JP2013015590A - Actinic ray-sensitive or radiation-sensitive resin composition, and actinic ray-sensitive or radiation-sensitive film and pattern forming method using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic ray-sensitive or radiation-sensitive resin composition that satisfies demands for high sensitivity, good roughness characteristics, a good pattern profile and reduction in development defects all together, and to provide an actinic ray-sensitive or radiation-sensitive film and a pattern forming method using the composition.SOLUTION: The actinic ray-sensitive or radiation-sensitive resin composition comprises: a resin (Aa) including a repeating unit containing a fluorine atom; and a resin (Ab) that shows changes in alkali solubility by an action of an acid and includes a repeating unit (B) having a structural moiety that is decomposed by irradiation with actinic rays or radiation to generate an acid.

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film using the same, and a pattern forming method. More specifically, the present invention relates to an ultra-microlithographic process applicable to a manufacturing process of a VLSI and a high-capacity microchip, a process for producing a mold for nanoimprinting, a manufacturing process of a high-density information recording medium, and other photofabrication. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a process, an actinic ray-sensitive or radiation-sensitive film using the same, and a pattern forming method.

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this trend, the trend of shortening the exposure wavelength from g-line to i-line and further to KrF excimer laser light has been observed. Currently, an exposure machine using an ArF excimer laser having a 193 nm wavelength as a light source has been developed. ing. In addition, as a technique for further increasing the resolution, a so-called immersion method, in which a projection lens and a sample are filled with a liquid having a high refractive index (hereinafter also referred to as an “immersion liquid”), or more recently, In addition to excimer laser light, lithography using electron beams, X-rays, EUV light, etc. is also being developed.

  In particular, electron beam lithography is positioned as a next-generation or next-generation pattern formation technique, and a resist with high sensitivity and high resolution is desired. In particular, high sensitivity is a very important issue for shortening the wafer processing time, but in electron beam resists, when trying to increase the sensitivity, not only the resolution is lowered but also the line edge roughness is reduced. Deterioration occurs, and development of a resist that satisfies these characteristics at the same time is strongly desired. Here, the line edge roughness means that when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Say that the edge looks uneven. The unevenness is transferred by an etching process using a resist as a mask, and the electrical characteristics are deteriorated, so that the yield is lowered. Particularly in the ultrafine region of 0.25 μm or less, the line edge roughness is an extremely important improvement issue. High sensitivity and good line edge roughness are in a trade-off relationship, and it is very important how to satisfy them simultaneously.

  Development defects are also desired to be suppressed, and it is very important how to simultaneously satisfy high sensitivity, high resolution, good line edge roughness, and development defect suppression.

  Electron beam lithography, which is used as an ultrafine processing technique, has become an indispensable technique as a method for processing a photomask blank when manufacturing a photomask for semiconductor manufacturing.

  The ArF excimer laser lithography described above is becoming mainstream at present, but when a chemically amplified resist is applied to immersion exposure, the resist layer comes into contact with the immersion liquid at the time of exposure. It has been pointed out that components that adversely affect the immersion liquid are leached from the resist layer. On the other hand, for example, Patent Documents 1 and 2 disclose a technique of adding an acid-decomposable group and a compound that is immiscible with the main polymer, but has high sensitivity and good roughness characteristics. In fact, it cannot be said that the development defects are sufficiently reduced.

JP 2006-309245 A Japanese Patent Laid-Open No. 2007-187887

  An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that simultaneously satisfies high sensitivity, good roughness characteristics, good pattern shape, and reduction in development defects, and actinic ray sensitivity using the same Alternatively, a radiation-sensitive film and a pattern forming method are provided.

In one aspect, the present invention is as follows.
[1] Resin (Aa) containing a repeating unit containing a fluorine atom, and a resin whose alkali solubility is changed by the action of an acid, and having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (Ab) comprising the repeating unit (B) provided.

[2] At least one of the resin (Aa) and the resin (Ab) includes at least one repeating unit represented by the following general formula (A3), wherein the actinic ray-sensitive property according to [1] Or a radiation sensitive resin composition.

In general formula (A3),
AR represents an aryl group.
Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.
R represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.

[3] The composition according to [2], wherein the resin (Ab) contains at least one repeating unit represented by the general formula (A3).
[4] The composition according to [2] or [3], wherein the resin (Aa) contains at least one repeating unit represented by the general formula (A3).
[5] Any one of [2] to [4], wherein both the resin (Aa) and the resin (Ab) contain at least one repeating unit represented by the general formula (A3) A composition according to 1.

[6] The composition according to any one of [1] to [5], wherein the resin (Ab) contains at least one repeating unit represented by the general formula (A).

In the formula, n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5.
S ₁ represents a substituent. When m is 2 or more, the plurality of S ₁ may be the same as or different from each other.

[7] The composition according to [6], which contains at least a repeating unit represented by the following formula as the repeating unit represented by the general formula (A).

[8] The composition according to any one of [1] to [7], wherein the resin (Aa) contains at least one repeating unit represented by the general formula (A).

In the formula, n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5.
S ₁ represents a substituent. When m is 2 or more, the plurality of S ₁ may be the same as or different from each other.

[9] The composition according to [8], which contains at least a repeating unit represented by the following formula as the repeating unit represented by the general formula (A).

[10] The resin (Aa) contains at least one repeating unit containing a group represented by the general formula (F2), the general formula (F3), or the general formula (F4) as the repeating unit containing a fluorine atom. [1] The composition according to any one of [9].

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, in each of _{R 57 ~R 61, R 62 ~R} 64 and R ₆₅ to R _68, at least one represents a fluorine atom or a fluoroalkyl group. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

[11] The resin (Ab) contains, as the repeating unit (B), at least one selected from the group consisting of repeating units represented by the following general formulas (B1), (B2) and (B3) [ The composition according to any one of [1] to [10].

In general formulas (B1), (B2) and (B3),
A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₆ represents a cyano group, a carboxy group, —CO—OR ₂₅ or —CO—N (R ₂₆ ) (R ₂₇ ). R ₂₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ may be bonded to each other to form a ring together with the nitrogen atom.
X ₁ , X ₂ and X ₃ are each independently a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R ₃₃ ) —, or these Represents a divalent linking group in combination of a plurality. R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.

  [12] The structure according to any one of claims 1 to 11, wherein the structural site in the repeating unit (B) is decomposed by irradiation with an actinic ray or radiation to generate an acid anion in the repeating unit. A composition according to 1.

  [13] The composition according to any one of [1] to [12], wherein the structural moiety in the repeating unit (B) is an ionic structural moiety having a sulfonium salt structure or an iodonium salt structure.

[14] The composition according to any one of [1] to [13], wherein the content of the resin (Aa) is in the range of 0.01 to 20% by mass based on the total solid content in the composition. object.
[15] The composition according to any one of [1] to [14], wherein the content of the resin (Aa) is in the range of 0.01 to 10% by mass based on the total solid content in the composition. object.
[16] The composition according to any one of [1] to [15], wherein the content of the resin (Aa) is in the range of 0.01 to 5% by mass based on the total solid content in the composition. object.

[17] The composition according to any one of [1] to [16], wherein the resin (Aa) further contains at least one repeating unit represented by the general formula (A1) and the general formula (A2). .

In general formula (A1),
n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5.
S ₁ represents a substituent, and when m is 2 or more, the plurality of S ₁ may be the same as or different from each other.
A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one A ₁ represents a group capable of leaving by the action of an acid. When n ≧ 2, the plurality of A ₁ may be the same as or different from each other.

In general formula (A2),
X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, alkyl Represents a carbonyloxy group or an aralkyl group.
A ₂ represents a group capable of leaving by the action of an acid.

[18] The composition according to any one of [1] to [17], wherein the resin (Ab) contains at least one repeating unit represented by the general formula (A1) and the general formula (A2).

In general formula (A1),
n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5.
S ₁ represents a substituent, and when m is 2 or more, the plurality of S ₁ may be the same as or different from each other.
A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one A ₁ represents a group capable of leaving by the action of an acid. When n ≧ 2, the plurality of A ₁ may be the same as or different from each other.

In general formula (A2),
X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, alkyl Represents a carbonyloxy group or an aralkyl group.
A ₂ represents a group capable of leaving by the action of an acid.

  [19] The composition according to any one of [1] to [18], wherein the resin (Ab) has a weight average molecular weight in the range of 1,000 to 200,000.

  [20] The composition according to [19], wherein the resin (Ab) has a weight average molecular weight in the range of 1000 to 100,000.

  [21] The composition according to [20], wherein the resin (Ab) has a weight average molecular weight in the range of 1000 to 50000.

  [22] The composition according to [21], wherein the resin (Ab) has a weight average molecular weight in the range of 1000 to 25000.

  [23] The composition according to any one of [1] to [22], further comprising a basic compound.

  [24] The basic compound has a proton acceptor functional group and is decomposed by irradiation with actinic rays or radiation, whereby the proton acceptor property is reduced, disappeared, or changed from proton acceptor property to acidity. The composition according to [23], which is a compound that generates the compound obtained.

  [25] The composition according to any one of [1] to [24], further comprising a surfactant.

  [26] The composition according to any one of [1] to [27], further comprising a solvent.

  [27] The composition according to [26], wherein the solvent contains propylene glycol monomethyl ether acetate.

  [28] The composition according to [27], wherein the solvent further comprises propylene glycol monomethyl ether.

  [29] The composition according to any one of [1] to [28], which is for EUV exposure.

  [30] The composition according to any one of [1] to [28], which is for KrF excimer laser, electron beam or X-ray exposure.

  [31] An actinic ray-sensitive or radiation-sensitive film formed using the composition according to any one of [1] to [30].

  [31] A pattern forming method comprising forming a film using the composition according to any one of [1] to [30], exposing the film, and developing the exposed film.

  [32] The pattern forming method according to [31], wherein the exposure is performed using EUV.

  [33] A semiconductor device manufactured through a process including the pattern forming method according to [31] or [32].

  According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition that simultaneously satisfies high sensitivity, good roughness characteristics, good pattern shape, and reduction in development defects, and actinic ray sensitivity or A radiation-sensitive film and a pattern forming method can be provided.

Hereinafter, 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.

  In addition, here, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet (EUV) ray, an X-ray or an electron beam (EB). Yes. In the present invention, “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 composition of the present invention is a resin (Aa) containing a repeating unit containing a fluorine atom and a resin whose alkali solubility is changed by the action of an acid, and decomposes upon irradiation with actinic rays or radiation to generate an acid. The resin (Ab) containing the repeating unit (B) provided with the structural site to be contained is contained.

In one embodiment of the composition of the present invention, at least one of the resin (Aa) and the resin (Ab) contains at least one repeating unit represented by the general formula (A3) described later.
In another aspect, the composition of the present invention preferably contains at least one repeating unit in which both the resin (Aa) and the resin (Ab) are represented by the general formula (A3).

[Resin (Aa)]
The resin (Aa) is a resin including a repeating unit containing a fluorine atom. As will be described in detail later, the resin (Ab) does not contain a fluorine atom or the resin (Aa) contains a repeating unit containing a fluorine atom when the resin (Ab) contains a fluorine atom. The resin (Aa) is unevenly distributed in the surface layer of the film formed from the composition of the present invention.
As described above, the resin (Aa) contains at least one repeating unit represented by the following general formula (A3) in one embodiment.

In general formula (A3),
AR represents an aryl group.

Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.
R represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.
The repeating unit represented by formula (A3) will be described in detail.
AR represents an aryl group as described above. The aryl group for AR is preferably a group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, or a fluorene group, and more preferably a group having 6 to 15 carbon atoms.

  When AR is a naphthyl group, anthryl group, or fluorene group, the bonding position between the carbon atom to which Rn is bonded and AR is not particularly limited. For example, when AR is a naphthyl group, this carbon atom may be bonded to the α-position of the naphthyl group or may be bonded to the β-position. Alternatively, when AR is an anthryl group, this carbon atom may be bonded to the 1-position, the 2-position, or the 9-position of the anthryl group.

  The aryl group as AR may have one or more substituents. Specific examples of such substituents include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and dodecyl group. A linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group containing these alkyl group parts, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkoxy group containing these cycloalkyl group parts, a hydroxyl group , Halogen atom, aryl group, cyano group, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, thiophenecarbonyloxy group, thiophenemethylcarbonyloxy group, and pyrrolidone residue And heterocyclic residues such as groups. As this substituent, a linear or branched alkyl group having 1 to 5 carbon atoms and an alkoxy group containing the alkyl group portion are preferable, and a paramethyl group or a paramethoxy group is more preferable.

  When the aryl group as AR has a plurality of substituents, at least two of the plurality of substituents may be bonded to each other to form a ring. The ring is preferably a 5- to 8-membered ring, and more preferably a 5- or 6-membered ring. Moreover, this ring may be a heterocycle containing a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.

  Furthermore, this ring may have a substituent. As this substituent, the thing similar to what is mentioned later about the further substituent which Rn may have is mentioned.

  Moreover, it is preferable that the repeating unit represented by general formula (A3) contains two or more aromatic rings from a viewpoint of roughness performance. The number of aromatic rings contained in this repeating unit is usually preferably 5 or less, and more preferably 3 or less.

  In the repeating unit represented by formula (A3), from the viewpoint of roughness performance, AR preferably contains two or more aromatic rings, and AR is more preferably a naphthyl group or a biphenyl group. . The number of aromatic rings possessed by AR is usually preferably 5 or less, and more preferably 3 or less.

As described above, Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
The alkyl group of Rn may be a straight chain alkyl group or a branched chain alkyl group. The alkyl group is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc. A thing with 1-20 carbon atoms is mentioned. The alkyl group of Rn preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms.

  Examples of the cycloalkyl group represented by Rn include those having 3 to 15 carbon atoms such as a cyclopentyl group and a cyclohexyl group.

  As the aryl group of Rn, for example, those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthryl group are preferable.

  Each of the alkyl group, cycloalkyl group and aryl group as Rn may further have a substituent. Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a dialkylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and a thiophenecarbonyloxy group. , Thiophenemethylcarbonyloxy group, and heterocyclic residues such as pyrrolidone residues. Among these, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, and a sulfonylamino group are particularly preferable.

  As described above, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.

  Examples of the alkyl group and cycloalkyl group of R include the same as those described above for Rn. Each of these alkyl groups and cycloalkyl groups may have a substituent. Examples of this substituent include the same as those described above for Rn.

  When R is an alkyl group or a cycloalkyl group having a substituent, particularly preferable R is, for example, a trifluoromethyl group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, or an alkoxymethyl group. Can be mentioned.

  Examples of the halogen atom for R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is particularly preferable.

  As the alkyl group moiety contained in the alkyloxycarbonyl group of R, for example, the configuration described above as the alkyl group of R can be employed.

Rn and AR are preferably bonded to each other to form a non-aromatic ring, and in particular, roughness performance can be further improved.
The non-aromatic ring that may be formed by bonding Rn and AR to each other is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.

The non-aromatic ring may be an aliphatic ring or a heterocycle containing a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
The non-aromatic ring may have a substituent. As this substituent, the thing similar to having demonstrated previously about the further substituent which Rn may have is mentioned, for example.
Specific examples of the repeating unit represented by the general formula (A3) are shown below, but are not limited thereto.

Especially, the repeating unit shown below is more preferable.

In one embodiment, the resin (Aa) preferably contains at least one repeating unit represented by the following general formula (A).

  In the formula, n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5. n is preferably 1 or 2, more preferably 1. m is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

S ₁ represents a substituent. When m is 2 or more, the plurality of S ₁ may be the same as or different from each other.
Examples of the substituent represented by S ₁ include an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a hydroxy group, a halogen atom, a cyano group, and a nitro group. , A sulfonylamino group, an alkylthio group, an arylthio group, and an aralkylthio group.

  For example, as an alkyl group and a cycloalkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group, A linear or branched alkyl group having 1 to 20 carbon atoms such as a dodecyl group or a cycloalkyl group is preferable. These groups may further have a substituent.

  Further preferred substituents that may be included are alkyl group, alkoxy group, hydroxyl group, halogen atom, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, thiophenecarbonyloxy Group, a thiophenemethylcarbonyloxy group, a heterocyclic residue such as a pyrrolidone residue, and the like, and a substituent having 12 or less carbon atoms is preferable.

  Examples of the alkyl group having a substituent include a cyclohexylethyl group, an alkylcarbonyloxymethyl group, an alkylcarbonyloxyethyl group, a cycloalkylcarbonyloxymethyl group, a cycloalkylcarbonyloxyethyl group, an arylcarbonyloxyethyl group, and an aralkylcarbonyloxyethyl group. , Alkyloxymethyl group, cycloalkyloxymethyl group, aryloxymethyl group, aralkyloxymethyl group, alkyloxyethyl group, cycloalkyloxyethyl group, aryloxyethyl group, aralkyloxyethyl group, alkylthiomethyl group, cycloalkylthiomethyl Group, arylthiomethyl group, aralkylthiomethyl group, alkylthioethyl group, cycloalkylthioethyl group, arylthioethyl group, aralkyl Oechiru group, and the like.

  The alkyl group and cycloalkyl group in these groups are not particularly limited, and may further have a substituent such as the aforementioned alkyl group, cycloalkyl group, or alkoxy group.

  Examples of the alkylcarbonyloxyethyl group and cycloalkylcarbonyloxyethyl group include cyclohexylcarbonyloxyethyl group, t-butylcyclohexylcarbonyloxyethyl group, n-butylcyclohexylcarbonyloxyethyl group, and the like.

The aryl group is not particularly limited, but generally includes those having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group, an anthracenyl group, and the above-mentioned alkyl groups and cycloalkyl groups. And may have a substituent such as an alkoxy group.
Examples of the aryloxyethyl group include a phenyloxyethyl group, a cyclohexylphenyloxyethyl group, and the like. These groups may further have a substituent.

Aralkyl is not particularly limited, and examples thereof include a benzyl group.
Examples of the aralkylcarbonyloxyethyl group include a benzylcarbonyloxyethyl group. These groups may further have a substituent.

Examples of the repeating unit represented by the general formula (Aa1) include the following.

In one embodiment, the resin (Aa) contains at least a repeating unit represented by the following formula as the repeating unit represented by the general formula (A).

  The content of the repeating unit represented by the general formula (A) in the resin (Aa) is preferably 0 to 90 mol%, more preferably 5 to 80 mol% with respect to all the repeating units in the resin (Aa). More preferably, it is 10-70 mol%, Most preferably, it is 20-60 mol%.

  The resin (Aa) further includes a repeating unit containing a fluorine atom. On the other hand, as described above, the resin (Ab) does not have a fluorine atom or has a relatively small number of repeating units containing a fluorine atom relative to the resin (Aa). Thereby, resin (Aa) is unevenly distributed in the surface layer of the film | membrane formed from the actinic-ray-sensitive or radiation-sensitive resin composition of this invention. The resin (Aa) is unevenly distributed at the interface as described above. However, unlike the surfactant, the resin (Aa) does not necessarily have a hydrophilic group in the molecule, and the polar / nonpolar substance is mixed uniformly. It does not have to contribute to When the resin (Aa) contains a fluorine atom, the hydrophobicity of the film surface is improved and the development defect (Blob) is reduced.

  Furthermore, the uneven distribution of the resin (Aa) containing fluorine atoms on the surface of the film is effective in increasing the sensitivity particularly in exposure using EUV. That is, to increase the sensitivity, it is considered necessary to increase the amount of EUV energy absorbed in the actinic ray-sensitive or radiation-sensitive film, that is, to improve the absorption coefficient of the composition with respect to EUV. At that time, rather than uniformly distributing fluorine atoms with a high EUV absorption coefficient in the film, the fluorine atoms are unevenly distributed on the film surface to which the EUV light is irradiated most strongly, thereby efficiently increasing the amount of energy absorption. By doing so, it is possible to realize further higher sensitivity.

  The fluorine atom may be contained in the main chain in the resin (Aa) or may be substituted on the side chain. The repeating unit having a fluorine atom is preferably, for example, a (meth) acrylate repeating unit or a styryl repeating unit.

  In one embodiment, the repeating unit containing a fluorine atom is preferably a repeating unit having an alkyl group having a fluorine atom as a partial structure, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

  The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.

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

  Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.

As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom, a group represented by any one of the following general formulas (F2) to (F4) is preferable. However, the present invention is not limited to this.

In general formulas (F2) to (F4), R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (chain-like). However, at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ represent a fluorine atom or a fluoroalkyl group. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

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

  Specific examples of the group represented by the general formula (F3) include 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 , 3,3-tetrafluorocyclobutyl group, perfluorohexyl group and the like. Among them, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, hexafluoroisopropyl group, heptafluoroisopropyl group Groups are more preferred.

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH _(CF 3) OH and the like, _{C (CF 3)} 2 OH is preferred.

The partial structure containing a fluorine atom may be directly bonded to the main chain, and further comprises a group consisting of an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a ureylene group. You may couple | bond with a principal chain through the combination of single or 2 or more groups selected from.
Preferred examples of the repeating unit having a fluorine atom include those shown below.

In the formula, R ₁₀ and R ₁₁ are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and particularly as an alkyl group having a substituent, Fluorinated alkyl group can be mentioned).

W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups represented by the general formulas (F2) to (F4) described above.
Moreover, resin (Aa) may contain the unit represented by general formula (C-II) or (C-III) in another aspect.

In general formula (C-II), R _{4 to} R ₇ are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms). As the alkyl group having a fluorinated alkyl group, a fluorinated alkyl group can be mentioned in particular. However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.

In general formula (C-III), Q represents an alicyclic structure.
W ₂ represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups represented by the general formulas (F2) to (F4).
L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or an alkyl group), —NHSO ₂ —, or a divalent linking group obtained by combining a plurality of these.

Hereinafter, although the specific example of the repeating unit containing a fluorine is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ , and X ₂ represents —F or —CF ₃ .

  The content of the repeating unit containing a fluorine atom in the resin (Aa) is preferably 1 to 90 mol%, more preferably 5 to 85 mol%, still more preferably 10 with respect to all repeating units in the resin. It is -80 mol%, Most preferably, it is 15-75 mol%.

  As described above, the resin (Ab) to be described later preferably does not contain a fluorine atom, and the content of the repeating unit containing a fluorine atom in the resin (Aa) is the fluorine that can be contained in the resin (Ab). It is larger than the content of the repeating unit containing an atom. From the viewpoint of uneven distribution of the resin (Aa) on the film surface, the content of the repeating unit containing a fluorine atom in the resin (Aa) is 5 mol% or more than the content when the resin (Ab) contains a fluorine atom. It is preferably large, more preferably 10 mol% or more, particularly preferably 15 mol% or more.

  The resin (Aa) may have at least one group selected from the following groups (x) and (z).

(X) an alkali-soluble group,
(Z) A group that decomposes by the action of an acid.

  (X) Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.

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

  Examples of the repeating unit having an alkali-soluble group (x) include a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a main group of the resin via a linking group. Examples include repeating units in which an alkali-soluble group is bonded to the chain. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be used at the time of polymerization to be introduced at the end of the polymer chain. Is also preferable.

  The content of the repeating unit having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 30 mol%, based on all repeating units in the resin (C). is there.

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

  Examples of the repeating unit having a group (z) (hereinafter also referred to as “acid-decomposable group”) that decomposes under the action of an acid in the resin (Aa) include a general formula (CAI) described below, The repeating unit represented by general formula (A1) and general formula (A2) is mentioned, Furthermore, the thing similar to the repeating unit which has an acid-decomposable group mentioned by resin (Ab) mentioned later is mentioned. Here, the “acid-decomposable group” refers to a group that generates a group that is decomposed by the action of an acid to increase the solubility in an alkali developer, and will be described in detail in the resin (Ab) described later. The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following general formula (CAI).

In the general formula (CAI),
Xa ₁ represents a hydrogen atom, a methyl group or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group or a — (CH ₂ ) ₃ — group.

Examples of the alkyl group rx ₁ to Rx _3, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, those having 1 to 4 carbon atoms such as t- butyl group.

Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, A polycyclic cycloalkyl group such as an adamantyl group is preferred.

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

  Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, An alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.

In another embodiment, the resin (Aa) preferably contains at least one repeating unit represented by the following general formulas (A1) and (A2). Here, the general formula (A3) described above is one form of the general formula (A2).

In general formula (A1),
n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5.
S ₁ represents a substituent (excluding a hydrogen atom), and when m is 2 or more, the plurality of S ₁ may be the same as or different from each other.
A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one A ₁ represents a group capable of leaving by the action of an acid. When n ≧ 2, the plurality of A ₁ may be the same as or different from each other.

In general formula (A2),
X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, alkyl Represents a carbonyloxy group or an aralkyl group.
A ₂ represents a group capable of leaving by the action of an acid.

First, the repeating unit represented by formula (A1) will be described.
As described above, n represents an integer of 1 to 5, preferably 1 or 2, and particularly preferably 1.
As described above, m represents an integer of 0 to 4 that satisfies the relationship of 1 ≦ m + n ≦ 5, preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.
S ₁ represents a substituent (excluding a hydrogen atom) as described above. Examples of this substituent include the same as those described above for S ₁ in the general formula (A).

As described above, A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid, and at least one A ₁ is a group capable of leaving by the action of an acid.

Examples of the group capable of leaving by the action of an acid include tertiary alkyl groups such as t-butyl group and t-amyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, and formula -C (L ₁ ) (L ₂ ) —O—Z ₂ represents an acetal group.

Hereinafter, the acetal group represented by the formula —C (L ₁ ) (L ₂ ) —O—Z ₂ will be described. In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl group. Z ₂ represents an alkyl group, a cycloalkyl group, or an aralkyl group. Z ₂ and L ₁ may be bonded to each other to form a 5-membered or 6-membered ring.

The alkyl group may be a linear alkyl group or a branched alkyl group.
As a linear alkyl group, a C1-C30 thing is preferable and a C1-C20 thing is more preferable. Examples of such linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, and n- A heptyl group, n-octyl group, n-nonyl group, and n-decanyl group are mentioned.

  As a branched alkyl group, a C3-C30 thing is preferable and a C3-C20 thing is more preferable. Examples of such branched alkyl groups include i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, i-hexyl group, thexyl group, i-heptyl group. , T-heptyl group, i-octyl group, t-octyl group, inonyl group and t-decanoyl group.

  These alkyl groups may further have a substituent. Examples of the substituent include a hydroxyl group; a halogen atom such as fluorine, chlorine, bromine and iodine atoms; a nitro group; a cyano group; an amide group; a sulfonamide group; a methyl group, an ethyl group, a propyl group, an isopropyl group, n- Alkyl groups such as butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; Examples include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; acyl groups such as formyl group, acetyl group and benzoyl group; acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group.

  As the alkyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexylethyl group, a phenylmethyl group, or a phenylethyl group is particularly preferable.

  The cycloalkyl group may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

  As the monocyclic cycloalkyl group, those having 3 to 8 carbon atoms are preferable. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group.

  Examples of the polycyclic cycloalkyl group include groups having a bicyclo, tricyclo or tetracyclo structure. The polycyclic cycloalkyl group preferably has 6 to 20 carbon atoms. Examples of such cycloalkyl groups include an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclododecyl group, and androstanyl group.

Examples of the aralkyl group in L ₁ , L ₂ and Z ₂ include those having 7 to 15 carbon atoms such as a benzyl group and a phenethyl group.

  These aralkyl groups may further have a substituent. Preferred examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, and an aralkylthio group. Examples of the aralkyl group having a substituent include an alkoxybenzyl group, a hydroxybenzyl group, and a phenylthiophenethyl group. In addition, carbon number of the substituent which these aralkyl groups may have is preferably 12 or less.

Examples of the 5-membered or 6-membered ring that can be formed by bonding Z ₂ and L ₁ to each other include a tetrahydropyran ring and a tetrahydrofuran ring. Of these, a tetrahydropyran ring is particularly preferred.

Z ₂ is preferably a linear or branched alkyl group. Thereby, the effect of the present invention becomes more remarkable.
Although the specific example of the repeating unit represented by general formula (A1) below is given, it is not limited to these.

Next, the repeating unit represented by general formula (A2) is demonstrated.
X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyl as described above. An oxycarbonyl group, an alkylcarbonyloxy group or an aralkyl group is represented.

  The alkyl group as X may have a substituent, and may be linear or branched. As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. As a branched alkyl group, Preferably it is C3-C30, More preferably, it is 3-20, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like.

  The alkoxy group as X may have a substituent, for example, the above alkoxy group having 1 to 8 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group. And a cyclohexyloxy group.

  Examples of the halogen atom as X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

  The acyl group as X may have a substituent, for example, an acyl group having 2 to 8 carbon atoms, specifically, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group. Preferred examples include benzoyl group.

  The acyloxy group as X may have a substituent, and is preferably an acyloxy group having 2 to 8 carbon atoms. For example, an acetoxy group, a propionyloxy group, a butyllioxy group, a valeryloxy group, a pivaloyloxy group, hexanoyl An oxy group, an octanoyloxy group, a benzoyloxy group, etc. can be mentioned.

  The cycloalkyl group as X may have a substituent, may be monocyclic, polycyclic, or bridged. For example, the cycloalkyl group may have a bridged structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, Examples thereof include a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetocyclododecyl group, and an androstanyl group. 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 X may have a substituent, and preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group, and an anthracenyl group. .

  The alkyloxycarbonyl group as X may have a substituent, and preferably has 2 to 8 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group.

  The alkylcarbonyloxy group as X may have a substituent, and preferably has 2 to 8 carbon atoms, and examples thereof include a methylcarbonyloxy group and an ethylcarbonyloxy group.

  The aralkyl group as X may have a substituent and is preferably an aralkyl group having 7 to 16 carbon atoms, for example, a benzyl group.

  Substituents that the alkyl group, alkoxy group, acyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, alkylcarbonyloxy group, aralkyl group as X may further have include a hydroxyl group, a fluorine atom, chlorine Atom, bromine atom, iodine atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, aryl group, carboxyl group, alkyloxycarbonyl group, alkylcarbonyloxy group Or an aralkyl group etc. are mentioned.

A ₂ represents a group capable of leaving by the action of an acid as described above. That is, the repeating unit represented by the general formula (A2) includes a group represented by “—COOA ₂ ” as an acid-decomposable group. The A _2, for example, those previously described for A ₁ in the general formula (A1) similar to the.

A ₂ is preferably a hydrocarbon group (preferably having a carbon number of 20 or less, more preferably 4 to 12), and a t-butyl group, a t-amyl group, or a hydrocarbon group having an alicyclic structure (for example, an alicyclic ring). The group itself and a group in which an alicyclic group is substituted on the alkyl group) are more preferable.
A ₂ is preferably a tertiary alkyl group or a tertiary cycloalkyl group.

The alicyclic structure may be monocyclic or polycyclic. Specific examples include monocyclo, bicyclo, tricyclo, and tetracyclo structures having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These hydrocarbon groups having an alicyclic structure may have a substituent.
Examples of alicyclic structures are shown below.

  In the present invention, the alicyclic structure is preferably a monovalent alicyclic group as an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, or a norbornyl group. And cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, and cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

  Examples of the substituent that the alicyclic ring may have include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group, more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The alkyl group and the alkoxy group may have a further substituent. Examples of further substituents on the alkyl group and alkoxy group include a hydroxyl group, a halogen atom, and an alkoxy group.

As the acid-decomposable group having an alicyclic structure, groups represented by the following general formula (pI) to general formula (pV) are preferable.

In the 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 forms an alicyclic hydrocarbon group together with a carbon atom. Represents the necessary atomic group.

R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon 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 an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.

R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ Represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In the general formulas (pI) to (pV), the alkyl group in R _{12 to} R ₂₅ may be either substituted or unsubstituted, and a linear or branched alkyl group having 1 to 4 carbon atoms Represents. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

  Further, the further substituent of the alkyl group includes an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, A carboxy group, an alkoxycarbonyl group, a nitro group, etc. can be mentioned.

Examples of the alicyclic hydrocarbon group in R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom include those described above as the alicyclic structure.

In one embodiment, the repeating unit represented by the general formula (A2) is preferably a repeating unit represented by the following formula.

  Moreover, the repeating unit represented by the general formula (A2) is also preferably a repeating unit represented by the general formula (A3) described above in another embodiment.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (A2) are shown below, but are not limited thereto.

Although the specific example of the structure of the repeating unit represented by general formula (A2) below is given, it is not limited to these.

  In one embodiment, the repeating unit represented by formula (A2) is preferably a repeating unit of t-butyl methacrylate or ethylcyclopentyl methacrylate.

  The monomer corresponding to the repeating unit represented by the general formula (A2) includes (meth) acrylic acid chloride and an alcohol compound in a solvent such as THF, acetone and methylene chloride, and a basic catalyst such as triethylamine, pyridine and DBU. It can be synthesized by esterification below. A commercially available product may be used.

The resin (Aa) preferably further contains a repeating unit represented by the following general formula (A4). By adopting such a configuration, for example, it is possible to further improve the film quality and further suppress the film loss of the unexposed portion.

In general formula (A4),
R ₂ represents a hydrogen atom, a methyl group, a cyano group, a halogen atom, or a C 1-4 perfluoro group.
R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, an aryl group, an alkoxy group or an acyl group.
q represents an integer of 0 to 4.
W represents a group or a hydrogen atom that is not decomposed by the action of an acid (hereinafter also referred to as an acid stabilizing group).

  The acid stabilizing group for W is preferably an acyl group, an alkylamide group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group or an aryloxy group, and more preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group. A group, a cycloalkyloxy group or an aryloxy group.

  As the alkyl group for W, those having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group are preferable.

  As the cycloalkyl group of W, those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group are preferable.

  As the alkenyl group for W, those having 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group are preferable.

  As the aryl group for W, those having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group and an anthryl group are preferable.

  Examples of the alkyl group in the acyl group, alkylamide group, alkylcarbonyloxy group, and alkyloxy group of W include the same groups as those described above for the alkyl group of W.

Examples of the cycloalkyl group in the cycloalkyloxy group of W include the same groups as those described above for the cycloalkyl group of W.
Examples of the aryloxy group, arylamidomethyl group, and arylamide group of W include the same groups as those described above for the aryl group of W.

  W can substitute any hydrogen atom contained in the benzene ring in the styrene skeleton as shown in the general formula (A4). The substitution position of W is not particularly limited, but is preferably a meta position or a para position, and particularly preferably a para position.

Although the specific example of the repeating unit represented by general formula (A4) below is given, it is not limited to these.

The resin (Aa) may further contain a repeating unit composed of a (meth) acrylic acid derivative that is not decomposed by the action of an acid. Although the specific example is given to the following, it is not limited to these.

The resin (Aa) may further include a repeating unit having an acid-decomposable group represented by the formula —C (═O) —X ₁ —R ₀ . Wherein, _{X 1} is an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. R ₀ is a group capable of leaving by the action of an acid, such as a tertiary alkyl group such as a t-butyl group and a t-amyl group, an isobornyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, 1- 1-alkoxyethyl groups such as isobutoxyethyl group and 1-cyclohexyloxyethyl group, alkoxymethyl groups such as 1-methoxymethyl group and 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group , Trialkylsilyl ester groups, 3-oxocyclohexyl ester groups, 2-methyl-2-adamantyl groups, and mevalonic lactone residues.

Further, the resin (Aa) may further have a repeating unit having a group that decomposes by the action of an alkali developer and increases the dissolution rate in the alkali developer.
Examples of the group that decomposes by the action of an alkali developer and increases the dissolution rate in the alkali developer include a lactone structure and a phenyl ester structure.
As the repeating unit, a repeating unit represented by the following general formula (AII) is more preferable.

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).
Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl 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, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic aliphatic hydrocarbon ring structure, an ether group, an ester group, a carbonyl group, or a divalent linking group obtained by combining these. . Preferably a single _bond, -Ab 1 -CO ₂ - is a divalent linking group represented by.

Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic aliphatic hydrocarbon ring group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

  V represents a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer. A group having an ester bond is preferable, and a group having a lactone structure is more preferable.

As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in the form to be formed are preferred. V is more preferably a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The resin may contain a repeating unit in which a lactone structure is directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC14), (LC1-5), (LC1-6), (LC1-13) and (LC1-14).

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent aliphatic hydrocarbon ring group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Examples include an alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
Although the specific example of the repeating unit (D) in resin is shown below, this invention is not limited to this. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (Aa) may further contain other repeating units having an alkali-soluble group such as a phenolic hydroxyl group and a carboxy group in order to maintain good developability for an alkali developer. Moreover, in order to further improve the film quality, a hydrophobic repeating unit obtained from a monomer such as alkyl acrylate and alkyl methacrylate may be further included.

[Other repeat units]
The resin (Aa) is a repeating unit other than the repeating units described above, and may further have a repeating unit having a polar group. Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, a sulfonylimide group, a bissulfonylimide group, and an alcoholic hydroxyl group in which the α-position is substituted with an electron withdrawing group (for example, hexafluoroisopropanol group: —C (CF ₃ ) ₂ OH). Since the resin (Aa) has such a repeating unit, it is possible to improve substrate adhesion and developer compatibility. The repeating unit having a polar group other than the repeating unit described above is preferably a repeating unit having a hydroxyl group or a cyano group, more preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. Preferably, it has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferable.

In the general formulas (VIIa) to (VIIc), R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms.

Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c. The resin (Aa) may or may not contain a repeating unit having a polar group. However, when it is contained, the content is 1 to 60 mol% with respect to all repeating units in the resin (Aa). Preferably, it is 5 to 50 mol%.
Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited thereto.

The resin (Aa) of the present invention can further have a repeating unit having a cyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability. An example of such a repeating unit is a repeating unit represented by the general formula (VII).

In general formula (VII), R ₅ represents a hydrocarbon group having at least one cyclic hydrocarbon structure and having no polar group (such as a hydroxyl group or a cyano group).
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic hydrocarbon structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Preferable monocyclic hydrocarbon groups are monocyclic hydrocarbon groups having 3 to 7 carbon atoms, and more preferable examples include a cyclopentyl group and a cyclohexyl group.

  The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Preferred examples of the bridged cyclic hydrocarbon group include a norbornyl group, an adamantyl group, a bicyclooctanyl group, and tricyclo [5.2. 1.02, 6] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These cyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom (bromine, chlorine, fluorine atom) and an alkyl group (methyl, ethyl, butyl, t-butyl group). . The above alkyl group may further have a substituent, and examples of the substituent that may further have a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom Can be mentioned.

  Examples of the substituent that replaces the hydrogen atom include an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms. The resin (Aa) has a cyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. 1) to 40 mol% is preferable, and more preferably 5 to 20 mol%, based on all repeating units in ().

Specific examples of the repeating unit having a cyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CHOH, or CF ₃ .

  The resin (Aa) of the present invention has, in addition to the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties of resist, resolving power, heat resistance, sensitivity. Various repeating structural units can be included for the purpose of adjusting the etc.

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

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

  As such monomers, for example, addition polymerization selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic esters, and the like. Examples include compounds having one unsaturated bond. Other examples include maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, and maleilonitrile.

In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.
Although the preferable specific example of the repeating unit derived from such another polymerizable monomer is given to the following, it is not limited to these.

  In the resin (Aa) used in the composition of the present invention, the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required performance of the resist. It is appropriately set to adjust the resolving power, heat resistance, sensitivity and the like.

  The content of the repeating unit having an acid-decomposable group in the resin (Aa) is preferably 0 to 95 mol%, more preferably 10 to 60 mol%, more preferably 15 to 15 mol% based on all repeating units. It is especially preferable to set it as 50 mol%.

  The content of the repeating unit represented by the general formula (A1) in the resin (Aa) is preferably 0 to 90 mol%, more preferably 0 to 85 mol%, based on all repeating units. 0 to 80 mol% is particularly preferable.

  The content of the repeating unit represented by the general formula (A2) in the resin (Aa) is preferably 0 to 90 mol%, more preferably 0 to 75 mol%, based on all repeating units. 0 to 60 mol% is particularly preferable.

  The content of the repeating unit represented by the general formula (A3) in the resin (Aa) is preferably 0 to 70 mol%, and preferably 1 to 50 mol% based on all repeating units in the resin. Is more preferable, and it is especially preferable that it is 5-40 mol%.

  The content of the repeating unit represented by the general formula (A4) in the resin (Aa) is preferably 0 to 50 mol%, more preferably 0 to 40, based on all repeating units. It is especially preferable to set it as -30 mol%.

  When the resin (Aa) contains a repeating unit having a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer, the content is based on the total repeating units in the resin. 0.5-80 mol% is preferable, More preferably, it is 1-60 mol%, More preferably, it is 2-40 mol%.

The resin (Aa) may further have other repeating units. Preferred examples of other repeating units include the following.
(Cy1) A repeating unit having a fluorine atom and / or a silicon atom, stable to an acid, and hardly soluble or insoluble in an alkali developer.

(Cy2) A repeating unit which does not have a fluorine atom or a silicon atom, is stable to an acid, and hardly soluble or insoluble in an alkali developer.

(Cy3) A repeating unit having a fluorine atom and / or a silicon atom and having a polar group other than the above (x) and (z).

(Cy4) A repeating unit having no fluorine atom or silicon atom and having a polar group other than the above (x) and (z).

  In the repeating unit of (cy1) and (cy2), insoluble or insoluble in an alkali developer is a group in which (cy1) and (cy2) generate an alkali-soluble group by the action of an acid or an alkali developer. (For example, an acid-decomposable group or a polar converting group) is not contained. The repeating units (cy1) and (cy2) preferably have an alicyclic hydrocarbon structure having no polar group.

The preferred embodiments of the repeating units (cy1) to (cy4) are shown below.
The repeating units (cy1) and (cy2) are preferably repeating units represented by the following general formula (CIII).

In general formula (CIII):
R _c31 represents a hydrogen atom, an alkyl group _optionally substituted with fluorine, a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group. These groups may be substituted with a fluorine atom or a silicon atom.
L _c3 represents a single bond or a divalent linking group.
In general formula (CIII), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of Lc3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).
The repeating units (cy1) and (cy2) are preferably repeating units represented by the following general formula (C4) or (C5).

The repeating unit (CIII) is preferably a repeating unit represented by the following general formula (C4) or (C5).

In general formula (C4), Rc5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Rac represents a hydrogen atom, an alkyl group optionally substituted with fluorine, a cyano group, or a —CH ₂ O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. Rac is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R _c5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms and a cycloalkenyl group having 3 to 12 carbon atoms. A preferable monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms.

  The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the bridged cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. The bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring (for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed). Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

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

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

In General Formula (C5), R _c6 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxycarbonyl group, or an alkylcarbonyloxy group. These groups may be substituted with a fluorine atom or a silicon atom.
The alkyl group for R _c6 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.
The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 20 carbon atoms.
n represents an integer of 0 to 5. When n is 2 or more, the plurality of R _c6 may be the same or different.
R _c6 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom, particularly preferably a trifluoromethyl group or a t-butyl group.

(Cy1) and (cy2) are preferably repeating units represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _{c11 ′} and R _{c12 ′} each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

The general formula (CII-AB) is more preferably the following general formula (CII-AB1) or general formula (CIIAB2).

In the formulas (CII-AB1) and (CII-AB2),
R _{c13 ′ to} R _{c16 ′} each independently represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group.
Further, the ring may be formed by combining at least two of Rc _{l3 '~R c16'.}
n represents 0 or 1.

Specific examples of (cy1) and (cy2) are listed below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

  (Cy3) and (cy4) are preferably repeating units having a hydroxyl group or a cyano group as a polar group. This improves developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornyl group. Preferred examples of the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group include a monohydroxyadamantyl group, a dihydroxyadamantyl group, a monohydroxydiamantyl group, a dihydroxyadamantyl group, and a norbornyl group substituted with a cyano group.

Examples of the repeating unit having the atomic group include repeating units represented by the following general formulas (CAIIa) to (CAIId).

In the general formulas (CAIIa) to (CAIId),
R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R _{2c to} R _4c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R _{2c to} R _4c represents a hydroxyl group or a cyano group. Preferably, one or two of R _{2c to} R _4c are a hydroxyl group and the rest are hydrogen atoms. In the general formula (CAIIa), more preferably, two of R _{2c to} R _4c are a hydroxyl group and the rest are hydrogen atoms.

Specific examples of the repeating unit represented by (cy3) and (cy4) are given below, but the present invention is not limited thereto.

The content of the repeating units represented by (cy1) to (cy4) is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 10%, based on all repeating units in the resin (Aa). 25 mol%.
The resin (Aa) may have a plurality of repeating units represented by (cy1) to (cy4).

  When resin (Aa) has a silicon atom, it is preferable that the content rate of a silicon atom is 2-50 mass% with respect to the molecular weight of resin (Aa), and it is more preferable that it is 2-30 mass%.

  Moreover, it is preferable that it is 10-90 mass%, and, as for the repeating unit containing a silicon atom with respect to all the repeating units of resin (Aa), it is more preferable that it is 20-80 mass%.

  The weight average molecular weight in terms of standard polystyrene of the resin (Aa) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.

  The resin (Aa) can be synthesized and purified in the same manner as the resin (Ab) described later, and it is natural that there are few impurities such as metals, and the residual monomer and oligomer components are 0 to 10% by mass. It is preferable that there is, more preferably 0 to 5% by mass, and still more preferably 0 to 1% by mass. Thereby, a resist having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

Various commercially available products can be used as the resin (Aa), and the resin (Aa) can be synthesized according to a conventional method (for example, radical polymerization) in the same manner as the resin (Ab) described later.
Specific examples of the resin (Aa) are shown below.

  The content of the resin (Aa) in the composition is preferably 0.01 to 20% by mass, more preferably 0.01 to 20% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is 10 mass%, More preferably, it is 0.01-5 mass%.

[Resin (Ab)]
As described above, the resin (Ab) is a resin whose alkali solubility is changed by the action of an acid, and is a repeating unit (B) having a structural part that decomposes upon irradiation with actinic rays or radiation to generate an acid. including.

First, the repeating unit (B) will be described.
The repeating unit (B) includes a structural portion that decomposes upon irradiation with actinic rays or radiation to generate an acid.
This structural site may be, for example, a structural site that generates an acid anion in the repeating unit (B) by being decomposed by irradiation with an actinic ray or radiation, or the repeating unit (B ) May be a structural site that generates a cation structure.

  Moreover, it is preferable that this structure site | part is an ionic structure site | part provided with the sulfonium salt structure or the iodonium salt structure, for example.

  This structural site may be, for example, a structural site similar to the structural site represented by A in the general formulas (B1), (B2), and (B3) described below.

In one aspect, the repeating unit (B) is preferably at least one selected from the group consisting of repeating units represented by the following general formulas (B1), (B2), and (B3). Among these, the repeating unit represented by the following general formula (B1) or (B3) is more preferable, and the repeating unit represented by the following general formula (B1) is particularly preferable.

In general formulas (B1), (B2) and (B3),
A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₆ represents a cyano group, a carboxy group, —CO—OR ₂₅ or —CO—N (R ₂₆ ) (R ₂₇ ). R ₂₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ may be bonded to each other to form a ring together with the nitrogen atom.

X ₁ , X ₂ and X ₃ are each independently a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R ₃₃ ) —, or these Represents a divalent linking group in combination of a plurality. R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.

The alkyl group of R _{04, R 05} and _R 07 _{to R 09,} preferably one having 20 or less carbon atoms, more preferably those having a carbon number of 8 or less. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group. These alkyl groups may further have a substituent.

The cycloalkyl group of R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ may be monocyclic or polycyclic. As this cycloalkyl group, a C3-C8 thing is preferable. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the halogen atom for R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom is particularly preferable.

As the alkyl group contained in the alkoxycarbonyl group of R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ , for example, those exemplified above as the alkyl group of R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ are preferable.

As the alkyl group for R _{25 to} R ₂₇ and R ₃₃ , for example, those exemplified above as the alkyl groups for R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ are preferable.
As the cycloalkyl group represented by R _{25 to} R ₂₇ and R ₃₃ , for example, those exemplified above as the cycloalkyl groups represented by R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ are preferable.

The alkenyl group of R ₂₅ to R ₂₇ and _{R 33,} preferably having a carbon number of 2-6. Examples of such an alkenyl group include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.

The cycloalkenyl group R ₂₅ to R ₂₇ and _{R 33,} preferably having a carbon number of 3-6. Examples of such a cycloalkenyl group include a cyclohexenyl group.

The aryl group represented by R _{25 to} R ₂₇ and R ₃₃ may be a monocyclic aromatic group or a polycyclic aromatic group. As this aryl group, a C6-C14 thing is preferable. This aryl group may further have a substituent. In addition, aryl groups may be bonded to each other to form a multicycle. Examples of the aryl group of R _{25 to} R ₂₇ and R ₃₃ include a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, and a naphthyl group.

As the aralkyl group of R _{25 to} R ₂₇ and R ₃₃ , those having 7 to 15 carbon atoms are preferable. This aralkyl group may further have a substituent. Examples of the aralkyl group of R _{25 to} R ₂₇ and R ₃₃ include a benzyl group, a phenethyl group, and a cumyl group.

The ring formed by combining R ₂₆ and R ₂₇ together with the nitrogen atom is preferably a 5- to 8-membered ring, and specific examples include pyrrolidine, piperidine, and piperazine.

The arylene group X ₁ to X _3, preferably having a carbon number of 6-14. Examples of such an arylene group include a phenylene group, a tolylene group, and a naphthylene group. These arylene groups may further have a substituent.

Examples of the alkylene group of X ₁ to X _3, preferably having a carbon number of 1-8. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. These alkylene groups may further have a substituent.

The cycloalkylene group X ₁ to X _3, is preferably from 5 to 8 carbon atoms. Examples of such a cycloalkylene group include a cyclopentylene group and a cyclohexylene group. These cycloalkylene groups may further have a substituent.

  Preferred substituents that each group in the general formulas (B1) to (B3) may have include, for example, a hydroxyl group; a halogen atom (fluorine, chlorine, bromine, iodine); a nitro group; a cyano group; an amide group; Groups; alkyl groups as R04, R05 and R07 to R09; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; methoxycarbonyl and ethoxycarbonyl An alkoxy group such as a formyl group, an acetyl group and a benzoyl group; an acyloxy group such as an acetoxy group and a butyryloxy group; and a carboxy group. These substituents preferably have 8 or less carbon atoms.

  A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion. Specifically, photoinitiator of photocationic polymerization, photoinitiator of photoradical polymerization, photodecoloration of pigments Examples thereof include structural sites possessed by compounds that generate acid by known light used in agents, photochromic agents, and microresists.

Moreover, as A, the ionic structure site | part provided with the sulfonium salt structure or the iodonium salt structure is more preferable. More specifically, A is preferably a group represented by the following general formula (ZI) or (ZII).

In 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 generally 1-30, preferably 1-20. Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include alkylene groups such as a butylene group and a pentylene group.

Z ⁻ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation. Z ⁻ is preferably a non-nucleophilic anion. Examples of the non-nucleophilic anion include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  The non-nucleophilic anion means an anion having an extremely low ability to cause a nucleophilic reaction. When a non-nucleophilic anion is used, degradation with time due to intramolecular nucleophilic reaction can be suppressed. This makes it possible to improve the temporal stability of the resin and the composition.

Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the groups represented by (ZI-1), (ZI-2) and (ZI-3) described later.

  More preferable examples of the group represented by (ZI) include the (ZI-1) group, (ZI-2) group, (ZI-3) group and (ZI-4) group described below.

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

All of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

  Examples of the (ZI-1) group include groups corresponding to triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, and aryldicycloalkylsulfonium.

  The aryl group in the arylsulfonium is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a heterocyclic structure containing a hetero atom such as an oxygen atom, a nitrogen atom and a sulfur atom. Examples of this heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran and benzothiophene. When arylsulfonium has two or more aryl groups, these aryl groups may be the same as or different from each other.

  The alkyl group or cycloalkyl group which arylsulfonium has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. Examples of such an alkyl group or cycloalkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group. .

The aryl group, alkyl group or cycloalkyl group of R _{201 to} R ₂₀₃ is an alkyl group (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), or an aryl group (eg, having 6 to 14 carbon atoms). An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group or a phenylthio group may be substituted.

Preferred examples of the substituent include a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms. It is done. More preferable substituents include, for example, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with two or more of these. _Also, when R 201 _{to R 203} is a phenyl group, these substituents are preferably substituted at the p- position of the phenyl group.

Next, the (ZI-2) group will be described.
The (ZI-2) group is a group in which R _{201 to} R ₂₀₃ in the general formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes a heterocycle containing a hetero atom.

The organic group not containing an aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group, 2-oxocyclo group. An alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), and And a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. As the cycloalkyl group, a 2-oxocycloalkyl group is more preferable.

  The 2-oxoalkyl group may be linear or branched. As the 2-oxoalkyl group, a group having> C═O at the 2-position of the above alkyl group is preferable. As the 2-oxocycloalkyl group, a group having> C═O at the 2-position of the cycloalkyl group is preferably exemplified.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a 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, or a nitro group.

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

In General Formula (ZI-3), R _{1c to} R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.

Two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond and / or an amide bond. Examples of the group formed by bonding these to each other include a butylene group and a pentylene group.

Zc ^- represents a non-nucleophilic anion, for example, Z in formula (ZI) ^- the same as the like.

  Specific examples of the structure of the cation moiety of the general formula (ZI-3) include acids exemplified in paragraphs 0047 and 0048 of JP-A No. 2004-233661 and paragraphs 0040 to 0046 of JP-A No. 2003-35948. See the structure of the cation moiety of the generator.

Subsequently, the (ZI-4) group will be described.
The (ZI-4) group is a group represented by the following general formula (ZI-4). This group is effective for suppressing outgas.

In General Formula (ZI-4), 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.
Z is a single bond or a divalent linking group.
Z _c ⁻ represents a non-nucleophilic anion, and examples thereof include the same as Z ⁻ in the general formula (ZI).

When R _{1 to} R ₁₃ are substituents containing an alcoholic hydroxyl group, R _{1 to} R ₁₃ are preferably groups represented by — (WY). 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 -CH2CH2OH.

  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 carbons 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. R The number of alcoholic hydroxyl groups in substituent containing an alcoholic hydroxyl group as ₁ to R ₁₃ is a 1-6, preferably 1-3, more preferably 1.

The number of alcoholic hydroxyl groups contained in the (ZI-4) group is preferably 1 to 10, more preferably 1 to 6, more preferably 1 to 3 in total for all of R _{1 to} R _13. .

When R _{1 to} R ₁₃ do not contain an alcoholic hydroxyl group, R _{1 to} R ₁₃ are, for example, a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a complex Ring 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, complex 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 ], sulfato Examples include the group (—OSO ₃ H), as well as 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, a cyano group, an alkoxy group, an acyloxy group, an acylamino group, an amino group. A carbonylamino 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.

The (ZI-4) group preferably has a structure in which at least one of R _{1 to} R ₁₃ contains an alcoholic hydroxyl group, and more preferably at least one of R _{9 to} R ₁₃ is alcoholic. It has a structure containing a hydroxyl group.

  Z 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 bond, a thioether bond, 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. Examples of these substituents include those similar to those listed above for R _{1 to} R ₁₃ .

  Z is preferably a single bond, an ether bond or a thioether bond, and particularly preferably a single bond.

Next, general formula (ZII) will be described.
In General Formula (ZII), R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
Specific examples and preferred embodiments of the aryl group, alkyl group and cycloalkyl group of R ₂₀₄ and R ₂₀₅ are the same as those described for R _{201 to} R ₂₀₃ in the aforementioned compound (ZI-1).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have a substituent. Even the substituent include the same as those described for _R 201 _{to R 203} in the compound of the aforementioned (ZI-1).

Z ⁻ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion, and examples thereof include the same as Z ⁻ in formula (ZI).

Preferred examples of A also include groups represented by the following general formula (ZCI) or (ZCII).

In the above general formulas (ZCI) and (ZCII),
R ₃₀₁ and R ₃₀₂ each independently represents an organic group. The organic group generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. R ₃₀₁ and R ₃₀₂ may be bonded to each other to form a ring structure. This ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond and a carbonyl group in the ring. Examples of the group that can be formed by bonding R ₃₀₁ and R ₃₀₂ to each other include alkylene groups such as a butylene group and a pentylene group.

The organic group of R ₃₀₁ and _{R 302,} for example, aryl groups mentioned as examples of _R 201 _{to R 203} in formula (ZI), include alkyl groups and cycloalkyl groups.

  M represents an atomic group that forms an acid when a proton is added thereto. More specifically, a structure represented by any one of the general formulas AN1 to AN3 described later can be given. Of these, the structure represented by the general formula AN1 is particularly preferable.

R ₃₀₃ represents an organic group. The carbon number of the organic group as R ₃₀₃ is generally from 1 to 30, preferably 1 to 20. Specific examples of the organic group for R ₃₀₃ include an aryl group, an alkyl group, a cycloalkyl group, and the like given as specific examples of R ₂₀₄ and R ₂₀₅ in the general formula (ZII).

  Moreover, as a structural site | part which generate | occur | produces an acid by irradiation of actinic light or a radiation, the structural site | part used as the sulfonic acid precursor which the following photoacid generator has can be mentioned, for example. Examples of the photoacid generator include the following compounds (1) to (3).

(1) M.M. TUNOOKA et al. , PolymerPreprints Japan, 35 (8); Berneteral. , J .; Rad. Curing, 13 (4); J. et al. Mijsetal. , CoatingTechnol. 55
(697), 45 (1983); Adachietal. , Polymer Preprints, Japan, 37 (3); European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122, US Pat. Nos. 618,564, 4 , 371, 605, 4,431, 774, JP-A 64-18143, JP-A-2-245756, and JP-A-4-365048. A compound that generates sulfonic acid by photolysis, such as

(2) Disulfone compounds described in JP-A No. 61-166544.
(3) V. N. R. Pilla, Synthesis, (1), 1 (1980); Abadetal, Tetrahedron Lett. (47) 4555 (1971); H. R. Bartonetal. , J .; Chem. Soc. , (C), 329 (1970); U.S. Pat. No. 3,779,778; and European Patent No. 126,712 and the like.

  The repeating unit (B) preferably has a structural site that is converted to an acid anion by irradiation with actinic rays or radiation. For example, A in the general formulas (B1) to (B3) is preferably a structural site that is converted into an acid anion by irradiation with actinic rays or radiation.

  That is, it is more preferable that the repeating unit (B) has a structure in which an acid anion is generated in the side chain of the resin by irradiation with actinic rays or radiation. By adopting such a structure, the diffusion of the generated acid anions is suppressed, and the resolution and roughness characteristics can be further improved.

Formula sites _-X 1 -A in (B1), the general formula (B2) site _-X 2 -A in, and each of the sites _-X 3 -A in formula (B3), the following formula (L1), It is preferably represented by either (L2) or (L3).

_{-X 11 -L 11 -X 12 -Ar 1} -X 13 -L 12 -Z 1 (L1)
_{-Ar 2 -X 21 -L 21 -X 22} -L 22 -Z 2 (L2)
_{-X 31 -L 31 -X 32 -L 32} -Z 3 (L3)
First, the site | part represented by general formula (L1) is demonstrated.
X ₁₁ is —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or these Represents a combined group.
X ₁₂ and X ₁₃ each independently represent a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.

  The alkyl group of R may be linear or branched. Moreover, the alkyl group of R may further have a substituent. The alkyl group preferably has 20 or less carbon atoms, more preferably 8 or less carbon atoms, and still more preferably 3 or less carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

  The divalent nitrogen-containing non-aromatic heterocyclic group means a 3- to 8-membered non-aromatic heterocyclic group having at least one nitrogen atom.

X ₁₁ is more preferably —O—, —CO—, —NR— (R is a hydrogen atom or an alkyl group), or a combination thereof, and —COO— or —CONR— (R is hydrogen). Particularly preferred is an atom or an alkyl group.

L ₁₁ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a group obtained by combining two or more thereof. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent They may be linked via an aromatic ring group or a group obtained by combining these.

The alkylene group for L ₁₁ may be linear or branched. As this alkylene group, a C1-C8 thing is preferable, a C1-C6 thing is more preferable, and a C1-C4 thing is still more preferable.

As the alkenylene group for L ₁₁ , for example, a group having a double bond at any position of the above alkylene group can be mentioned.

The divalent aliphatic hydrocarbon ring group as L ₁₁ may be monocyclic or polycyclic. The divalent aliphatic hydrocarbon ring group preferably has 5 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.

  The divalent aromatic ring group as the linking group may be an arylene group or a heteroarylene group. The aromatic ring group preferably has 6 to 14 carbon atoms. This aromatic ring group may further have a substituent.

In addition, —NR— as a linking group and a divalent nitrogen-containing non-aromatic heterocyclic group are the same as, for example, each of X ₁₁ described above.

L ₁₁ is an alkylene group, a divalent aliphatic hydrocarbon ring group, or a combination of an alkylene group and a divalent aliphatic hydrocarbon ring group via —OCO—, —O— or —CONH—. Group (for example, -alkylene group-O-alkylene group-, -alkylene group-OCO-alkylene group- or -valent aliphatic hydrocarbon ring group-O-alkylene group-, -alkylene group-CONH-alkylene group- Is particularly preferred.

Specific examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₁₂ and X ₁₃ are the same as those in X ₁₁ described above, and preferred examples are also the same.

X ₁₂ is more preferably a single bond, —S—, —O—, —CO—, —SO ₂ — or a combination thereof, and a single bond, —S—, —OCO— or —OSO ₂ —. Is particularly preferred.

X ₁₃ is more preferably —O—, —CO—, —SO ₂ —, or a combination thereof, and particularly preferably —OSO ₂ —.

Ar ₁ represents a divalent aromatic ring group. The divalent aromatic ring group may be an arylene group or a heteroarylene group. This divalent aromatic ring group may further have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and an aryl group.

Ar ₁ is more preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, or an aralkylene group in which an arylene group having 6 to 18 carbon atoms and an alkylene having 1 to 4 carbon atoms are combined. A phenylene group, a naphthylene group, a biphenylene group, or a phenylene group substituted with a phenyl group is particularly preferable.

L ₁₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these, and these groups are a part of hydrogen atoms or All are substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, and a cyano group. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

As L ₁₂ , an alkylene group, a divalent aromatic ring group, or a combination thereof, in which some or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group) A group is more preferable, and an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable. L ₁₂ is particularly preferably an alkylene group or a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

The alkylene group for L ₁₂ may be linear or branched. The alkylene group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

Examples of the alkenylene group for L ₁₂ include a group having a double bond at an arbitrary position of the alkylene group.

The divalent aliphatic hydrocarbon ring group represented by L ₁₂ may be monocyclic or polycyclic. The divalent aliphatic hydrocarbon ring group is preferably one having 3 to 17 carbon atoms.

Examples of the divalent aromatic ring group for L ₁₂ include the same groups as those described above as the linking group for L ₁₁ .

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₁₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

Z ₁ represents a site that becomes a sulfonic acid group upon irradiation with actinic rays or radiation, and specifically includes, for example, a structure represented by the above formula (ZI).

Next, the site | part represented by general formula (L2) is demonstrated.
Ar ₂ represents a divalent aromatic ring group. The divalent aromatic ring group may be an arylene group or a heteroarylene group. These divalent aromatic ring groups preferably have 6 to 18 carbon atoms. These divalent aromatic ring groups may further have a substituent.

X ₂₁ represents —O—, —S—, —CO—, —SO ₂ —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or these Represents a combined group.
Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₂₁ include the same as those described above for X ₁₁ .

The _{X 21, -O -, - S} -, - CO -, - SO 2 -, or, more preferably a group composed of a combination of these, -O -, - OCO- or -OSO ₂ - is particularly preferred.

X ₂₂ represents a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or And represents a combination of these. Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₂₂ include the same as those described above for X ₁₁ .

The _{X 22, -O -, - S} -, - CO -, - SO 2 -, or, more preferably a group composed of a combination of these, -O -, - OCO- or -OSO ₂ - is particularly preferred.

L ₂₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

Examples of the alkylene group, alkenylene group, and divalent aliphatic hydrocarbon ring group for L ₂₁ include the same groups as those described above for L ₁₁ .

The divalent aromatic ring group of L ₂₁ may be an arylene group or a heteroarylene group. The divalent aromatic ring group preferably has 6 to 14 carbon atoms.

Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in L ₂₁ include the same as those described above for X ₁₁ .

L ₂₁ includes, for example, a single bond, an alkylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these (for example, -alkylene group-2 divalent aromatic ring group- Or a group in which two or more of these are combined through a linking group such as -OCO-, -COO-, -O-, and -S- For example, -alkylene group-OCO-2 valent aromatic ring group-, -alkylene group-S-2 valent aromatic ring group-, or -alkylene group-O-alkylene group-2 valent aromatic ring group-). Particularly preferred.

L ₂₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these, and these groups are a part of hydrogen atoms or All may be substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, and a cyano group. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O-, S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent They may be linked via an aromatic ring group or a group obtained by combining these.

L ₂₂ is an alkylene group, a divalent aromatic ring group, or a combination of these, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable.

Specific examples of the alkylene group, the alkenylene group, the group aliphatic hydrocarbon ring group, the divalent aromatic ring group, and a combination of two or more of these represented by L ₂₂ include L ₁₂ in the general formula (L1). The same group as the specific example illustrated previously is mentioned.

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₂₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

Z ₂ represents a site that becomes a sulfonic acid group upon irradiation with actinic rays or radiation. Specific examples of Z ₂ are the same as those described above for Z 1.

Then, the site | part represented by general formula (L3) is demonstrated.
X ₃₁ and X ₃₂ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.

Examples of —NR— and a divalent nitrogen-containing non-aromatic heterocyclic group in each of X ₃₁ and X ₃₂ include the same as those described above for X ₁₁ .

X ₃₁ is preferably a single bond, —O—, —CO—, —NR— (wherein R is a hydrogen atom or an alkyl group), or a combination thereof, and more preferably a single bond, —COO— or —CONR—. (R is a hydrogen atom or an alkyl group) is particularly preferred.

X ₃₂ is more preferably —O—, —S—, —CO—, —SO ₂ —, a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof, —O—, — OCO- or -OSO ₂ - is particularly preferred.

L ₃₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

Examples of the alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, and divalent aromatic ring group of L ₃₁ include the same as those described above for L ₂₁ .

Specific examples of -NR- and a divalent nitrogen-containing non-aromatic heterocyclic group in L ₃₁ include the same specific examples as those in X ₁₁ described above, and preferred examples are also the same.

L ₃₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

L _{32 is} an alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, divalent aromatic ring group, or a combination of two or more thereof, wherein a part or all of the hydrogen atoms are fluorine atoms, It is preferably substituted with a substituent selected from a fluorinated alkyl group, a nitro group, and a cyano group.

L ₃₂ is an alkylene group, a divalent aromatic ring group, or a combination of these, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable.

Examples of the L ₃₂ alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, divalent aromatic ring group, and a group obtained by combining two or more of these include L ₁₂ described above. The same thing is mentioned. Specific examples of the —NR— of the linking group and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₃₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

In the case where X ₃ is a single bond and L ₃₁ is an aromatic ring group, when R ₃₂ forms a ring with the aromatic ring group of L ₃₁ , the alkylene group represented by R ₃₂ has 1 carbon atom -8 are preferable, those having 1 to 4 carbon atoms are more preferable, and those having 1 to 2 carbon atoms are still more preferable.

Z ₃ represents an onium salt that becomes an imido acid group or a methide acid group by irradiation with actinic rays or radiation. The onium salt represented by Z ₃ is preferably a sulfonium salt or an iodonium salt, and a structure represented by the following general formula (ZIII) or (ZIV) is preferred.

In general formulas (ZIII) and (ZIV), Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ each independently represent —CO— or —SO ₂ —, and more preferably —SO ₂ —. It is.

Rz ₁ , Rz ₂ and Rz ₃ each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group. An embodiment in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluoroalkyl group (more preferably a perfluoroalkyl group) is more preferable.

The alkyl groups of Rz ₁ , Rz ₂ and Rz ₃ may be linear or branched. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.

The monovalent aliphatic hydrocarbon ring group represented by Rz ₁ , Rz ₂ and Rz ₃ preferably has 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms.

The aryl group of Rz ₁ , Rz ₂ and Rz ₃ preferably has 6 to 18 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. As this aryl group, a phenyl group is particularly preferable.

Preferable examples of the aralkyl group of Rz ₁ , Rz ₂ and Rz ₃ include those in which an alkylene group having 1 to 8 carbon atoms and the aryl group are bonded. An aralkyl group formed by bonding an alkylene group having 1 to 6 carbon atoms and the aryl group is more preferable, and an aralkyl group formed by bonding an alkylene group having 1 to 4 carbon atoms and the aryl group is particularly preferable.

A ⁺ represents a sulfonium cation or an iodonium cation. Preferable examples of A ⁺ include a sulfonium cation in the general formula (ZI) or an iodonium cation structure in the general formula (ZII).

Specific examples of the repeating unit (B) are shown below, but the scope of the present invention is not limited thereto.

  The content of the repeating unit (B) in the resin (Ab) is preferably from 0.1 to 80 mol%, more preferably from 0.5 to 60 mol%, based on all repeating units in the resin (Ab). Preferably it is 1-40 mol%.

The resin (Ab) is preferably insoluble or hardly soluble in an alkaline developer.
The resin (Ab) preferably has a repeating unit having an acid-decomposable group.

  Examples of the acid-decomposable group include a group in which a hydrogen atom of an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group is protected with a group capable of leaving by the action of an acid. .

Examples of the group capable of leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), —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 the like can be mentioned.

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

The resin (Ab) preferably contains at least one repeating unit represented by the general formula (A3) as a repeating unit having an acid-decomposable group. Here, general formula (A3) is the same as general formula (A3) which resin (Aa) demonstrated previously may contain. As described above, at least one of the resin (Aa) and the resin (Ab) contains at least one repeating unit represented by the general formula (A3).

  Specific examples of the repeating unit represented by the general formula (A3) that can be contained in the resin (Ab) include the same specific examples as described above with respect to the resin (Aa).

  As the repeating unit having an acid-decomposable group that can be contained in the resin (Ab), in addition to the repeating unit represented by the general formula (A3) described above, for example, the resin (Aa) described above can contain in general The repeating unit represented by Formula (A1) and General Formula (A2) can be given. Further, an acid-decomposable group may be introduced by reacting a vinyl ether compound with a resin having no repeating unit having an acid-decomposable group.

In one embodiment, the resin (Ab) preferably contains at least one repeating unit represented by the general formula (A1b) and the general formula (A2b). Here, the general formula (A3b) described above is one form of the general formula (A2b).

The resin (Ab) may further contain a repeating unit represented by the following general formula (A5).

In formula (A5),
X is a hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, aryl group, carboxyl group, alkyloxycarbonyl group, alkylcarbonyloxy group, or Represents an aralkyl group and is the same as X in formula (A2b).
A ₄ represents a hydrocarbon group that is not eliminated by the action of an acid.

In the general formula (A5), examples of the hydrocarbon group that is not eliminated by the action of the acid A ₄ include hydrocarbon groups other than the acid-decomposable groups, such as an alkyl that is not eliminated by the action of the acid. A group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms) which is not eliminated by the action of an acid, an aryl group (preferably having 6 to 15 carbon atoms) which is not eliminated by the action of an acid, etc. Can be mentioned.

The hydrocarbon group that is not eliminated by the action of the acid of A ₄ may be further substituted with a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or the like.

It is also preferred that the resin (Ab) further has a repeating unit represented by the general formula (A6).

In general formula (A6),
R ₂ represents a hydrogen atom, a methyl group, a cyano group, a halogen atom, or a perfluoro group having 1 to 4 carbon atoms.
R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, an aryl group, an alkoxy group or an acyl group.
q represents an integer of 0 to 4.
Ar represents a q + 2 valent aromatic ring.
W represents a group or a hydrogen atom that is not decomposed by the action of an acid.

  As the aromatic ring represented by Ar, a benzene ring, a naphthalene ring and an anthracene ring are preferable, and a benzene ring is more preferable.

  W represents a group that is not decomposed by the action of an acid (also referred to as an acid-stable group), and examples include groups other than the above-mentioned acid-decomposable groups. Specifically, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, An aryl group, an acyl group, an alkylamide group, an arylamidomethyl group, an arylamide group, etc. are mentioned. The acid stabilizing group is preferably an acyl group or an alkylamide group, more preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group.

In the acid stable group of W, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group. As the alkyl group, those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group are preferable, and as the alkenyl group, carbon number such as vinyl group, propenyl group, allyl group and butenyl group. Those having 2 to 4 carbon atoms are preferable, those having 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group are preferable as alkenyl groups, and phenyl group, xylyl group and toluyl group are preferable as aryl groups. And those having 6 to 14 carbon atoms such as cumenyl group, naphthyl group and anthracenyl group are preferable. W may be at any position on the benzene ring, but is preferably a meta position or a para position of the styrene skeleton, particularly preferably a para position.
Specific examples of the repeating unit represented by formula (A6) are shown below, but are not limited thereto.

The resin (Ab) preferably further has a repeating unit composed of a (meth) acrylic acid derivative that is not decomposed by the action of acid. Although a specific example is given below, it is not limited to this.

  The content of the repeating unit having an acid-decomposable group in the resin (Ab) is preferably 5 to 95 mol%, more preferably 10 to 60 mol%, and particularly preferably 15 to 50 mol% in all repeating units. It is.

The content of the repeating unit represented by the general formula (A1) in the resin (Ab) is preferably from 0 to 70 mol%, more preferably from 0 to 50 mol%, particularly preferably from 0 to 0 in all repeating units. 40 mol%.
The content of the repeating unit represented by the general formula (A2) in the resin (Ab) is preferably 0 to 90 mol%, more preferably 5 to 75 mol%, and particularly preferably 10 to 10 mol% in all repeating units. 60 mol%.

  As for the content rate of the repeating unit represented by general formula (A3) in resin (Ab), 0-50 mol% is preferable in all the repeating units, More preferably, it is 1-40 mol%, Most preferably, it is 5-5. 30 mol%.

  The content of the repeating unit represented by the general formula (A4) in the resin (Ab) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and particularly preferably 0 to 40 mol% in all repeating units. 30 mol%.

  The resin (Ab) may further have a repeating unit represented by the general formula (A5), which is preferable from the viewpoints of improving the film quality and suppressing the decrease in the film thickness of the unexposed area. The content of the repeating unit represented by the general formula (A5) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and particularly preferably 0 to 40 mol% in each of all the repeating units. 30 mol%.

  In addition, the resin (Ab) is copolymerized with other polymerizable monomers suitable so that an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group can be introduced in order to maintain good developability for an alkali developer. In order to improve the film quality, other hydrophobic polymerizable monomers such as alkyl acrylate and alkyl methacrylate may be copolymerized.

  The monomer corresponding to the repeating unit represented by the general formula (A2) includes (meth) acrylic acid chloride and an alcohol compound in a solvent such as THF, acetone and methylene chloride, and a basic catalyst such as triethylamine, pyridine and DBU. It can be synthesized by esterification below. A commercially available product may be used.

  The monomer corresponding to the repeating unit represented by the general formula (A1) is a hydroxy-substituted styrene monomer and a vinyl ether compound in a solvent such as THF and methylene chloride, such as p-toluenesulfonic acid and p-toluenesulfonic acid pyridine salt. It can be synthesized by acetalization in the presence of an acidic catalyst or by t-Boc protection using t-butyl dicarbonate in the presence of a basic catalyst such as triethylamine, pyridine, DBU or the like. A commercially available product may be used.

It is preferable that resin (Ab) contains the repeating unit represented by general formula (A) which resin (Aa) demonstrated previously can contain.

The resin (Ab) preferably has a repeating unit represented by the following general formula. In the following general formula, j represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.

Specific examples of the repeating unit represented by these general formulas include the following.

  The weight average molecular weight (Mw) of the resin (Ab) is preferably in the range of 1000 to 200,000, respectively. 200,000 or less is preferable from the viewpoint of the dissolution rate and sensitivity of the resin itself with respect to alkali. The dispersity (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and particularly preferably 1.0 to 2.0.

Among them, the weight average molecular weight (Mw) of the resin is preferably in the range of 1,000 to 200,000, more preferably in the range of 1,000 to 100,000, and particularly preferably 1,000. Is in the range of ~ 50,000, most preferably in the range of 1,000-25,000.
Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  Resin (Ab) having a dispersity of 2.0 or less can be synthesized by performing radical polymerization using an azo polymerization initiator. A resin (Ab) having a more preferable dispersity of 1.0 to 1.5 can be synthesized by living radical polymerization, for example.

The resin (Ab) is preferably polymerized by a known anionic polymerization method or radical polymerization method.
The anionic polymerization method is usually performed at a temperature of −100 to 90 ° C. in an organic solvent in an inert gas atmosphere such as nitrogen or argon using an alkali metal or an organic alkali metal as a polymerization initiator. In the copolymerization, a block copolymer is obtained by sequentially adding monomers to the reaction system for polymerization, and a random copolymer is obtained by adding a mixture of monomers to the reaction system for polymerization. can get.

  Examples of the alkali metal of the polymerization initiator include lithium, sodium, potassium, cesium and the like, and examples of the organic alkali metal include alkylated products, allylated products and arylated products of the alkali metals, specifically Is ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, ethyl sodium, lithium biphenyl, lithium naphthalene, lithium triphenyl, sodium naphthalene, α-methylstyrene sodium dianion, 1,1-diphenylhexyl lithium 1,1-diphenyl-3-methylpentyl lithium and the like can be mentioned.

  The radical polymerization method is a known radical polymerization start such as azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, and organic oxides such as benzoyl peroxide, methyl ethyl ketone peroxide and cumene hydroperoxide. If necessary, a known chain transfer agent such as 1-dodecanethiol is used in combination with an inert gas atmosphere such as nitrogen or argon in an organic solvent at a temperature of 50 to 200 ° C. .

Examples of organic solvents include aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane and cyclopentane, aromatic hydrocarbons such as benzene and toluene, and ketones such as methyl ethyl ketone and cyclohexanone. Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether, etc. Polyhydric alcohol derivatives, ethers such as diethyl ether, tetrahydrofuran and dioxane, anisole, hex It can be mentioned organic solvents which are usually used in anionic polymerization such as methyl phosphoramide, which are used as a single solvent or two or more kinds of mixed solvents. More preferable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone.

  In addition, when exposing the positive resist of the present invention with an ArF excimer laser, it is preferable that the resin does not have an aromatic ring at a site other than the repeating unit (B) from the viewpoint of transparency to the ArF excimer laser. .

  Hereinafter, a resin suitable for ArF excimer laser exposure (hereinafter, also referred to as resin (A ′)) will be described.

  Examples of the acid-decomposable group possessed by the resin (A ′) include those similar to those in the resin (A). The repeating unit containing an acid-decomposable group is preferably represented by the general formula (A2). Repeating units.

  The content of the repeating unit having an acid-decomposable group is preferably from 20 to 50 mol%, more preferably from 25 to 45 mol%, based on all repeating units in the resin (A ′).

The resin (A ′) preferably further has a repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group.

The repeating unit having a lactone group that can be contained in the resin (A ′) will be described.
Any lactone group can be used as long as it has a lactone structure, but it is preferably a 5- to 7-membered ring lactone structure, and forms a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure. The other ring structure is preferably condensed. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). The lactone structure may be directly bonded to the main chain.

Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and a specific lactone structure is used. This improves line edge roughness and development defects.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring.

Examples of the repeating unit having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-16) include a repeating unit represented by the following general formula (AII).

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group represented by Rb ₀ may have include a hydroxyl 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. Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferred.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group obtained by combining these. Preferably a single bond, -Ab ₁ -CO ₂ - is a divalent linking group represented by.

Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-16).

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

The content of the repeating unit having a lactone group is preferably from 15 to 60 mol%, more preferably from 20 to 50 mol%, still more preferably from 30 to 50 mol%, based on all repeating units in the resin (A ′).
Specific examples of the repeating unit having a lactone group are listed below, but the present invention is not limited thereto.

The resin (A ′) preferably has a repeating unit having a hydroxyl group or a cyano group. This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

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

Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ (VIIc), same meanings as R ₂ c~R ₄ c.

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

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

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

As for the content rate of the repeating unit which has an alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in resin (A '), More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.
Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.

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

  In addition to the above repeating structural unit, the resin (A ′) has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general necessary characteristics of resist, such as resolution, heat resistance, and sensitivity. It can have various repeating structural units for adjusting purposes.

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

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

  The resin (A ′) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the positive resist composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

  The weight average molecular weight of the resin (A ′) is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000, and even more preferably from 3,000 to 200 in terms of polystyrene by GPC method. 15,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

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

Two or more types of resins (Ab) may be used in combination.
The total amount of the resin (Ab) added is generally 10 to 99% by mass, preferably 20 to 99% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Preferably it is 30-99 mass%.
Although the specific example of resin (Ab) is shown below, it is not limited to these.

  In the resin (Ab), the content of the repeating unit containing a fluorine atom is preferably 1 mol% or less, and more preferably no fluorine atom is contained.

[Compound that generates acid upon irradiation with actinic ray or radiation]
The composition of 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”).

  Examples of the photoacid generator include photo-initiators of photo-cationic polymerization, photo-initiators of photo-radical polymerization, photo-decoloring agents, photo-discoloring agents, and acid by irradiation with actinic rays or radiation used in micro-resist. A known compound that generates a salt, and a mixture 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 (ZI), (ZII) and (ZIII).

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.

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 ₁ represents an aryl group and may further have a substituent other than the — (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 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and each of R ₁ and R ₂ when there are a plurality of R ₁ and 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 ₁ is preferably an aromatic ring having 6 to 30 carbon atoms. Specifically, Ar ₁ is, for example, a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indecene ring, a perylene ring, a pentacene ring, an acetaphthalene ring, a phenanthrene ring, an anthracene ring, a 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 , Thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring or 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 ₁ further has a substituent other than the — (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 alkyl group; vinyl group, propenyl group and hexenyl group, etc. Alkenyl group; ace 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; alkylene group and sulfonic acid group. Of these, straight chain alkyl groups and branched 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 this branched 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. It is done.

  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, dodecyl group and 2-ethylhexyl group; branched alkyl group; cycloalkyl group such as cyclohexyl group; vinyl group , Propenyl group Alkenyl groups such as fine hexenyl group; acetylene group; hydroxy group; a carboxy group; a sulfonic group; an aryl group such as a phenyl group and tolyl group; an alkynyl group such as propynyl group and hexynyl group and a carbonyl group, and the like. Among these, a straight chain alkyl group and a branched alkyl group are preferable from the viewpoint of achieving both improvement in 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 or _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 ring structure. Examples of E 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 benzene ring, naphthalene ring, phenanthrene ring or anthracene ring.

  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, an alkoxy group. Groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups and sulfonic acid ester groups.

Examples of the sulfonate anion represented by the general formula (SA1) or (SA2) include the following.

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

  More preferred (ZI) components include compounds (ZI-1) to (ZI-4) described below.

In the compound (ZI-1), at least one of R _{201 to} R _{203 in} the general formula (ZI) is an aryl group. That is, the compound (ZI-1) is an arylsulfonium compound, that is, a compound having arylsulfonium as a cation.

The compound (ZI-1), all of 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 compound (ZI-1) include triarylsulfonium compounds, diarylalkylsulfonium compounds, and aryldialkylsulfonium compounds.

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

  The alkyl group which the compound (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- Examples include a butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

  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 include, 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.

Compound (ZI-1) is, for example, a compound represented by the following general formula (ZI-1A).

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 or an alkoxycarbonyl group.
When a plurality of R ₁₄ are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group or a cycloalkylsulfonyl group.

R ₁₅ each independently represents an alkyl group or a cycloalkyl 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.
X ⁻ represents a non-nucleophilic anion, and examples thereof include the same as X ⁻ in the general formula (ZI).

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 and cyclooctadienyl groups. Can be mentioned. 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 described 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 described 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 described as the alkyl group of _{R 13, R 14} or _{R 15. Further,} the cycloalkyl group moiety cycloalkylsulfonyl group _{R 14,} for example, those previously described 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.

  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 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.

Below, the preferable specific example of the cation in the compound represented by general formula (ZI-1A) is shown.

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

Compound (ZI-2) is a compound in the case where R _{201 to} R ₂₀₃ in 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 compound (ZI-3) will be described.
The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In the formula, R _{1c to} R _5c each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. As for carbon number of an alkyl group and an alkoxy group, 1-6 are preferable.
R _6c and R _7c represent a hydrogen atom or an alkyl group. As for carbon number of an alkyl group, 1-6 are preferable.
R _x and R _y each independently represents an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl 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.

X in the general formula (ZI-3) ^- is, X in formula (ZI) ^- is synonymous.

  Specific examples of the compound (ZI-3) are described in the compounds exemplified in paragraphs 0047 and 0048 of JP-A No. 2004-233661 or paragraphs 0040 to 0046 of JP-A No. 2003-35948. Compounds.

Subsequently, the compound (ZI-4) will be described.
The compound (ZI-4) is a compound having a cation represented by the following general formula (ZI-4). This compound (ZI-4) is effective in suppressing outgassing.

In general formula (ZI-4),
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.
Z 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 possessed by the compound represented by the general formula (ZI-4) 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.

The compound (ZI-4) preferably has a structure in which at least one of R ^{1 to} R ¹³ contains an alcoholic hydroxyl group, and more preferably at least one of R ^{9 to} R ¹³ is alcoholic. It has a structure containing a hydroxyl group.

  Z 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.

  Z 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 A group, more preferably a single bond, an ether group or a thioether group, and particularly preferably a single bond.

  Hereinafter, general formulas (ZII) and (ZIII) will be described.

In formula (ZII) and (ZIII), 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 linear, branched or cycloalkyl groups listed above for R _{201 to} R ₂₀₃ in compound (ZI-2).

In addition, X < ^- > in general formula (ZII) and (ZIII) is synonymous with X < ^- > in general formula (ZI).

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 withdrawing 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 the photoacid generator, compounds represented by general formulas (ZI) to (ZIII) are more preferable, compounds represented by general formula (ZI) are more preferable, and compounds (ZI-1) to (ZI-3) are more preferable. Is particularly preferred.

Specific examples of the photoacid generator are shown below, but are not limited thereto.

In addition, a photo-acid generator may be used individually by 1 type, and may be used in combination of 2 or more type. In the latter case, it is preferable to combine two types of compounds that generate two kinds of organic acids whose total number of atoms excluding hydrogen atoms is 2 or more.
The content of the photoacid generator is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and still more preferably 1 to 50% by mass, based on the total solid content of the composition. 30% by mass.

(Basic compound)
The composition according to the present invention may further contain a basic compound. The basic compound is preferably a compound having a stronger basicity than phenol. Moreover, this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.

Although the nitrogen-containing basic compound which can be used is not specifically limited, For example, the following (1)-(5)
A compound classified as follows can be used.

(1) Compound represented by general formula (BS-1)

In general formula (BS-1),
Each R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.

Although carbon number of the alkyl group as R is not specifically limited, Usually, it is 1-20, Preferably it is 1-12.
Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, it is 3-20, Preferably it is 5-15.

Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20, Preferably it is 7-11. Specific examples include a benzyl group.

  In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.

  In the compound represented by the general formula (BS-1), it is preferable that at least two of R are organic groups.

  Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexyl. Methylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

  Moreover, as a preferable basic compound represented by the general formula (BS-1), a compound in which at least one R is an alkyl group substituted with a hydroxy group can be given. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.

  In addition, the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH 2 CH 2 O— is preferable. Specifically, for example, tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.

As a basic compound represented by general formula (BS-1), the following are mentioned, for example.

(2) Compound having nitrogen-containing heterocyclic structure This nitrogen-containing heterocyclic ring may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Furthermore, you may contain hetero atoms other than nitrogen. Specifically, for example, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.

This compound more preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is particularly preferable.

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and paragraph [0066] of US2007 / 0224539A1. ] Compounds (C1-1) to (C3-3) exemplified in the above.

  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 chloroform. 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.

(4) Ammonium salt As the basic compound, an ammonium salt can also be used as appropriate. Examples of the anion of the ammonium salt include halides, sulfonates, borates, and phosphates. Of these, halides and sulfonates are particularly preferred.

As the halide, chloride, bromide and iodide are particularly preferable.
As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.

  The alkyl group contained in the alkyl sulfonate may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.

  Examples of the aryl group contained in the aryl sulfonate include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent. As this substituent, a C1-C6 linear or branched alkyl group and a C3-C6 cycloalkyl group are preferable, for example. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferable. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The ammonium salt may be hydroxide or carboxylate. In this case, the ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.). It is particularly preferred.

  Preferred basic compounds include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholine. . These may further have a substituent.

  Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.

  Particularly preferable basic compounds include, for example, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2 -Phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- Diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5 methylpyrazine, Examples include pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine and N- (2-aminoethyl) morpholine.

(5) A compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from proton acceptor property to acidity ( PA)
The composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. It may further contain a compound that generates a compound that has been changed to acidity (hereinafter also referred to as compound (PA)).

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

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

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

  Proton acceptor property can be confirmed by measuring pH. In the present invention, the acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1. And more preferably −13 <pKa <−3.

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

Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)
The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. The compound represented by the general formula (PA-1) has an acidic group as well as a proton acceptor functional group, so that the proton acceptor property is reduced or disappeared compared to the compound (PA), or from the proton acceptor property. It is a compound that has changed to acidic.

In general formula (PA-1),
Q _represents -SO 3 H, _-CO 2 H, or _-X 1 _NHX 2 Rf. Here, Rf represents an alkyl group, a cycloalkyl group or an aryl group, and X ₁ and X ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or -N (Rx) Ry-. Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a divalent organic group. It may combine with Ry to form a ring, or may combine with R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

General formula (PA-1) is demonstrated still in detail.
The divalent linking group in A is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferably, it is an alkylene group having at least one fluorine atom, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

  The monovalent organic group in Rx preferably has 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent.

  The alkyl group in Rx may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. May be.

Preferred examples of the divalent organic group for Ry include an alkylene group.
Examples of the ring structure which Rx and Ry may be bonded to each other include a 5- to 10-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring.

  Examples of the alkyl group having a substituent include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). .

The cycloalkyl group in Rx may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring.
The aryl group in Rx may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.

The aralkyl group in Rx may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms.
The alkenyl group in Rx may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group mentioned as Rx.

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

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

Examples of the substituent that each of the above groups may have include, for example, a halogen atom, a hydroxyl group, a nitro group,
A cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably 3 to 10 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably Include an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably 2 to 20 carbon atoms), an aminoacyl group (preferably 2 to 20 carbon atoms), and the like. As for the cyclic structure in the aryl group, cycloalkyl group and the like, and the aminoacyl group, examples of the substituent further include an alkyl group (preferably having 1 to 20 carbon atoms).

  When B is -N (Rx) Ry-, R and Rx are preferably bonded to each other to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.

  Examples of the monocyclic structure include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures. The monocyclic structure and polycyclic structure may have a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), Aryl group (preferably having 6 to 14 carbon atoms), alkoxy group (preferably having 1 to 10 carbon atoms), acyl group (preferably having 2 to 15 carbon atoms), acyloxy group (preferably having 2 to 15 carbon atoms), alkoxycarbonyl A group (preferably having 2 to 15 carbon atoms), an aminoacyl group (preferably having 2 to 20 carbon atoms) and the like are preferable. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).

As Rf in _-X 1 _NHX 2 Rf represented by Q, preferably an alkyl group which may have a fluorine atom having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms is there. Further, as X ₁ and X ₂ , at least one is preferably —SO ₂ —, and more preferably, both X ₁ and X ₂ are —SO ₂ —.

  Among the compounds represented by the general formula (PA-1), a compound in which the Q site is a sulfonic acid can be synthesized by using a general sulfonamidation reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring-opening by reacting with an amine compound.

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

In the general formulas (4) to (6), A, X, n, B, R, Rf, X ₁ and X ₂ have the same meanings as those in the general formula (PA-1).
C ⁺ represents a counter cation.

The counter cation is preferably an onium cation. More specifically, in the photoacid generator, the sulfonium cation described above as S ⁺ (R _{201 ′} ) (R _{202 ′} ) (R _{203 ′} ) in general formula (ZI), I ⁺ (in general formula (ZII) A preferred example is the iodonium cation described as R204 _′ ) ( _{R205 ′} ).

Hereinafter, although the specific example of a compound (PA) is shown, it is not limited to these.

Moreover, in this invention, compounds (PA) other than the compound which generate | occur | produces the compound represented by general formula (PA-1) can also be selected suitably. For example, an ionic compound that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

In the formula, A represents a sulfur atom or an iodine atom.
m represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.
R represents an aryl group.
R _N represents an aryl group substituted with a proton acceptor functional group.
X ⁻ represents a counter anion.

Specific examples of X ⁻ include the same as X− in the general formula (ZI) described above.
Specific examples of the aryl group of R and R _N is a phenyl group are preferably exemplified.

  Specific examples of the proton acceptor functional group possessed by RN are the same as the proton acceptor functional group described in the above formula (PA-1).

  In the composition of the present invention, the compounding ratio of the compound (PA) in the whole composition is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass in the total solid content.

(6) Guanidine Compound The composition of the present invention may further contain a guanidine compound having a structure represented by the following formula.

The guanidine compound exhibits strong basicity because the positive charge of the conjugate acid is dispersed and stabilized by three nitrogens.
The basicity of the guanidine compound (A) of the present invention is preferably such that the pKa of the conjugate acid is 6.0 or more, and 7.0 to 20.0 is highly neutralizing reactivity with the acid, Since it is excellent in a roughness characteristic, it is preferable and it is more preferable that it is 8.0-16.0.

  Due to such strong basicity, it is possible to suppress acid diffusibility and contribute to the formation of an excellent pattern shape.

  Here, “pKa” means pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value, the higher the acid strength. Specifically, pKa in an aqueous solution can be actually measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the software package 1 below, A value based on a database of constants and known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

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

  In the present invention, log P is a logarithmic value of n-octanol / water partition coefficient (P), and is an effective parameter that can characterize the hydrophilicity / hydrophobicity of a wide range of compounds. In general, the distribution coefficient is obtained by calculation without experimentation. In the present invention, CSChemDrawUltraVer. The value calculated by 8.0 software package (Crippen's fragmentation method) is shown.

  Moreover, it is preferable that logP of a guanidine compound (A) is 10 or less. By being below the above value, it can be contained uniformly in the resist film.

  The log P of the guanidine compound (A) in the present invention is preferably in the range of 2 to 10, more preferably in the range of 3 to 8, still more preferably in the range of 4 to 8.

  Moreover, it is preferable that the guanidine compound (A) in this invention does not have a nitrogen atom other than a guanidine structure.

Hereinafter, although the specific example of a guanidine compound is shown, it is not limited to these.

  Other examples that can be used in the composition according to the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, and compounds described in paragraph 0108 of JP-A No. 2007-298869. It is done.

  A photosensitive basic compound may be used as the basic compound. As the photosensitive basic compound, for example, JP-T-2003-524799 and J. Org. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) etc. can be used.

  The molecular weight of the basic compound is usually 100-1500, preferably 150-1300, and more preferably 200-1000.

  These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

  When the composition according to the present invention contains a basic compound, the content is preferably 0.01 to 8.0% by mass based on the total solid content of the composition, More preferably, it is 5.0 mass%, and it is especially preferable that it is 0.2-4.0 mass%.

  The molar ratio of the basic compound to the photoacid generator is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, More preferably, it is 0.1-3. The photoacid generator at the molar ratio is based on the total amount of the repeating unit (B) of the resin and the photoacid generator that the resin may further contain.

(Surfactant)
The composition according to the present invention may further contain a surfactant. As this surfactant, fluorine-based and / or silicon-based surfactants are particularly preferable.

  Examples of the fluorine-based and / or silicon-based surfactant include Megafac F176 and Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656 and PF6320 manufactured by OMNOVA, and Troisol S manufactured by Troy Chemical Co., Ltd. -366, Fluorard FC430 manufactured by Sumitomo 3M Limited, and polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

  Surfactants other than fluorine and / or silicon may be used. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] and after in US 2008 / 0248425A1.

One type of surfactant may be used alone, or two or more types may be used in combination.
When the composition according to the present invention further contains a surfactant, the amount used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 2, based on the total solid content of the composition. 1% by mass.

(dye)
The composition according to the present invention may further contain a dye. Suitable dyes include, for example, oily dyes and basic dyes. Specifically, for example, oil yellow # 101, oil yellow # 103, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, and oil black T-505 (or above) Orient Chemical Industry Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), and methylene blue (CI522015).

(Photobase generator)
The composition according to the present invention may further contain a photobase generator. When a photobase generator is contained, a more favorable pattern can be formed.

  Examples of the photobase generator include JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, JP-A-5-5995, JP-A-6-194634, JP-A-8-146608, and JP-A-10-83079. And compounds described in European Patent No. 622682.

  Preferred photobase generators include 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide and 1,1-dimethyl-2-phenylethyl- N-isopropyl carbamate may be mentioned.

(Antioxidant)
The composition according to the present invention may further contain an antioxidant. When the antioxidant is contained, it is possible to suppress the oxidation of the organic material in the presence of oxygen.

  Examples of antioxidants include phenolic antioxidants, antioxidants composed of organic acid derivatives, sulfur-containing antioxidants, phosphorus antioxidants, amine antioxidants, and antioxidants composed of amine-aldehyde condensates. And an antioxidant comprising an amine-ketone condensate. Of these antioxidants, it is particularly preferable to use an antioxidant comprising a phenolic antioxidant and an organic acid derivative. If it carries out like this, the function as antioxidant can be expressed, without reducing the performance of a composition.

  As the phenolic antioxidant, for example, substituted phenols, bis, tris, or polyphenols can be used.

  Examples of substituted phenols include 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4ethylphenol, and 2,6-diphenyl. -Tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, butylhydroxyanisole, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,4-dimethyl 6-tert-butylphenol, 2-methyl-4,6-dinonylphenol, 2,6 di-tert-butyl-α-dimethylamino-p-cresol, 6- (4-hydroxy-3,5-di-tert-butylanilino ) 2,4-Bis-octyl-thio-1,3,5 triazine, n-octadecyl-3- (4 - hydroxy -3 ', 5'-di -tert-butyl-phenyl) propionate, octyl phenol, aralkyl-substituted phenols, alkylated -p- cresol, and include hindered phenols.

  Examples of bis, tris, or polyphenols include 4,4′-dihydroxydiphenyl, methylene bis (dimethyl-4,6-phenol), and 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol). 2,2′-methylene-bis- (4-methyl-6-cyclohexyl phenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4′-methylene- Bis- (2,6-di-tert-butylphenol), 2,2′-methylene-bis- (6-alphamethyl-benzyl-p-cresol), methylene-bridged polyhydric alkylphenol, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1-bis- (4-hydroxyphenyl) -cyclohexane Sun, 2,2′-dihydroxy-3,3′-di- (α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane, alkylated bisphenol, hindered bisphenol, 1,3,5-trimethyl-2,4 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and tetrakis- [methylene-3- ( 3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane.

  The antioxidant is preferably 2,6-di-t-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,2′-methylenebis (4-methyl- 6-t-butylphenol), butylhydroxyanisole, t-butylhydroquinone, 2,4,5-trihydroxybutyrophenone, nordihydroguaiaretic acid, propyl gallate, octyl gallate, lauryl gallate, and isopropyl citrate. Can be mentioned. Of these, 2,6-di-t-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, butylhydroxyanisole, and t-butylhydroquinone are more preferable. Di-t-butyl-4-methylphenol or 4-hydroxymethyl-2,6-di-t-butylphenol is more preferred.

One type of antioxidant may be used alone, or two or more types may be used in combination.
When the composition according to the present invention contains an antioxidant, the amount added is preferably 1 ppm or more, more preferably 5 ppm or more, still more preferably 10 ppm or more, still more preferably 50 ppm or more, particularly preferably. Is 100 ppm or more, and most preferably 100 to 1000 ppm.

(solvent)
The composition according to the present invention may further contain a solvent. Typically, an organic solvent is used as this solvent. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and a ring. Good monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate are mentioned.

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

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

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

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

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

Examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include, for example, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate 2-propyl is mentioned.
Examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

  As the solvent, it is preferable to use a solvent having a boiling point of 130 ° C. or higher under normal temperature and pressure. Specifically, for example, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, PGMEA, ethyl ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid-2- (2-Ethoxyethoxy) ethyl and propylene carbonate are mentioned.

  These solvents may be used alone or in combination of two or more. In the latter case, it is preferable to use a mixed solvent of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group.

  Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, PGME, propylene glycol monoethyl ether, and ethyl lactate. Of these, PGME and ethyl lactate are particularly preferred.

  Examples of the solvent not containing a hydroxyl group include PGMEA, ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate can be mentioned. Of these, PGMEA, ethyl ethoxypropionate and 2-heptanone are particularly preferred.

  When using a mixed solvent of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group, these mass ratios are preferably 1/99 to 99/1, more preferably 10/90 to 90/10, More preferably, it is set to 20/80 to 60/40.

  When a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is used, particularly excellent coating uniformity can be achieved. The solvent is particularly preferably a mixed solvent of PGMEA and one or more other solvents.

  The content of the solvent in the composition of the present invention can be appropriately adjusted according to the desired film thickness and the like, but generally the total solid content concentration of the composition is 0.5 to 30% by mass, preferably It is prepared so that it may become 1.0-20 mass%, More preferably, it is 1.5-10 mass%.

<Pattern formation method>
The present invention relates to an actinic ray-sensitive or radiation-sensitive film formed using the above-described composition of the present invention. Moreover, the pattern formation method of this invention has the process of exposing and developing the said actinic-light sensitive or radiation sensitive film | membrane.

  The composition according to the present invention is typically used as follows. That is, the composition according to the present invention is typically applied on a support such as a substrate to form a film. The thickness of this film is preferably 0.02 to 0.1 μm. As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

  This composition can be applied to, for example, a spinner and a substrate on a substrate (eg, silicon / silicon dioxide coating, silicon nitride and chromium-deposited quartz substrate) used for manufacturing precision integrated circuit elements and imprint molds. It is applied using a coater or the like. Thereafter, this is dried to form an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as a resist film). In addition, a known antireflection film can be applied in advance.

  Next, the actinic ray-sensitive or radiation-sensitive film is irradiated with actinic rays or radiation, and preferably baked (usually 80 to 150 ° C., more preferably 90 to 130 ° C.), followed by development. By performing baking, a more favorable 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. Preferable actinic rays or radiations include, for example, KrF excimer laser, electron beam, X-ray and EUV light. More preferred are electron beam, X-ray and EUV light.

  That is, the present invention also relates to an actinic ray-sensitive or radiation-sensitive resin composition for KrF excimer laser, electron beam, X-ray or EUV light (more preferably for electron beam, X-ray or EUV light).

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 alcohols and / or surfactant may be added to the alkaline developer.
The concentration of the alkali developer is usually from 0.1 to 20% by mass. PH of alkaline developer
Is usually 10.0 to 15.0.

  In addition, you may produce the mold for imprint using the composition which concerns on this invention, For the details, for example, the patent 4109085 gazette, Unexamined-Japanese-Patent No. 2008-162101, and "the foundation and technique of nanoimprint" See “Development and Application Development-Nanoimprint Substrate Technology and Latest Technology Development-Editing: Yoshihiko Hirai (Frontier Publishing)”.

Hereinafter, the embodiments of the present invention will be described in more detail by way of examples, but the contents of the present invention are not limited thereto.
[Synthesis Example 1: Resin (Aa-6)]
The resin (Aa-6) listed above was synthesized according to the following scheme.
14.42 g of p-hydroxystyrene (50.00 wt% propylene glycol monomethyl ether acetate solution), 9.44 g of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate and 1.15 g Polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 6.11 g of propylene glycol monomethyl ether acetate (PGMEA). 3.33 g of PGMEA was put in the reaction vessel, and dropped into the system at 85 ° C. in a nitrogen gas atmosphere over 2 hours. The reaction solution was heated and stirred for 4 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 50 g of acetone. The diluted solution was dropped into 850 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and filtered. The filtered solid was washed with 250 g of hexane. Thereafter, the washed solid was subjected to vacuum drying to obtain 9.99 g of resin (Aa-6).

  About this resin (Aa-6), the weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were measured using GPC (the Tosoh Corporation make; HLC-8120; Tsk gel Multipore HXL-M). The results are shown in the following table together with the composition ratio. In this GPC measurement, THF was used as a solvent.

[Other resins (Aa)]
Each of the resins shown in the following table was synthesized in the same manner as described in Synthesis Example 1 from the resins (Aa-1) to (Aa-46) listed above. For these resins, the weight average molecular weight (Mw) and dispersity (Mw / Mn) were measured in the same manner as described in Synthesis Example 1. The results are shown in Table 1 below together with the composition ratio.

[Synthesis Example 2: Resin (Ab-42)]
Resin Ab-42 was synthesized according to the following scheme.

<Synthesis of Compound (5)>
100.00 g of compound (1) was dissolved in 400 g of ethyl acetate. The obtained solution was cooled to 0 ° C., and 47.60 g of sodium methoxide (28 mass% methanol solution) was added dropwise over 30 minutes. This was then stirred at room temperature for 5 hours. Ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with distilled water and then dried over anhydrous sodium sulfate, and the solvent was distilled off. In this way, 131.70 g of Compound (2) (54% by mass ethyl acetate solution) was obtained.

  56.00 g of ethyl acetate was added to 18.52 g of compound (2) (54 mass% ethyl acetate solution). To this, 31.58 g of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride was added and cooled to 0 ° C. A solution prepared by dissolving 12.63 g of triethylamine in 25.00 g of ethyl acetate was added dropwise over 30 minutes, and the mixture was stirred for 4 hours while maintaining the liquid temperature at 0 ° C. Ethyl acetate was added, and the organic layer was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. In this way, 32.90 g of compound (3) was obtained.

  35.00 g of compound (3) was dissolved in 315 g of methanol, cooled to 0 ° C., 245 g of 1N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 2 hours. After the solvent was distilled off, ethyl acetate was added, and the organic layer was washed 3 times with saturated brine and then dried over anhydrous sodium sulfate, and the solvent was distilled off. In this way, 34.46 g of compound (4) was obtained.

  28.25 g of compound (4) was dissolved in 254.25 g of methanol, 23.34 g of triphenylsulfonium bromide was added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off, distilled water was added, and the mixture was extracted 3 times with chloroform. The obtained organic layer was washed 3 times with distilled water, and then the solvent was distilled off. In this way, 42.07 g of compound (5) was obtained.

<Synthesis of Resin (Ab-42)>
8.15 g of p-hydroxystyrene (6) (53.1 wt% propylene glycol monomethyl ether solution), 8.22 g of compound (7), 7.31 g of compound (5), and 2.07 g of polymerization Initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 34.00 g of propylene glycol monomethyl ether (PGME). 8.50 g of PGME was put in the reaction vessel, and dropped into the system at 85 ° C. over 2 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 4 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 33 g of acetone. The diluted solution was dropped into 1000 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and filtered. The filtered solid was washed with 250 g of hexane / ethyl acetate = 8/2. The obtained solid was dissolved in 80 g of acetone and dropped into 600 g of methanol / distilled water = 1/9 to precipitate the polymer, followed by filtration. The filtered solid was washed with 150 g of methanol / distilled water = 1/9. Thereafter, the washed solid was dried under reduced pressure to obtain 12.90 g of Resin Ab-42.

[Other resins (Ab)]
Each of the resins shown in the table below was synthesized in the same manner as described in Synthesis Example 2 from the resins (Ab-1) to (Ab-91) listed above. For these resins, the weight average molecular weight (Mw) and dispersity (Mw / Mn) were measured in the same manner as described in Synthesis Example 2. The results are shown in Table 2 below together with the composition ratio.

<Basic compound>
Any of the following N-1 to N-7 was used as the basic compound. N-7 corresponds to the compound (PA) described above.

[Synthesis Example 3: Compound N-7]
Compound N-7 was synthesized based on the description in [0354] of JP-A-2006-330098.

<Surfactant>
Any of the following W-1 to W-4 was used as the surfactant.
W-1: Megafuck R08 (Dainippon Ink Chemical Co., Ltd .; fluorine and silicon)
W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
W-3: Troisol S-366 (manufactured by Troy Chemical Co .; fluorine type)
W-4: PF6320 (manufactured by OMNOVA; fluorine-based)
<Solvent>
As the solvent, any one of the following S-1 to S-4 was appropriately mixed and used.
S-1: PGMEA (bp = 146 ° C.)
S-2: PGME (bp = 120 ° C.)
S-3: Methyl lactate (bp = 145 ° C.)
S-4: Cyclohexanone (bp = 157 ° C.)
<Resist evaluation (EB)>
Each component shown in the following Table 3 was dissolved in the solvent shown in the same table to prepare a solution having a solid content concentration of 3.0% by mass. This solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a positive resist solution.

  The numerical value of “mass%” shown in Table 3 is a value based on the total solid content excluding the surfactant in the composition. In addition, the content rate of surfactant is 0.01 mass% with respect to the total solid content except surfactant of a composition.

  The positive resist solution was applied onto a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. This was heated and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having an average film thickness of 100 nm.

[Sensitivity, pattern shape, roughness characteristics and development defects]
The resist film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd .; acceleration voltage 50 keV). Immediately after irradiation, it was heated on a hot plate at 130 ° 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% by mass, rinsed with pure water for 30 seconds, and then dried. Thereby, a line and space pattern (line: space = 1: 1) was formed.

(sensitivity)
First, the cross-sectional shape of the obtained line and space pattern was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). And the minimum irradiation energy at the time of resolving a line with a line width of 100 nm was calculated | required, and this value was made into "sensitivity ((micro | micron | mu) C / cm < ² >)."

(Pattern shape)
The cross-sectional shape of a 100 nm line pattern (line: space = 1: 1) at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). Then, the shape was evaluated in two stages of “rectangle” or “taper”.

(Roughness characteristics: Line edge roughness (LER))
The 100 nm line pattern (line: space = 1: 1) was observed using a scanning electron microscope (S-9260, manufactured by Hitachi, Ltd.). And the distance between the reference line which should have an edge and the actual edge was measured about 30 points | pieces equally spaced in the length direction 50 micrometers. And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. This 3σ was defined as “LER (nm)”.

[Development defect evaluation]
For the pattern formed on the silicon wafer as described above, the defect inspection apparatus KLA2360 (trade name) manufactured by KLA-Tencor Corporation is used, the pixel size of the defect inspection apparatus is set to 0.16 μm, and the threshold value is set. Was set to 20 and measured in a random mode. Development defects extracted from a difference caused by superimposition of a comparison image and a pixel unit were detected, and the number of development defects per unit area was calculated. A value of less than 1.0 was indicated as a double circle, a value of 1.0 or more and less than 5.0 was evaluated as ◯, a value of 5.0 or more and less than 10.0 was evaluated as Δ, and a value of 10.0 or more was evaluated as ×. A smaller value indicates better performance.

  As shown in Table 3, the compositions of the examples were superior in sensitivity, pattern shape, LER, and development defects compared to the compositions of the comparative examples.

<Resist evaluation (EUV)>
Each component shown in the following Table 4 was dissolved in the solvent shown in the same table to prepare a solution having a solid content concentration of 1.5% by mass. This solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a positive resist solution.

  The numerical value of “mass%” shown in Table 4 is a value based on the total solid content excluding the surfactant in the composition. In addition, content of surfactant is 0.01 mass% with respect to the total solid content except surfactant of a composition.

  The positive resist solution was applied onto a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. This was heated and dried on a hot plate at 120 ° C. for 90 seconds to obtain a resist film having an average film thickness of 50 nm.

[Sensitivity, pattern shape and roughness characteristics]
The resist film was irradiated with EUV light using an EUV exposure apparatus. Immediately after irradiation, it was heated on a hot plate at 130 ° 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% by mass, rinsed with pure water for 30 seconds, and then dried. Thereby, a line and space pattern (line: space = 1: 1) was formed.

(sensitivity)
First, the cross-sectional shape of the obtained line and space pattern was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). And the minimum irradiation energy at the time of resolving a line with a line width of 50 nm was calculated | required, and this value was made into "sensitivity (mJ / cm < ² >)".

(Pattern shape)
The cross-sectional shape of a 100 nm line pattern (line: space = 1: 1) at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). Then, the shape was evaluated in two stages of “rectangle” or “taper”.

(Roughness characteristics: LER)
The 100 nm line pattern (line: space = 1: 1) was observed using a scanning electron microscope (S-9260, manufactured by Hitachi, Ltd.). And the distance between the reference line which should have an edge, and the actual edge was measured about 30 equally spaced points included in the length direction of 50 μm. And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. This 3σ was defined as “LER (nm)”.
These evaluation results are shown in Table 4 below.

  As shown in Table 4, the compositions of the examples were superior in all of sensitivity, pattern shape, and LER as compared with the compositions of the comparative examples.

Claims (23)

  A resin (Aa) containing a repeating unit containing a fluorine atom, and a resin whose alkali solubility is changed by the action of an acid, and having a structural part that decomposes upon irradiation with actinic rays or radiation to generate an acid An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (Ab) containing a unit (B). At least one of resin (Aa) and resin (Ab) contains the at least 1 sort (s) of repeating unit represented by the following general formula (A3), The actinic-ray-sensitive or radiation-sensitive of Claim 1 characterized by the above-mentioned. Resin composition.

In general formula (A3),
AR represents an aryl group.
Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.
R represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.   Resin (Ab) contains the at least 1 sort (s) of repeating unit represented by general formula (A3), The composition of Claim 2 characterized by the above-mentioned.   The composition according to claim 2 or 3, wherein the resin (Aa) contains at least one repeating unit represented by the general formula (A3).   Both resin (Aa) and resin (Ab) contain the at least 1 sort (s) of repeating unit represented by general formula (A3), The composition of any one of Claims 2-4 characterized by the above-mentioned. . Resin (Ab) contains the at least 1 sort (s) of repeating unit represented by general formula (A), The composition of any one of Claims 1-5 characterized by the above-mentioned.

In the formula, n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5.
S ₁ represents a substituent. When m is 2 or more, the plurality of S ₁ may be the same as or different from each other. The composition according to claim 6, comprising at least a repeating unit represented by the following formula as the repeating unit represented by the general formula (A).

The composition according to any one of claims 1 to 7, wherein the resin (Aa) contains at least one repeating unit represented by the general formula (A).

In the formula, n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5.
S ₁ represents a substituent. When m is 2 or more, the plurality of S ₁ may be the same as or different from each other. The composition according to claim 8, comprising at least a repeating unit represented by the following formula as the repeating unit represented by the general formula (A).

The resin (Aa) contains at least one repeating unit containing a group represented by the general formula (F2), the general formula (F3) or the general formula (F4) as a repeating unit containing a fluorine atom. The composition of any one of -9.

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, in each of _{R 57 ~R 61, R 62 ~R} 64 and R ₆₅ to R _68, at least one represents a fluorine atom or a fluoroalkyl group. R ₆₂ and R ₆₃ may be connected to each other to form a ring. The resin (Ab) contains at least one selected from the group consisting of repeating units represented by the following general formulas (B1), (B2) and (B3) as the repeating unit (B). 11. The composition according to any one of 10 above.

In general formulas (B1), (B2) and (B3),
A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₆ represents a cyano group, a carboxy group, —CO—OR ₂₅ or —CO—N (R ₂₆ ) (R ₂₇ ). R ₂₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ may be bonded to each other to form a ring together with the nitrogen atom.
X ₁ , X ₂ and X ₃ are each independently a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R ₃₃ ) —, or these Represents a divalent linking group in combination of a plurality. R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.   12. The acid anion is produced in the repeating unit by decomposing the structural site in the repeating unit (B) by irradiation with actinic rays or radiation. Composition.   The composition according to any one of claims 1 to 12, wherein the structural moiety in the repeating unit (B) is an ionic structural moiety having a sulfonium salt structure or an iodonium salt structure.   The composition according to any one of claims 1 to 13, wherein the content of the resin (Aa) is in the range of 0.01 to 20% by mass based on the total solid content in the composition.   The composition according to any one of claims 1 to 14, wherein the content of the resin (Aa) is in the range of 0.01 to 10% by mass based on the total solid content in the composition.   The composition according to any one of claims 1 to 15, wherein the content of the resin (Aa) is in the range of 0.01 to 5 mass% based on the total solid content in the composition. The composition according to any one of claims 1 to 16, wherein the resin (Aa) further contains at least one repeating unit represented by the general formula (A1) and the general formula (A2).

In general formula (A1),
n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5.
S ₁ represents a substituent, and when m is 2 or more, the plurality of S ₁ may be the same as or different from each other.
A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one A ₁ represents a group capable of leaving by the action of an acid. When n ≧ 2, the plurality of A ₁ may be the same as or different from each other.
In general formula (A2),
X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, alkyl Represents a carbonyloxy group or an aralkyl group.
A ₂ represents a group capable of leaving by the action of an acid. The composition of any one of Claims 1-17 in which resin (Ab) contains at least 1 sort (s) of the repeating unit represented by general formula (A1) and general formula (A2).

In general formula (A1),
n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5.
S ₁ represents a substituent, and when m is 2 or more, the plurality of S ₁ may be the same as or different from each other.
A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one A ₁ represents a group capable of leaving by the action of an acid.
When n ≧ 2, the plurality of A ₁ may be the same as or different from each other. In general formula (A2),
X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, alkyl Represents a carbonyloxy group or an aralkyl group.
A ₂ represents a group capable of leaving by the action of an acid.   The composition according to claim 1, which is for EUV exposure.   The actinic-ray-sensitive or radiation-sensitive film formed using the composition of any one of Claims 1-19.   A pattern forming method comprising forming a film using the composition according to claim 1, exposing the film, and developing the exposed film.   The pattern forming method according to claim 21, wherein the exposure is performed using EUV.   The semiconductor device manufactured through the process including the pattern formation method of Claim 21 or 22.