic group necessary for forming an alicyclic structure with two bonded carbon atoms (C—C).

The general formula (II-AB) is more preferably the following general formula (II-AB1) or general formula (II-AB2).

In general formulas (II-AB1) and (II-AB2),
R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, —COOH, —COOR ₅ , a group that decomposes by the action of an acid, —C (═O) —XA '-R ₁₇ ' represents an alkyl group or a cycloalkyl group. Here, R ₅ represents an alkyl group, a cycloalkyl group, or a group having a lactone structure. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A ′ represents a single bond or a divalent linking group. R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxy group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or a group having a lactone structure. Here, R ₆ represents an alkyl group or a cycloalkyl group. In addition, at least two of R ₁₃ ′ to R ₁₆ ′ may be bonded to each other to form a ring structure.
n represents 0 or 1.

In general formulas (pI) to (pV), the alkyl group in R _{12 to} R ₂₅ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. , N-butyl group, sec-butyl group and t-butyl group.

The cycloalkyl group in R _{12 to} R ₂₅ or the cycloalkyl group formed by Z and a carbon atom may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Specific examples include groups having a monocyclo, bicyclo, tricyclo, and tetracyclo structure having 5 or more carbon atoms. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable.

  Preferred cycloalkyl groups include, for example, adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group. Group, cyclodecanyl group and cyclododecanyl group. More preferably, an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group, and a tricyclodecanyl group are exemplified.

  These alkyl groups and cycloalkyl groups may have a substituent. As this substituent, an alkyl group (C1-C4), a halogen atom, a hydroxy group, an alkoxy group (C1-C4), a carboxy group, and an alkoxycarbonyl group (C2-C6) are mentioned, for example. . These substituents may have further substituents. As this further substituent, a hydroxy group, a halogen atom, and an alkoxy group are mentioned, for example.

  The structures represented by the general formulas (pI) to (pV) can be used for protecting alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field.

  Specifically, for example, a structure in which a hydrogen atom such as a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group is substituted with a structure represented by general formulas (pI) to (pV) can be given. A structure in which a hydrogen atom of a carboxylic acid group or a sulfonic acid group is substituted with a structure represented by general formulas (pI) to (pV) is preferable.

As the repeating unit having an alkali-soluble group protected by the structure represented by the general formulas (pI) to (pV), a repeating unit represented by the following general formula (pA) is preferable.

In general formula (pA),
R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. Each of the plurality of Rs may be the same as or different from each other.
A is selected from the group consisting of a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, a urea group, and combinations of two or more thereof, preferably It is a single bond.
Rp ₁ is a group represented by any one of the general formulas (pI) to (pV).

  The repeating unit represented by the general formula (pA) is most preferably a repeating unit of 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate.

Specific examples of the repeating unit represented by the general formula (pA) are shown below.

In the above structural formulas, Rx is _H, represent CH 3, CF ₃ or _CH 2 OH, Rxa and Rxb each independently represents an alkyl group having 1 to 4 carbon atoms.

The halogen atom as R ₁₁ ′ or R ₁₂ ′ in the general formula (II-AB) is, for example, a chlorine atom, a bromine atom, a fluorine atom or an iodine atom.

The alkyl group as R ₁₁ ′ or R ₁₂ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a linear group Or a branched butyl group, a pentyl group, a hexyl group, and a heptyl group are mentioned.

  The atomic group represented by Z ′ is an atomic group that forms a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin. As this atomic group, those forming a repeating unit of a bridged alicyclic hydrocarbon are preferable.

Examples of the skeleton of the alicyclic hydrocarbon formed include the same cycloalkyl groups as R _{12 to} R ₂₅ in the general formulas (pI) to (pVI).

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the above general formulas (II-AB1) and (II-AB2).

  In the alicyclic hydrocarbon-based acid-decomposable resin, the group capable of decomposing by the action of an acid is a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pI) to the general formula (pV). , At least one of the repeating unit represented by the general formula (II-AB) and the repeating unit of the copolymer component described later.

Each substituent of R ₁₃ ′ to R ₁₆ ′ in the general formulas (II-AB1) and (II-AB2) is an alicyclic structure or a bridged alicyclic structure in the general formula (II-AB). It can also be a substituent of the atomic group Z ′ to form.

Specific examples of the repeating unit represented by the general formula (II-AB1) or (II-AB2) are shown below, but the present invention is not limited to these examples.

  The alicyclic hydrocarbon-based acid-decomposable resin preferably has a repeating unit containing a lactone group. This lactone group is preferably a group having a 5- to 7-membered ring lactone structure, and in particular, other ring structures are condensed to form a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure. Is preferred.

This alicyclic hydrocarbon-based acid-decomposable resin more preferably contains a repeating unit having a group containing a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). Yes. The group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures include (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17). . By using specific lactone structures, line edge roughness and development defects can be further reduced.

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include, for example, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, Examples include a carboxy group, a halogen atom, a hydroxy group, a cyano group, and an acid-decomposable group.

n ₂ represents an integer of 0-4. When n ₂ is an integer of 2 or more, a plurality of Rb ₂ may be the same or different from each other. In this case, a plurality of Rb2s may be bonded to each other to form a ring structure.

Examples of the repeating unit having a group containing a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-17) include those in the general formulas (II-AB1) and (II-AB2). Wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by general formulas (LC1-1) to (LC1-17), and a repeating unit represented by the following general formula (AI) Is mentioned. Examples of the former include structures in which R _{5 of} —COOR ₅ is a group represented by general formulas (LC1-1) to (LC1-17).

In general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
The alkyl group as Rb ₀ is, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group or a t-butyl group. These alkyl groups may have a substituent. Examples of the substituent include a hydroxy group and a halogen atom.

Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Rb ₀ is preferably a hydrogen atom or a methyl group.

Ab represents an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxy group, or a combination thereof. Ab is preferably a single bond or a linking group represented by —Ab ₁ —CO ₂ —.
Ab ₁ is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

  V is a group represented by any one of the general formulas (LC1-1) to (LC1-17).

  The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity thereof is preferably 90% ee or more, more preferably 95% ee or more.

Particularly preferred repeating units having a lactone group include the following repeating units. By selecting an optimal lactone group, the pattern profile and the density dependency are improved. In the formula, Rx and R represent H, CH ₃ , CH ₂ OH or CF ₃ .

  The alicyclic hydrocarbon-based acid-decomposable resin preferably has a repeating unit containing an alicyclic hydrocarbon structure substituted with a polar group. Thereby, substrate adhesiveness and developer affinity can be improved. As this polar group, a hydroxy group or a cyano group is preferable. In addition, the hydroxy group as a polar group forms an alcoholic hydroxy group.

Examples of the alicyclic hydrocarbon structure substituted with a polar group include structures represented by the following general formula (VIIa) or (VIIb).

In General Formula (VIIa), R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxy group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxy group or a cyano group. Preferably, a one or two hydroxy groups of the R ₂ c to R 4 _c, and the remainder is a hydrogen atom. More preferably, a two are hydroxyl groups of R ₂ c to R 4 _c, the remaining one is a hydrogen atom.

  The group represented by the general formula (VIIa) is preferably a dihydroxy body or a monohydroxy body, and more preferably a dihydroxy body.

The repeating unit having a group represented by the general formula (VIIa) or (VIIb) includes at least one of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2). Examples thereof include those having a group represented by the above general formula (VIIa) or (VIIb) and repeating units represented by the following general formula (AIIa) or (AIIb). Examples of the former include structures in which R _{5 of} —COOR ₅ is a group represented by the general formula (VIIa) or (VIIb).

In general formulas (AIIa) and (AIIb),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c have the same meanings as _{R 2} c to R ₄ c in the general formula (VIIa).

Specific examples of the repeating unit represented by the general formula (AIIa) or (AIIb) are shown below, but the present invention is not limited thereto.

The alicyclic hydrocarbon-based acid-decomposable resin may have a repeating unit represented by the following general formula (VIII).

In General Formula (VIII), Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxy group, an alkyl group, or —OSO ₂ —R ₄₂ . Wherein R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group as R ₄₁ or R ₄₂ may be substituted with a halogen atom or the like. In this case, the halogen atom is preferably a fluorine atom.

Examples of the repeating unit represented by the general formula (VIII) include the following specific examples, but the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin preferably has a repeating unit containing an alkali-soluble group, and more preferably has a repeating unit containing a carboxy group. Thereby, the resolution in contact hole use can be improved.

  As the repeating unit containing a carboxy group, any of a repeating unit in which a carboxy group is directly bonded to the main chain of the resin and a repeating unit in which a carboxy group is bonded to the main chain of the resin via a linking group. preferable.

  As an example of the former, a repeating unit by acrylic acid or methacrylic acid can be mentioned. The linking group in the latter may have a monocyclic or polycyclic cycloalkyl structure.

  The repeating unit containing a carboxy group is most preferably a repeating unit of acrylic acid or methacrylic acid.

The resin containing the repeating unit (A) may further contain a repeating unit which has an alicyclic hydrocarbon structure having no polar group and does not exhibit acid decomposability. Examples of such a repeating unit include a repeating unit represented by the following general formula (IV).

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxy group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group, or a group represented by —CH ₂ —O—Ra ₂ . Here, Ra2 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 particularly preferably a hydrogen atom or a methyl group.

Examples of the cyclic structure provided in R ₅ include a monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group, and 3 carbon atoms such as a cyclohexenyl group. ˜12 cycloalkenyl groups. Preferred monocyclic hydrocarbon groups include those having 3 to 7 carbon atoms. Examples of such monocyclic hydrocarbon groups include a cyclopentyl group and a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group.
Examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group.

Examples of the bridged cyclic hydrocarbon group include pinane, bornane, norpinane, norbornane, and bicyclooctane ring (for example, bicyclo [2.2.2] octane ring or bicyclo [3.2.1] octane ring). Tricyclic hydrocarbon groups such as bicyclic hydrocarbon groups, homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane and tricyclo [4.3.1.1 ^2,5 ] undecane rings , And tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane and tetracyclic hydrocarbon groups such as perhydro-1,4-methano-5,8-methanonaphthalene ring.

  The bridged cyclic hydrocarbon group includes a condensed cyclic hydrocarbon group. Examples of the condensed cyclic hydrocarbon group include 5 to 5 such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene ring. And a group formed by condensing a plurality of 8-membered cycloalkane rings.

Preferred examples of the bridged cyclic hydrocarbon group include a norbornyl group, an adamantyl group, a bicyclooctanyl group, and a tricyclo [5,2,1,0 ^2,6 ] decanyl group. More preferable examples of the bridged cyclic hydrocarbon group include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may further have a substituent. Preferable substituents include a halogen atom, an alkyl group, a hydroxy group protected with a protective group, and an amino group protected with a protective group.

Preferred halogen atoms include bromine, chlorine and fluorine atoms.
Preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. This alkyl group may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group, a hydroxy group protected with a protecting group, and an amino group protected with a protecting group.

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

Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below. In these specific examples, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

  The content of the repeating unit having an alicyclic hydrocarbon structure not having a polar group and not exhibiting acid decomposability is preferably 0 to 40 mol% with respect to all repeating units in the resin. More preferably, it is -20 mol%.

  Resins suitable for KrF, EB, EUV and the like may have a repeating unit other than the repeating units described above. Examples of such a repeating unit include a repeating unit that is stable against the action of an acid.

Examples of the repeating unit stable to the action of an acid include a non-acid-decomposable aryl structure or cycloalkyl structure in the side chain of the acrylic structure, such as the repeating unit represented by the general formula (IV) described above. The repeating unit which has is mentioned. In the repeating unit represented by the general formula (IV), R ₅ is preferably a hydrocarbon group and has a cyclic structure therein. Specific examples in the case of having a cyclic structure include a monocyclic or polycyclic cycloalkyl group (preferably having 3 to 12 carbon atoms, more preferably 3 to 7 carbon atoms, and particularly preferably a cyclohexyl group), monocyclic or polycyclic A cycloalkenyl group (preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 12 carbon atoms, particularly preferably a phenyl group or a naphthyl group), and an aralkyl group (preferably C7-20, more preferably C7-12, and particularly preferably benzyl group). By having such a structure, adjustment of contrast and improvement of etching resistance can be expected.

  The content of the repeating unit that is stable with respect to the action of the acid is preferably 0 to 40 mol%, more preferably 1 to 20 mol%, based on all repeating units in the acid-decomposable resin. .

Specific examples of the repeating unit that is stable against the action of an acid include the following in addition to the specific examples of the repeating unit represented by the general formula (IV). In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The weight average molecular weight of the acid-decomposable resin is preferably in the range of 2,000 to 200,000 as a polystyrene conversion value determined by the GPC method. By setting the weight average molecular weight to 2,000 or more, heat resistance and dry etching resistance can be particularly improved. When the weight average molecular weight is 200,000 or less, the developability can be particularly improved, and the film forming property can also be improved due to the decrease in the viscosity of the composition.

  A more preferable molecular weight is in the range of 2,500 to 50,000, and still more preferably in the range of 3,000 to 20,000. Moreover, in the fine pattern formation using an electron beam, X-rays, and a high energy ray (for example, EUV) having a wavelength of 50 nm or less, the weight average molecular weight is most preferably in the range of 3,000 to 10,000. By adjusting the molecular weight, an improvement in the heat resistance and resolution of the composition and a reduction in development defects can be achieved at the same time.

  The resin dispersibility (Mw / Mn) which decomposes by the action of an acid and increases the solubility in an alkali developer is preferably from 1.0 to 3.0, more preferably from 1.2 to 2.5. 2 to 1.6 is more preferable. By adjusting the degree of dispersion, for example, the line edge roughness performance can be improved.

  The blending ratio of the acid-decomposable resin in the composition according to the present invention is preferably 0 to 99.9% by mass, more preferably 50 to 95% by mass, and 60 to 93% by mass based on the total solid content. Is more preferable.

[4] Alkali-soluble resin The alkali dissolution rate of the alkali-soluble resin is preferably 2 nm / second or more as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, this rate is 20 nm / second or more.

  Examples of the alkali-soluble resin include novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen or alkyl-substituted poly. Hydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, partially O-alkylated product with respect to hydroxy group of polyhydroxystyrene (for example, 5 to 30 mol%) O-methylated product, O- (1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product or O- (t-butoxycarbonyl) methylated product) or O-acyl (E.g. 5-30 mol% O-acetylated) Or O- (t-butoxy) carbonylated), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxy group-containing methacrylic resin and derivatives thereof, In addition, examples include, but are not limited to, polyvinyl alcohol derivatives.

  Preferred alkali-soluble resins include, for example, novolak resins, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, and partly O- of polyhydroxystyrene. Examples include alkylated or O-acylated products, styrene-hydroxystyrene copolymers, and α-methylstyrene-hydroxystyrene copolymers.

  In particular, a resin having a hydroxystyrene structure is preferable. Of the hydroxystyrene structures, the m-hydroxystyrene structure is particularly preferable.

  The novolak resin can be obtained, for example, by subjecting a predetermined monomer as a main component to addition condensation with aldehydes in the presence of an acidic catalyst.

  Moreover, the weight average molecular weight of alkali-soluble resin is 2000 or more, Preferably it is 5000-200000, More preferably, it is 5000-100000. Here, the weight average molecular weight is defined by a polystyrene conversion value obtained by GPC (gel permeation chromatography).

These alkali-soluble resins may be used alone or in combination of two or more.
The content of the alkali-soluble resin is, for example, 40 to 97% by mass, preferably 60 to 90% by mass, based on the total solid content in the composition.

[5] Acid cross-linking agent Any acid cross-linking agent can be used as long as it is a compound that cross-links a resin soluble in an alkali developer by the action of an acid, but the following (1) to (3) are preferred. .

(1) A hydroxymethyl body, an alkoxymethyl body or an acyloxymethyl body of a phenol derivative.
(2) A compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group.
(3) A compound having an epoxy group.

  Here, as an alkoxymethyl group, a C6 or less thing is preferable. Moreover, as an acyloxymethyl group, a C6 or less thing is preferable.

Among these acid crosslinking agents, particularly preferred are listed below.

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

  The addition amount of the acid crosslinking agent is, for example, 3 to 70% by mass, preferably 5 to 50% by mass, based on the total solid content of the composition.

[6] Dissolution-inhibiting compound As the dissolution-inhibiting compound, an alicyclic or aliphatic compound containing an acid-decomposable group is preferable because it does not lower the permeability at 220 nm or less. Examples of such a compound include cholic acid derivatives containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996). Examples of these alicyclic structures and acid-decomposable groups include those described for the alicyclic hydrocarbon-based acid-decomposable resin.

  When the composition according to the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, the dissolution inhibiting compound may contain a structure in which the phenolic hydroxy group in the phenol compound is substituted with an acid-decomposable group. preferable. As this phenol compound, those containing 1 to 9 phenol skeletons are preferred, and those containing 2 to 6 are more preferred.

The molecular weight of the dissolution inhibiting compound is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.
The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total solid content in the composition.
Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

  The composition according to the present invention further comprises [A5] a basic compound, [A6] a fluorine-based and / or silicon-based surfactant, [A7] a hydrophobic resin, [A8] an organic solvent, and / or [A9]. Other additives may further be included.

[7] Basic Compound The composition according to the present invention preferably contains a basic compound in order to reduce a change in performance over time from exposure to heating. The basic compound plays a role of quenching the deprotection reaction by the acid generated by exposure, and its diffusibility, basicity, etc. can affect the effective diffusibility of the acid.
Preferable basic compounds include ammonium salts represented by the following formula (A) and basic compounds having a structure represented by formulas (B) to (E).

In the formula (A), R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group. (Preferably having 6 to 20 carbon atoms). R ²⁵⁰ and R ²⁵¹ may be bonded to each other to form a ring structure. Moreover, these groups may have a substituent.

Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or 3 to 20 carbon atoms. Of these, a hydroxycycloalkyl group is preferred.
These may contain an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain.

In formula (E), R ^{253 to} R ²⁵⁶ each independently represents an alkyl group (preferably having 1 to 6 carbon atoms) or a cycloalkyl group (preferably having 3 to 6 carbon atoms).

  Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and piperidine. These compounds may have a substituent.

  More preferable compounds include compounds having an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having a hydroxy group and / or an ether bond, and , An aniline derivative having a hydroxy group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole; 2,4,5-triphenylimidazole; and benzimidazole.

  Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane; 1,5-diazabicyclo [4,3,0] non-5-ene; and 1,8-diazabicyclo [5. , 4,0] undec-7-ene.

  Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. Specifically, for example, triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophene. And nium hydroxide.

  The compound having an onium carboxylate structure is a compound in which the anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate.

  Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.

  Examples of aniline compounds include 2,6-diisopropylaniline and N, N-dimethylaniline.

  Examples of the alkylamine derivative having a hydroxy group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine.

  Examples of aniline derivatives having a hydroxy group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Examples of the other basic compound include at least one nitrogen-containing compound selected from 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. In addition to the alkyl group, the amine compound may be a cycloalkyl group (preferably a carbon number of 3 to 20) or an aryl group, provided that at least one alkyl group (preferably having a carbon number of 1 to 20) is bonded to the nitrogen atom. A group (preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.

The amine compound preferably contains an oxygen atom in the alkyl chain and has one or more oxyalkylene groups. The number of oxyalkylene groups is preferably 3-9, and more preferably 4-6. The oxyalkylene group is preferably 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—). Groups are more preferred.

  As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.

The ammonium salt compound contains an oxygen atom in the alkyl chain and may have one or more oxyalkylene groups. The number of oxyalkylene groups is preferably 3-9, and more preferably 4-6. The oxyalkylene group is preferably 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—). Groups are more preferred.

Examples of the anion of the ammonium salt compound include halides, sulfonates, borates, phosphates, hydroxides, and the like. Among these, hydroxides are preferable.
As the halide, chloride, bromide or iodide is particularly preferable.

  The amine compound having a phenoxy group is prepared by reacting, for example, a primary or secondary amine having a phenoxy group with a haloalkyl ether, and adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. And then extracted with an organic solvent such as ethyl acetate and roloform. In addition, the amine compound having a phenoxy group reacts by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal, and a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can also be obtained by adding an aqueous solution and then extracting with an organic solvent such as ethyl acetate and chloroform.

  In view of sensitivity, roughness, stability, etc., it is particularly preferable to use an ammonium salt compound as the basic compound, and it is most preferable to use a hydroxide of a quaternary ammonium salt compound.

These basic compounds may be used alone or in combination of two or more.
The molecular weight of the basic compound is preferably 250 to 1000, more preferably 250 to 800, and particularly preferably 400 to 800.
The content of the basic compound is preferably 1.0 to 8.0% by mass, more preferably 1.5 to 5.0% by mass, and still more preferably based on the total solid content of the composition. It is 2.0-4.0 mass%.

[8] Fluorine-based and / or silicon-based surfactant The composition according to the present invention may further contain a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include a fluorine-based surfactant, a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom, and a mixture thereof.

  By incorporating fluorine and / or silicon surfactant into the composition according to the present invention, when using an exposure light source of 250 nm or less, particularly 220 nm or less, with good sensitivity and resolution, there are few adhesion and development defects. A pattern can be given.

Examples of commercially available surfactants that can be used include F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (manufactured by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) And fluorine-based surfactants such as silicon-based surfactants. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A polymer containing a polymer having a fluoroaliphatic group may be used. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

  The polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate and / or (poly (oxyalkylene)) methacrylate. Even if it distributes, block copolymerization may be sufficient.

  Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group. In addition, units having different chain length alkylene in the same chain, such as poly (block connection body of oxyethylene, oxypropylene, and oxyethylene) and poly (block connection body of oxyethylene and oxypropylene) Also good.

  Further, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate has a monomer having two or more different fluoroaliphatic groups and two or more different (poly (oxyalkylene). )) It may be a ternary or higher copolymer obtained by copolymerizing acrylate or methacrylate simultaneously.

For example, Megafac F178, F-470, F-473, F-475, F-476 and F-472 (Dainippon Ink Chemical Co., Ltd.) are mentioned as commercially available surfactants. Further, a copolymer of an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate or methacrylate, an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyethylene)) acrylate or methacrylate And a copolymer of (poly (oxypropylene)) acrylate or methacrylate, a copolymer of an acrylate or methacrylate having a C ₈ F ₁₇ group and (poly (oxyalkylene)) acrylate or methacrylate, and C ₈ F ₁₇ And a copolymer of an acrylate or methacrylate having a group and (poly (oxyethylene)) acrylate or methacrylate and (poly (oxypropylene)) acrylate or methacrylate. That.

  The amount of fluorine and / or silicon-based surfactant used is preferably 0.0001 to 2 mass%, more preferably 0.001 to 1 mass%, based on the total solid content of the composition.

[9] Hydrophobic resin The composition according to the present invention may further contain a hydrophobic resin as described above. When the hydrophobic resin is further contained, the hydrophobic resin is unevenly distributed on the surface layer of the film formed using this composition, and the receding contact angle of the film with respect to the immersion liquid is improved when water is used as the immersion liquid. It becomes possible. Thereby, the immersion liquid followability of a film | membrane can be improved.

  The hydrophobic resin typically contains fluorine atoms and / or silicon atoms. These fluorine atoms and / or silicon atoms may be contained in the main chain of the resin or may be contained in the side chain.

  In the case where the hydrophobic resin contains a fluorine atom, the resin has an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl group containing a fluorine atom as a partial structure containing a fluorine atom. It is preferable to provide.

  The alkyl group containing a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.

  The cycloalkyl group containing a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The cycloalkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.

  An aryl group containing a fluorine atom is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom. Examples of the aryl group include a phenyl group and a naphthyl group. The aryl group containing a fluorine atom may further have a substituent other than the fluorine atom.

Preferable examples of the alkyl group containing a fluorine atom, the cycloalkyl group containing a fluorine atom, and the aryl group containing a fluorine atom include groups represented by the following general formulas (F2) to (F4).

In general formulas (F2) to (F4), R _{57 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{57 to} R ₆₁ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{62 to} R ₆₄ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{65 to} R ₆₈ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. These alkyl groups preferably have 1 to 4 carbon atoms.

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all 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, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be bonded to each other to form a ring.

  Examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

  Examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2- Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2, Examples include 3,3-tetrafluorocyclobutyl group and perfluorocyclohexyl group. Among these, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro (2-methyl) isopropyl group, an octafluoroisobutyl group, a nonafluoro-t-butyl group or a perfluoroisopentyl group is more preferable, and a hexafluoroisopropyl group or More preferred is a heptafluoroisopropyl group.

Examples of the group represented by the general formula (F4) include —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, and —CH. (CF ₃ ) OH. Of these, -C (CF _{3) 2} OH is particularly preferred.

Specific examples of the repeating unit containing a fluorine atom are shown below.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents —F or —CF ₃ .

When the hydrophobic resin contains a silicon atom, the resin preferably has an alkylsilyl structure or a cyclic siloxane structure as a partial structure containing a silicon atom. This allylsilyl structure is preferably a structure containing a trialkylsilyl group.
Preferable examples of the alkylsilyl structure and the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3), R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group or a cycloalkyl group. This alkyl group preferably has 1 to 20 carbon atoms. This cycloalkyl group preferably has 3 to 20 carbon atoms.

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, a urea group, or a combination thereof.
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

Below, the specific example of the repeating unit provided with group represented by general formula (CS-1)-(CS-3) is given. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

The hydrophobic resin may further include at least one group selected from the group consisting of the following (x) to (z).
(X) an alkali-soluble group;
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) an acid-decomposable group.

  (X) Alkali-soluble groups include, for example, phenolic hydroxy groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkyl Sulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and A tris (alkylsulfonyl) methylene group is mentioned. Preferred alkali-soluble groups include fluorinated alcohol groups, sulfonimide groups, and bis (carbonyl) methylene groups. Preferred fluorinated alcohol groups include hexafluoroisopropanol groups.

  The repeating unit having an alkali-soluble group is a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit by acrylic acid and methacrylic acid. Alternatively, this repeating unit may be a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent provided with the alkali-soluble group at the time of superposition | polymerization.

  The content of the repeating unit having an alkali-soluble group is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, based on all repeating units in the hydrophobic resin. More preferably, it is 20 mol%.

Specific examples of the repeating unit having an alkali-soluble group are shown below.

  (Y) Examples of the group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer include a group having a lactone structure, an acid anhydride group, and an acid imide group. Of these, a group having a lactone structure is particularly preferable.

  The repeating unit containing this group is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent provided with this group at the time of superposition | polymerization.

  Examples of the repeating unit having a group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer include the same as the repeating unit having a lactone structure described above in [1] Resin. Can be mentioned.

  The content of the repeating unit having a group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is 1 to 40 mol% based on all repeating units in the hydrophobic resin. Is more preferable, it is more preferable that it is 3-30 mol%, and it is still more preferable that it is 5-15 mol%.

Examples of the (z) acid-decomposable group include the same groups as those described above in [1] Resin.
The content of the repeating unit having an acid-decomposable group is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the hydrophobic resin. More preferably, it is -60 mol%.
The hydrophobic resin may further contain a repeating unit represented by the following general formula (III).

In formula (III), R _c31 represents a hydrogen atom, an alkyl group, an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, a cyano group, or a —CH ₂ —O—Rac ₂ group. Here, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group.

R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group containing an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a fluorine atom and / or a silicon atom.

The alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group preferably has 3 to 20 carbon atoms.
The alkenyl group preferably has 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

  The aryl group is preferably a phenyl group or naphthyl group having 6 to 20 carbon atoms, and these may have a substituent.

R _c32 is preferably an unsubstituted alkyl group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.

L _c3 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group (preferably having a carbon number of 1 to 5), an oxy group, a phenylene group, and an ester bond (a group represented by —COO—).

The hydrophobic resin may further contain a repeating unit represented by the following general formula (CII-AB).

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

Specific examples of the repeating unit represented by the general formula (III) or (CII-AB) are given below. In specific examples, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

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

[10] Organic Solvent The composition according to the present invention typically further contains a predetermined organic solvent that dissolves the above components.
Examples of the organic solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl. Ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran.

Examples of the solvent having a ketone structure include a chain ketone solvent and a cyclic ketone solvent. From the viewpoint of applicability, those having a total carbon number of 5 to 8 are particularly preferred.
Examples of the chain ketone solvent include 2-heptanone, methyl ethyl ketone, and methyl isobutyl ketone. Of these, 2-heptanone is particularly preferred.
Examples of the cyclic ketone solvent include cyclopentanone, 3-methyl-2-cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, cycloheptanone, cyclooctanone and isophorone. Of these, cyclohexanone and cycloheptanone are particularly preferred.

As the organic solvent, a solvent having a ketone structure is preferably used alone, or a mixed solvent of a solvent having a ketone structure and another solvent is preferably used.
Examples of other solvents (combined solvent) to be mixed with the solvent having a ketone structure include propylene glycol monoalkyl ether carboxylate, alkyl lactate, propylene glycol monoalkyl ether, alkyl alkoxypropionate, and lactone compounds.

Examples of the propylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate.
Examples of the alkyl lactate include methyl lactate and ethyl lactate.
Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether and propylene glycol monoethyl ether.
Examples of the alkyl alkoxypropionate include methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate and ethyl ethoxypropionate.
Examples of the lactone compound include γ-butyrolactone.

  Preferable combination solvents include propylene glycol monoalkyl ether carboxylate, alkyl lactate and propylene glycol monoalkyl ether. A more preferred combination solvent is propylene glycol monomethyl ether acetate.

  Further, from the viewpoint of film thickness uniformity and development defect performance, a high boiling point solvent having a boiling point of 200 ° C. or higher such as ethylene carbonate and propylene carbonate may be mixed.

  The amount of these high-boiling solvents added is usually 0.1 to 15% by mass, preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass in the total solvent.

In the present invention, typically, an actinic ray-sensitive or radiation-sensitive resin composition is prepared using an organic solvent, preferably two or more mixed solvents.
The solid content concentration of the composition is usually 1 to 25% by mass, preferably 2 to 20% by mass, and more preferably 2.5 to 10% by mass. In particular, when pattern formation is performed with an electron beam, EUV light or ArF light, the solid content concentration is preferably 2.5 to 20% by mass.

[11] Other additives In the composition according to the present invention, if necessary, a dye, a plasticizer, a surfactant other than the fluorine-based and / or silicon-based surfactants listed above, and a photosensitizer. Further, an additive such as a compound that promotes solubility in a developer may be further contained.

  The compound that promotes solubility in the developer (dissolution promoting compound) is, for example, a low molecular compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or an aliphatic compound is preferable.

  The addition amount of these dissolution promoting compounds is preferably 2 to 50% by mass, more preferably 5 to 30% by mass, based on the resin described above. From the viewpoint of suppressing development residue and preventing pattern deformation during development, the amount added is preferably 50% by mass or less.

  Such a phenol compound having a molecular weight of 1000 or less can be easily obtained by referring to the methods described in, for example, JP-A-4-1222938, JP-A-2-28531, U.S. Pat. No. 4,916,210 and European Patent 219294. Can be synthesized.

  Specific examples of the alicyclic or aliphatic compound having a carboxy group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid and lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, and Although cyclohexane dicarboxylic acid etc. are mentioned, it is not limited to these.

  Specific examples of surfactants other than fluorine and / or silicon surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers , Nonionic surfactants such as sorbitan aliphatic esters and polyoxyethylene sorbitan aliphatic esters. These surfactants may be added alone or in combination of two or more.

[Pattern formation method]
Hereinafter, a pattern forming method using the composition according to the present invention will be described.

  The composition according to the present invention is typically used after being dissolved in a predetermined organic solvent, preferably the above mixed solvent, and coated on a predetermined support. For example, the composition is applied on a substrate (eg, silicon, silicon / silicon dioxide coating, silicon nitride, quartz having a Cr layer) used for manufacturing a precision integrated circuit element or an imprint mold structure. It is applied by an appropriate application method such as a spinner or a coater. Thereafter, this is dried to obtain an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as a photosensitive film). Moreover, 60-150 degreeC is preferable for drying temperature, and 80-130 degreeC is more preferable. In addition, a known antireflection film can be applied in advance.

  Next, the photosensitive film is irradiated with actinic rays or radiation, preferably baked (heated), and then developed. The baking temperature is preferably 80 ° C. to 150 ° C., more preferably 90 to 130 ° C. from the viewpoints of sensitivity and stability. Thereby, a good pattern can be obtained.

Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. As these actinic rays or radiation, for example, those having a wavelength of 250 nm or less, particularly 220 nm or less are more preferable. Examples of such actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, and electron beams. Particularly preferred actinic rays or radiation include ArF excimer laser, F ₂ excimer laser, EUV (13 nm) and electron beam.

  Note that exposure may be performed by filling a liquid (such as pure water) having a higher refractive index than air between the photosensitive film and the lens. That is, immersion exposure may be performed. Thereby, the resolution can be further increased. In this case, an immersion liquid sparingly soluble film (also referred to as “topcoat”) is provided on the resist film between the resist film and the immersion liquid in order to avoid contact between the resist film and the immersion liquid. May be. Further, as another means for avoiding contact between the resist film and the immersion liquid, a hydrophobic resin (HR) may be added to the above-described composition in advance. Specific examples of the hydrophobic resin (HR) include resins described in paragraphs 0172 to 0253 of US2008 / 0305432A1.

In the development step, an alkali developer is usually used.
Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine and Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and fourth amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Examples include alkaline aqueous solutions containing a quaternary ammonium salt or cyclic amines such as pyrrole and pihelidine.

An appropriate amount of alcohol and / or surfactant may be added to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkali developer is usually from 10.0 to 15.0.

  For details of the process for producing an imprint mold using the composition of the present invention, see, for example, Japanese Patent No. 4109085, Japanese Patent Application Laid-Open No. 2008-162101, and “Nanoimprint Basics and Technology Development / Application development-Nanoimprint substrate technology and latest technological development-Editing: Yoshihiko Hirai (Frontier Publishing) "

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, the content of this invention is not limited by this.

<Compound (A) having amine oxide group and photoacid generating site>
[Synthesis]
As the compound (A) having an amine oxide group and a photoacid generation site, compounds 1 to 10 shown in Table 2 below were synthesized as follows.

<Synthesis of Compound 1>
Sulphonic acid A was synthesized by the method described in Journal of the American Chemical Society, 1955, vol. 77, p. 2903. Compound 1 was synthesized by salt exchange of sulfonic acid A and triphenylsulfonium bromide salt according to a conventional method.

<Synthesis of Compound 2>
The sulfonic acid B was synthesized by the method described in Chemische Berichte, 1932, vol.65, p.1801. Compound 2 was synthesized by salt exchange of sulfonic acid B and triphenylsulfonium bromide salt according to a conventional method.

<Synthesis of Compound 3>
Sodium sulfonate C was synthesized by the method described in Journal of Organic Chemistry, 1993, vol.58, 25 p.6964-6965. Compound 3 was synthesized by salt exchange between sodium sulfonate C and 5- (4- (2-hydroxyethyl) phenyl) -5H-dibenzo [b, d] thiophenium bromide according to a conventional method.

<Synthesis of Compound 4>
The sulfonic acid D was synthesized by the method described in Journal of Molecular Structure, 1980, vol.68, p.315-318. Compound 4 was synthesized by salt exchange of sulfonic acid D and 10-phenyl-10H-phenoxathiin-10-ium bromide according to a conventional method.

<Synthesis of Compound 5>
Chem. Abstr., 1960, vol. 80, 18525 p.339-343 was used to synthesize sulfonic acid E. Compound 5 was synthesized by salt exchange of sulfonic acid E and triphenylsulfonium bromide salt according to a conventional method.

<Synthesis of Compound 6>
Salt exchange of sodium 1,1,2,2,3,3-hexafluoro-3- (4-methyl-4-oxidopiperazin-1-ylsulfonyl) propane-1-carboxylate (F) and triphenylsulfonium bromide salt according to a conventional method Thus, the compound 6 was synthesized.

<Synthesis of Compound 7>
Sodium 2,2-difluoro-3- (2- (1-oxidopiperidin-1-yl) acetoxy) propanoate (G) and 1- (4-butoxynaphthalen-1-yl) tetrahydro-1H-thiophenium bromide according to conventional methods The compound 7 was synthesized by exchange.

<Synthesis of Compound 8>
The above compound 8 is obtained by salt exchange of sodium 1,1-difluoro-2- (2- (1-oxidopiperidin-1-yl) acetoxy) ethanesulfonate (H) and bis (4-tert-butylphenyl) iodonium bromide according to a conventional method. Was synthesized.

<Synthesis of Compound 9>
sodium 1,1,2,2,3,3-hexafluoro-3- (4-methyl-4-oxidopiperazin-1-ylsulfonyl) propane-1-sulfonate (F) and 1- (1- (4-cyclohexylphenyl)- Compound 9 was synthesized by salt exchange of 2-methyl-1-oxopropan-2-yl) tetrahydro-1H-thiophenium bromide according to a conventional method.

<Synthesis of Compound 10>
Compound 1 was synthesized by salt exchange of sodium 1,1-difluoro-2- (1-oxidopyridine-4-carbonyloxy) ethanesulfonate (F) and bis (4-tert-butylphenyl) iodonium bromide according to a conventional method.

<Photo acid generator>
As the photoacid generator, at least one of (z1) to (z102) listed above was used.

<Basic compound>
The following compounds C-1 to C-3 were used as basic compounds.
C-1: 2,4,5-triphenylimidazole C-2: Tetrabutylammonium hydroxide C-3: 1,5-diazabicyclo [4.3.0] non-5-ene <Surfactant>
The following W-1 to W-4 were used as the surfactant.
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd .; fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd .; fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd .; fluorine-based)
<Solvent>
As the solvent, the following A1 to A4 and B1 and B2 were used. In addition, these solvents were used by being appropriately mixed.
A1: Propylene glycol monomethyl ether acetate A2: 2-heptanone A3: Cyclohexanone A4: γ-butyrolactone B1: Propylene glycol monomethyl ether B2: Ethyl lactate <Example A>
(Examples 1A-9A and Comparative Examples 1A-3A)
(Resist preparation)
The components shown in Table 3 below were dissolved in a solvent to prepare a solution having a solid concentration of 4.0% by mass. This solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a positive resist solution.

(Resist evaluation)
First, an antireflection film DUV-42 manufactured by Brewer Science Co., Ltd. is uniformly applied to a film thickness of 60 nm on a silicon substrate that has been subjected to hexamethyldisilazane treatment using a spin coater, and is heated on a hot plate at 100 ° C. for 90 seconds. After drying, heat drying was performed at 190 ° C. for 240 seconds. Thereafter, each positive resist solution was applied using a spin coater and dried at 120 ° C. for 90 seconds to form a resist film having a thickness of 0.12 μm.

  This resist film was exposed with an ArF excimer laser stepper (manufactured by ISI; NA = 0.6) through a mask, and immediately after the exposure, it was heated on a hot plate at 120 ° C. for 90 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous 2.38 mass% tetramethylammonium hydroxide solution, rinsed with pure water for 30 seconds, and then dried to obtain a line pattern.

〔sensitivity〕
Surface exposure was performed while changing the exposure amount by 0.5 mJ in the range of 10 to 40 mJ / cm ² , and baking was performed at 110 ° C. for 90 seconds. Then, using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate at each exposure amount was measured to obtain a dissolution rate curve.
In this dissolution rate curve, the exposure amount when the resist dissolution rate is saturated was defined as sensitivity.

[Line edge roughness (LER)]
A 150 nm line pattern (L / S = 1/1) was formed at an irradiation dose showing the above sensitivity. And about arbitrary 30 points | pieces contained in the length direction 50 micrometers, the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed.

[Pattern shape]
The exposure amount for reproducing a mask pattern having a line width of 150 nm and a line and space (L / S = 1/1) was set as the optimum exposure amount, and the profile at the optimum exposure amount was observed with a scanning microscope (SEM).

[Stability over time]
Each composition was stored at room temperature for 1 month. Then, the degree of change in sensitivity before and after storage was evaluated. This evaluation was performed based on the following criteria.
(Criteria)
○ (Good): when the change in sensitivity is less than ^{1mJ / cm 2 △ (Fair)} : when the change in sensitivity was 1 mJ / cm ² or more and 3 mJ / cm ² or less × (Insufficient): Sensitivity variation of Is greater than 3 mJ / cm ² .

[PEB temperature dependence]
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 150 nm when post-heated at 120 ° C. for 90 seconds is the optimal exposure amount, and after performing exposure at the optimal exposure amount, Post-heating was carried out at two temperatures of + 2 ° C. and −2 ° C. (122 ° C., 118 ° C.), and the obtained line and space were measured to determine their line widths L1 and L2. The PEB temperature dependence (PEBS) was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ° C.) = | L1-L2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.
These measurement results are shown in Table 3 below.

The photoacid generator, the compound (A) having an amine oxide group and a photoacid generation site, a basic compound, a surfactant, and a solvent were appropriately selected from those shown above.
As the acid-decomposable resin, one of the following (RA-1), (RA-20), (RA-23) and (RA-25) was used. In the following formula, the number on the right side of the repeating unit represents the molar ratio. Mw represents the weight average molecular weight, and Mw / Mn represents the degree of dispersion.

  From the results shown in Table 3, it can be seen that the composition according to the present invention is excellent in sensitivity, LER, pattern shape, and temporal stability in ArF exposure, and has little PEB temperature dependency. That is, it can be seen that the composition of the present invention has excellent performance as a positive resist composition in ArF excimer laser exposure.

<Example B>
A resist solution was prepared and coated in the same manner as in Example A except that 0.06 g of the following polymer was added to the composition of Example 1A to obtain a resist film. The obtained resist film was subjected to pattern exposure through an immersion liquid (pure water) using an ArF excimer laser immersion scanner (XTML1250i; NA0.85 manufactured by ASML), and a pattern was formed in the same manner as in Example A. did. The obtained pattern was confirmed to have the same evaluation result in any of sensitivity, PEB temperature dependency, LER, pattern shape, and stability over time.

<Example C>
(Examples 1C to 10C and Comparative Examples 1C to 3C)
(Resist preparation)
The components shown in Table 4 below were dissolved in a solvent and then filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to prepare a positive resist solution having a solid content concentration of 4.5 mass%.

(Resist evaluation)
The prepared positive resist solution is uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 100 ° C. for 90 seconds to obtain a 0.4 μm resist. A film was formed.
The resist film was subjected to pattern exposure using a KrF excimer laser stepper (NA = 0.63) using a line and space mask, and immediately after the exposure, it was heated on a hot plate at 110 ° C. for 90 seconds. Thereafter, development was performed at 23 ° C. for 60 seconds using an aqueous 2.38 mass% tetramethylammonium hydroxide solution, rinsed with pure water for 30 seconds, and then dried to form a line pattern.

〔sensitivity〕
Sensitivity was determined in the same manner as described for Example A.

[Line edge roughness (LER)]
A 180 nm line pattern (L / S = 1/1) was formed at an irradiation dose showing the above sensitivity. And about arbitrary 30 points | pieces contained in the length direction 50 micrometers, the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed.

[Pattern shape]
The exposure amount for reproducing a line and space (L / S = 1/1) mask pattern having a line width of 180 nm was set as the optimal exposure amount, and the profile at the optimal exposure amount was observed with a scanning microscope (SEM).

[Stability over time]
The stability over time was evaluated in the same manner as described for Example A.

[PEB temperature dependence]
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 180 nm when post-heated at 120 ° C. for 90 seconds is the optimal exposure amount, and after performing exposure at the optimal exposure amount, + 2 ° C and -2 ° C (122 ° C, 118 ° C)
The post-heating was performed at the two temperatures, the obtained line and space was measured, and their line widths L1 and L2 were obtained. The PEB temperature dependence (PEBS) was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ° C.) = | L1-L2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.
These evaluation results are shown in Table 4 below.

The photoacid generator, the compound (A) having an amine oxide group and a photoacid generation site, a basic compound, a surfactant, and a solvent were appropriately selected from those shown above.
The acid-decomposable resin was appropriately selected from (R-1) to (R-31) exemplified above. (R-2), (R-10), (R-14), (R-17), (R-18), (R-18 (H)) listed in Table 3 and the following tables. , (R-18 (L)), (R-22), (R-23), and (R-27), the molar ratio and weight average molecular weight of each repeating unit are as shown in Table 5 below.

  From the results shown in Table 4, it can be seen that the composition according to the present invention is excellent in sensitivity, LER, pattern shape, and temporal stability in KrF exposure, and has little PEB temperature dependency. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition in KrF excimer laser exposure.

<Example D>
(Examples 1D to 15D and Comparative Examples 1D to 3D)
(Resist preparation)
The components shown in Table 5 below were dissolved in a solvent, and then filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to prepare a positive resist solution having a solid content concentration of 4.0% by mass.

(Resist evaluation)
The prepared positive resist solution was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and then heated and dried on a hot plate at 100 ° C. for 60 seconds to obtain 0.12 μm. A resist film having a film thickness was formed.
This resist film was irradiated with an electron beam projection lithography apparatus (acceleration voltage 100 keV) manufactured by Nikon Corporation, and immediately after the irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds. Thereafter, development was performed at 23 ° C. for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern.

〔sensitivity〕
The obtained pattern was observed using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.). The electron beam irradiation dose when resolving a line and space (L / S = 1/1) with a line width of 0.10 μm was defined as sensitivity (E ₀ ).

[Line edge roughness (LER)]
LER was determined in the same manner as described for Example A.

[Pattern shape]
The exposure amount for reproducing a line and space (L / S = 1/1) mask pattern with a line width of 50 nm was set as the optimum exposure amount, and the profile at the optimum exposure amount was observed with a scanning microscope (SEM).

[Stability over time]
After each composition was stored at room temperature for 1 month, the degree of change in sensitivity before and after storage was visually evaluated. This evaluation was performed based on the following criteria.
(Criteria)
○ (Good): When the variation in sensitivity was less than 1 μC / cm ² Δ (Fair): When the variation in sensitivity was 1 μC / cm ² or more and 3 μC / cm ² or less × (Insufficient): Variation in sensitivity Is greater than 3 μC / cm ² .

[PEB temperature dependence]
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 50 nm when post-heated at 120 ° C. for 90 seconds is the optimum exposure amount, and after performing exposure at the optimum exposure amount, Post-heating was carried out at two temperatures of + 2 ° C. and −2 ° C. (122 ° C., 118 ° C.), and the obtained line and space were measured to determine their line widths L1 and L2. The PEB temperature dependence (PEBS) was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ° C.) = | L1-L2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.
These evaluation results are shown in Table 6 below.

  From the results shown in Table 6, it can be seen that the composition according to the present invention is excellent in sensitivity, LER, pattern shape, and temporal stability in electron beam exposure, and has little PEB temperature dependency. That is, it can be seen that the composition of the present invention has excellent performance as a positive resist composition by electron beam irradiation.

<Example E>
(Examples 1E to 7E and Comparative Examples 1E to 3E)
(Resist preparation)
The components shown in Table 6 below were dissolved in a solvent and then filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to prepare a negative resist solution having a solid content concentration of 12% by mass.

(Resist evaluation)
The prepared negative resist solution was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and heated and dried on a hot plate at 120 ° C. for 60 seconds to obtain a 0.3 μm A resist film having a film thickness was formed.
This resist film was irradiated with an electron beam projection lithography apparatus (acceleration voltage 100 keV) manufactured by Nikon Corporation, and immediately after the irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds. Thereafter, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38 mass%, followed by rinsing with pure water for 30 seconds, followed by drying to form a line and space pattern.
Evaluation was performed in the same manner as described for Example D. The results are shown in Table 7.

Below, the structure of an alkali-soluble resin, molecular weight and molecular weight distribution, and the structure of an acid crosslinking agent are shown.

  From the results shown in Table 7, it can be seen that the composition according to the present invention is excellent in sensitivity, LER, pattern shape, and temporal stability in electron beam exposure, and has little PEB temperature dependency. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a negative resist composition by electron beam irradiation.

<Example F>
(Examples 1F to 10F and Comparative Examples 1F to 3F)
(Resist preparation)
The components shown in Table 7 below were dissolved in a solvent, which was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to prepare a positive resist solution having a solid content concentration of 8% by mass.

(Resist evaluation)
The prepared positive resist solution was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and then heated and dried on a hot plate at 100 ° C. for 60 seconds to obtain 0.12 μm. A resist film having a film thickness was formed.

〔sensitivity〕
The obtained resist film was subjected to surface exposure using EUV light (wavelength 13 nm) while changing the exposure amount by 0.5 mJ / cm ^{2 in} the range of 0 to 10.0 mJ / cm ² , and then at 110 ° C. Bake for 90 seconds. Then, using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate at each exposure amount was measured to obtain a dissolution rate curve.
In this dissolution rate curve, the exposure amount when the resist dissolution rate is saturated was defined as sensitivity.

[Pattern shape]
The exposure amount for reproducing a line and space (L / S = 1/1) mask pattern with a line width of 50 nm was set as the optimum exposure amount, and the profile at the optimum exposure amount was observed with a scanning microscope (SEM).

[Line edge roughness (LER)]
A 50 nm line pattern (L / S = 1/1) was formed at an irradiation dose showing the above sensitivity. And about arbitrary 30 points | pieces contained in the length direction 50 micrometers, the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed.

[PEB temperature dependence]
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 50 nm when post-heated at 120 ° C. for 90 seconds is the optimum exposure amount, and after performing exposure at the optimum exposure amount, Post-heating was carried out at two temperatures of + 2 ° C. and −2 ° C. (122 ° C., 118 ° C.), and the obtained line and space were measured to determine their line widths L1 and L2. The PEB temperature dependence (PEBS) was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ° C.) = | L1-L2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.
The evaluation results are shown in Table 8 below.

  From the results shown in Table 8, it can be seen that the composition according to the present invention is excellent in sensitivity, LER, pattern shape, and temporal stability in EUV exposure, and has little PEB temperature dependency. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition by EUV irradiation.

<Example G>
(Examples 1G-7G and Comparative Examples 1G-3G)
(Resist preparation)
The components shown in Table 9 below were dissolved in a solvent, and this was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to prepare a negative resist solution having a solid content concentration of 8% by mass. went.

<Resist evaluation>
The prepared negative resist solution was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and then heated and dried on a hot plate at 120 ° C. for 60 seconds to obtain a 0.15 μm film. A resist film having a film thickness was formed.

This resist film was evaluated in the same manner as described in Example F. The results are shown in Table 9 below.

  From the results shown in Table 9, it can be seen that the composition according to the present invention is excellent in sensitivity, LER, pattern shape, and temporal stability in EUV exposure, and has little PEB temperature dependency. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a negative resist composition by EUV irradiation.

Claims (10)

  An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (A) having an amine oxide group and a photoacid generating site. The composition according to claim 1, wherein the compound (A) is a compound represented by the general formula (I) or (II).

In general formulas (I) and (II),
A ^- _is, ^-SO 3 ^_-, -CO ₂ - or _R 4 -Z-N ^{- -} represents a.
Y represents a divalent linking group, and Y ′ represents a single bond or a divalent linking group.
R ₁ , R ₂ , R ₃ and R ₄ represent a monovalent organic group.
Z is, -SO ₂ - represents or -CO- group.
X ⁺ represents an onium ion.
n represents 0 or 1.

Represents a heterocycle containing an N atom.   Furthermore, the composition of Claim 1 or 2 containing resin (C) which decomposes | disassembles by the effect | action of an acid and the solubility to an alkali developing solution increases. The composition of Claim 3 in which resin (C) contains the repeating unit represented by the following general formula (VI).

Where
R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Ar ₁ represents an aromatic ring group.
Alternatively, R ₀₃ represents an alkylene group, and may be bonded to Ar ₁ as an aromatic ring group to form a ring together with the —C—C— chain. Alternatively, R ₀₃ and Ar ₁ may represent an alkylene group, and both may be bonded to each other to form a ring together with the —C—C— chain.
n represents an integer of 1 to 4.   The composition according to claim 1, further comprising a resin soluble in an alkali developer and an acid crosslinking agent that crosslinks with the resin soluble in the alkali developer by the action of an acid.   Furthermore, the composition in any one of Claims 1-5 containing the compound (B) which decomposes | disassembles by irradiation of actinic light or a radiation, and generate | occur | produces an acid.   The composition according to any one of claims 1 to 6, which is exposed to an electron beam, an X-ray or EUV light.   A resist film formed using the composition according to claim 1. Forming a film using the composition according to claim 1;
Exposing the film;
Developing a pattern of the exposed film.   The pattern formation method of Claim 9 exposed by an electron beam, X-rays, or EUV light.