JP5039581B2 - Positive resist composition and pattern forming method using the same - Google Patents

Description

  The present invention relates to a positive resist composition that can be suitably used in the manufacture of implantation resists, semiconductor integrated circuit elements, integrated circuit manufacturing masks, printed wiring boards, liquid crystal panels, and the like.

  An early chemically amplified positive resist composition comprising a photoacid generator and a resin protected with an acid-decomposable group is disclosed in, for example, Patent Document 1 (US Pat. No. 4,491,628). This chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as far ultraviolet light, and dissolves in the developer in the active radiation irradiated area and non-irradiated area by a reaction using this acid as a catalyst. It is a pattern forming material that changes the properties and forms a pattern on a substrate.

  Various positive resist compositions containing a resin protected with an acid-decomposable group have been known so far. For example, Patent Document 2 (Japanese Patent Application Laid-Open No. 5-249682) discloses an alkoxy (acetal) group. A resist composition using a protected polyhydroxystyrene resin is disclosed in Patent Document 3 (Japanese Patent Application Laid-Open No. 9-21866) using a polyhydroxystyrene resin protected with two different acid-decomposable groups. Patent Document 4 (Japanese Patent Laid-Open No. 2000-352822) discloses a resist composition using a resin protected by an acetal group having a heterocyclic group at the terminal via a linking group. (Patent Publication No. 2002-49156) discloses a resist composition using a polyhydroxystyrene resin protected with two different acetal groups.

  However, a general positive resist composition does not use an antireflective film as in the case of forming a pattern for implantation such as ion implantation, and has a strong standing when a highly reflective substrate is used as it is. Improvements were desired because of the generation of waves. Further, improvement in sensitivity and resolution has been desired.

U.S. Pat. No. 4,491,628 JP-A-5-249682 JP-A-9-21866 JP 2000-352822 A JP 2002-49156 A

  An object of the present invention is to provide a chemical that suppresses the generation of a standing wave, obtains a rectangular profile, and has high sensitivity and high resolution even when a high-reflection substrate is used as it is without using an antireflection film. An object of the present invention is to provide an amplification type positive resist composition.

As a result of intensive studies by the inventors, the object of the present invention has been achieved by the following constitution.
[1]
A positive resist composition comprising a resin (A) having a group represented by the following general formula (M′-2) at the main chain terminal.

In the above formula, Y ′ represents a group having at least absorption at 248 nm,
The group having at least absorption at 248 nm represents a group having one or more benzene rings and a conjugated double bond, a group having a biphenyl structure, or a group having a terphenyl structure.
[2]
A positive resist composition comprising a resin (A) having a group represented by the following general formula (M′-1) at the end of the main chain.

In the above formula, Y ″ represents a group having at least absorption at 248 nm,
The group having at least absorption at 248 nm represents a group having one or more benzene rings and a conjugated double bond, a group having two or more benzene rings, or a group having a hetero ring.
R ¹ and R ² are 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, alkylcarbonyl An oxy group or an aralkyl group is represented.
[3]
A positive resist composition comprising a resin (A) having a group represented by any one of the following formulas (M′-3) to (M′-5) at the end of the main chain.

In the above formula, Y represents a group having at least absorption at 248 nm.
R ¹ 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.
Met represents a metal atom.
[4]
The positive resist composition as described in [3] above, wherein the group having at least absorption at 248 nm has at least one benzene ring.
[5]
The positive resist composition as described in [3] above, wherein the group having at least absorption at 248 nm has at least two benzene rings.
[6]
The positive resist composition as described in any one of [1] to [5] above, wherein the resin (A) is decomposed by the action of an acid to increase the solubility in an alkali developer.
[7]
The resin (A) contains at least one of the repeating unit represented by the general formula (A1) and the repeating unit represented by (A2), according to any one of the above [1] to [6] The positive resist composition as described.

In general formula (A1),
n shows the integer of 0-5. m shows the integer of 0-5. However, m + n ≦ 5.
A ₁ represents a hydrogen atom or a group containing a group that decomposes under the action of an acid, and when there are a plurality of groups, they may be the same or different.
S ₁ represents an arbitrary substituent, and when there are a plurality of them, they may be the same or different.
In general formula (A2),
A ₂ represents a group containing a group that decomposes by the action of an acid.
In general formulas (A1) and (A2),
A ₃ 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 aralkyl. Represents a group.
[8]
The positive resist composition as described in any one of [1] to [7] above, further comprising (B) a compound that generates an acid upon irradiation with actinic rays or radiation.
[9]
It has a proton acceptor functional group and contains a compound that decomposes upon irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is reduced, disappeared, or changed from proton acceptor property to acidity. The positive resist composition as described in any one of [1] to [8] above.
[10]
A resist film formed of the positive resist composition according to any one of [1] to [9].
[11]
A pattern forming method comprising a step of exposing and developing the resist film according to the above [10].
The present invention has the above-mentioned configurations [1] to [11], and the other is described below for reference.

<1> A positive resist composition comprising a resin (A) having a group having absorption at 248 nm at the end of the main chain.
<2> The positive resist composition as described in <1> above, wherein the group having absorption at 248 nm has at least one benzene ring.
<3> The positive resist composition as described in <1> above, wherein the group having absorption at 248 nm has at least two benzene rings.
<4> The positive resist composition as described in any one of <1> to <3> above, wherein the resin (A) is decomposed by the action of an acid to increase the solubility in an alkali developer.
<5> The above-mentioned <1> to <4>, wherein the resin (A) contains at least one of the repeating unit represented by the general formula (A1) and the repeating unit represented by (A2). The positive resist composition according to any one of the above.

In general formula (A1),
n shows the integer of 0-5. m shows the integer of 0-5. However, m + n ≦ 5.
A ₁ represents a hydrogen atom or a group containing a group that decomposes under the action of an acid, and when there are a plurality of groups, they may be the same or different.
S ₁ represents an arbitrary substituent, and when there are a plurality of them, they may be the same or different.
In general formula (A2),
A ₂ represents a group containing a group that decomposes by the action of an acid.
In general formulas (A1) and (A2),
A ₃ 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 aralkyl. Represents a group.

<6> The positive resist composition as described in any one of <1> to <5>, further comprising (B) a compound that generates an acid upon irradiation with actinic rays or radiation.
<7> A compound which has a proton acceptor functional group and generates a compound which is decomposed by irradiation with actinic rays or radiation to decrease, disappear, or change the proton acceptor property to acidic. The positive resist composition as described in any one of <1> to <6> above, which is contained.

<8> The positive resist composition as described in any one of <1> to <7>, wherein the resin (A) has a weight average molecular weight (Mw) in the range of 1,000 to 200,000. .
<9> The positive resist composition according to any one of <1> to <7>, wherein the resin (A) has a weight average molecular weight (Mw) in the range of 1,000 to 100,000. .
<10> The positive resist composition as described in any one of <1> to <7>, wherein the resin (A) has a weight average molecular weight (Mw) in the range of 1,000 to 50,000. .
<11> The positive resist composition as described in any one of <1> to <7>, wherein the resin (A) has a weight average molecular weight (Mw) in the range of 1,000 to 25,000. .

<12> The positive resist composition as described in any one of <1> to <11> above, further comprising (C) an organic basic compound.
<13> The positive resist composition as described in any one of <1> to <12>, further comprising (D) a surfactant.

<14> The positive resist composition as described in any one of <1> to <13>, further comprising a solvent.
<15> The positive resist composition as described in <14> above, which contains propylene glycol monomethyl ether acetate as the solvent.
<16> The positive resist composition as described in <15> above, further containing propylene glycol monomethyl ether as the solvent.

<17> The positive resist composition as described in <1> to <16> above, which is exposed by irradiation with KrF, electron beam, X-ray or EUV.
<18> A pattern forming method comprising a step of forming a resist film, exposing and developing the positive resist composition according to any one of <1> to <17>.

  The positive resist composition of the present invention contains a resin having a group having absorption at 248 nm at the end of the main chain, so that the standing wave is substantially not generated, the profile is good, the sensitivity is high, and the resolution is high. Excellent effect that is characteristic.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

  The positive resist composition of the present invention contains a resin (A) having a group having absorption at 248 nm at the end of the main chain.

  Hereinafter, each component blended in the positive resist composition of the present invention will be described.

[1] Resin (A)
The resist composition of the present invention contains a resin (A) having a group having absorption at 248 nm at the end of the main chain.
The group having absorption at 248 nm may be any group as long as it has some absorption at 248 nm, but the absorption is preferably higher.
The group having at least absorption at 248 nm is, for example, a group having at least one benzene ring or at least a heterocycle, but preferably further has a conjugated double bond (including a carbonyl group). Or a group having two or more benzene rings.
It is more preferable that the group having at least absorption at 248 nm has 1 to 3 benzene rings.
The number of benzene rings corresponds to the number of benzene rings represented in the structural formula. For example, 2 naphthalene, 3 anthracene, 1 phthalimide ring, 1 1,4-naphthoquinone ring, biphenyl There are two structures, benzophenone structure, diphenyl ether structure, and phenyl benzoate structure, and three terphenyl structures.

An arbitrary substituent may be present on the benzene ring, and the substituent is preferably a substituent conjugated with the benzene ring (hereinafter referred to as a conjugated substituent).
Preferred examples of the conjugated substituent include groups represented by any of the following formulas (a) to (e).

In the formulas (a) to (e), R _i , R _j , R _k , R _l and R _m represent the same or different arbitrary substituents, for example, an alkyl group, an alkoxy group, an acyl group , Acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, hydroxy group, halogen atom, cyano group, nitro group, sulfonylamino group, alkylthio group, arylthio group, 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.

More preferred examples of the conjugated substituents (a) to (e) include (a), (b) and (c). More preferably, (c) can be mentioned.
The number of atoms constituting the group containing a group having absorption at 248 nm is preferably 100 or less, and more preferably 50 or less.

For example, an arylcarbonyl group, a heteroarylcarbonyl group, a condensed ring aryl group, a condensed ring heteroaryl group, a condensed ring arylcarbonyl group, a condensed ring heteroarylcarbonyl group, an alkyl group having an arylcarbonyl group, or a condensed ring aryl group Examples thereof include an alkyl group, an alkyl group having a condensed ring arylcarbonyl group, an alkyl group having a heteroarylcarbonyl group, an alkyl group having a condensed ring heteroaryl group, and an alkyl group having a condensed ring heteroarylcarbonyl group.
Moreover, it is not necessary to limit to aromatic rings, such as a phenyl group, and even a heterocyclic ring can be used as long as it is a group having absorption at 248 nm. In this case as well, it is more preferable to have a conjugated double bond (including a carbonyl group).

Specifically, having absorption at 248 nm is preferably a molar absorption coefficient ε at 248 nm of a compound containing a group having absorption at 248 nm of 200 or more, more preferably 200 to 500,000, more preferably 300 to 300,000. Particularly preferred is 500 to 200,000, and most preferred is 1000 to 100,000. The molar extinction coefficient ε here is a value in a tetrahydrofuran solution (23 ° C.).
In the present invention, since the resin has a group having absorption at 248 nm, the transmittance of light at 248 nm of the film after being applied to the substrate can be controlled to a desired value. Can be changed. Therefore, the transmittance can be controlled without depending on the film thickness.
For example, the transmittance at 248 nm with a film thickness of 4000 mm is 90% or less. Preferably, it is 30 to 85%, more preferably 35 to 80%, still more preferably 38 to 78%, and most preferably 40 to 75%.
For example, when the film thickness is 1900 mm, the transmittance at 248 nm is 90% or less. Preferably, it is 30 to 88%, more preferably 40 to 85%, still more preferably 50 to 83%, and most preferably 60 to 80%.
The transmittance is preferably larger in terms of resolution and sensitivity, and smaller in terms of standing wave suppression. The film thickness is not limited to the above example.

  As a method for introducing a group having at least absorption at 248 nm into the main chain terminal, a method using an initiator in which a group having at least absorption at 248 nm is introduced in advance, a main chain terminal treatment after polymerization, and a group having at least absorption at 248 nm And a method of introducing a group having at least absorption at 248 nm using a functional group at the end of the main chain after polymerization.

(2- (carbamoylazo) isobutyronitrile) (V-30), 2,2′-azobis {
2-Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} (VA-080), 2,2′-azobis {2-methyl-N- [2- (1- Hydroxybutyl)] propionamide (VA-085), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] (VA-086), dimethyl 2,2'-azobis (2 -Methylpropionate) (V-601), a group having at least absorption at 248 nm using a functional group of an azo initiator such as 4,4'-azobis (4-cyanovaleric acid (V-501). In the above example, the name in parentheses is a trade name of Wako Pure Chemical Industries, Ltd.

  Examples of the method using an initiator in which a group having at least absorption at 248 nm is introduced in advance include the following examples using an azo-based initiator.

Y represents a group having at least absorption at 248 nm.
R ¹ and R ² are 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, alkylcarbonyl An oxy group or an aralkyl group is represented.
The details of the group as R ¹ and R ^{2 are the same} as the group as A ₃ in the general formulas (A1) and (A2).

  Examples of the method for performing main chain terminal treatment after polymerization and introducing a group having at least absorption at 248 nm include the following methods.

Y, R ¹ and R ² are the same as above, and R ³ is the same group as R ¹ and R ² .

  Examples of a method for introducing a group having at least absorption at 248 nm using a functional group at the end of the main chain after polymerization include the following methods.

  Y represents a group having at least absorption at 248 nm.

Also, at least absorption at 248 nm is achieved by using a dissociation-bonding SFRP (Stable Free Radical Polymerization) agent containing a group having absorption at 248 nm, an exchange transfer chain type RAFT (Reversible Addition-Fragmentation chain Transfer) agent, or the like. Groups can be introduced. In general, when polymerization is performed using an SFRP agent or a RAFT agent, the SFRP agent or the RAFT agent is introduced into the main chain terminal of the polymer chain.
There are various methods for synthesizing the RAFT agent and the like, and a desired compound can be synthesized by using the method described in Japanese Patent No. 3639859.

  Specific examples of the polymerization method include radical polymerization, anionic polymerization, radical polymerization, living radical polymerization, and the like, but are not limited thereto.

Examples of the initiator, SFRP agent, and RAFT agent having a group having absorption at 248 nm include the following.

  Examples of the general formula of the main chain terminal include (M′-1) to (M′-5), but are not limited thereto.

Y represents a group having at least absorption at 248 nm.
R ¹ and R ² are 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, alkylcarbonyl An oxy group or an aralkyl group is represented.
The details of the group as R ¹ and R ^{2 are the same} as the group as A ₃ in the general formulas (A1) and (A2).
Met represents a metal atom, and Se, Te, Sb, and Bi are preferable.

  More preferable examples include (M′-1), (M′-2), and (M′-3), and more preferable examples include (M′-1) and (M′-2). .

  Specific examples of the main chain terminal are described below, but are not limited thereto.

  The resin (A) preferably contains at least one of the repeating units represented by the general formulas (A1) and (A2).

In general formula (A1),
n shows the integer of 0-5. m shows the integer of 0-5. However, m + n ≦ 5.
A ₁ represents a hydrogen atom or a group containing a group that decomposes under the action of an acid, and when there are a plurality of groups, they may be the same or different.
The group containing a group capable of decomposing by the action of an acid is a group in which A ₁ is eliminated, resulting in a hydroxyl group in the repeating unit represented by the general formula (A1), that is, an acid-decomposable group itself. It may be a group containing an acid-decomposable group, that is, a group in which an alkali-soluble group such as a hydroxyl group or a carboxyl group is generated in a residue that is decomposed by the action of an acid and bonded to a repeating unit.
Specifically, it is represented by a tertiary alkyl group such as t-butyl group or t-amyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, -C (L ₁ ) (L ₂ ) -O-Z. Such acetal groups.
L ₁ and L ₂ may be the same or different and each represents an atom or group selected from a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl group.
Z represents an alkyl group, a cycloalkyl group or an aralkyl group.
Z and L ₁ may be bonded to each other to form a 5- or 6-membered ring.

S ₁ represents an arbitrary substituent, and when there are a plurality of them, they may be the same or different. For example, 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 Group, halogen atom, cyano group, nitro group, sulfonylamino group, alkylthio group, arylthio group, 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 aralkyl group in L ₁ , L ₂ and Z include those having 7 to 15 carbon atoms such as benzyl group and phenethyl group. These groups may have a substituent.

Preferable substituents that the aralkyl group has 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, an aralkylthio group, and the like. Examples of the aralkyl group having a substituent include an alkoxybenzyl group, a hydroxybenzyl group, and a phenylthiophenethyl group.
The range of the carbon number of the substituent which the aralkyl group in L ₁ , L ₂ and Z may have is preferably 12 or less.

Examples of the 5- or 6-membered ring formed by combining Z and L ₁ with each other include a tetrahydropyran ring and a tetrahydrofuran ring.

  In the present invention, Z is preferably a linear or branched alkyl group. Thereby, the effect of the present invention becomes more remarkable.

A ₃ represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group, a cycloalkyl group, an aryl group, a carboxyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, or Represents an aralkyl group.

In formula (A2), A ₂ represents a group containing a group capable of decomposing by the action of an acid.
The group containing a group that decomposes due to the action of an acid is a group in which A ₂ is eliminated, resulting in a carboxyl group in the repeating unit represented by the general formula (A2), that is, an acid-decomposable group itself. It may be a group containing an acid-decomposable group, that is, a group in which an alkali-soluble group such as a hydroxyl group or a carboxyl group is generated in a residue that is decomposed by the action of an acid and bonded to a repeating unit.
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.
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.

Specific examples of groups (acid-decomposable groups) containing a group that decomposes by the action of an acid containing an alicyclic structure as A ₂ or a group that decomposes by the action of an acid are given below.

In the present invention, a group containing a group that is decomposed by the action of an acid is A ₁ or A ₂ leaving,
As a result, a group that generates a hydroxyl group in the repeating unit represented by the general formula (A1) or (A2),
That is, even if it is an acid-decomposable group itself, an acid-decomposable group-containing group, that is, an alkali-soluble group such as a hydroxyl group or a carboxyl group is decomposed by the action of an acid and bonded to a repeating unit May be a group in which

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.

  Although the specific example of the repeating unit represented by general formula (A1) below is given, it is not limited to these.

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

  In general formula (A2), the repetition represented by general formula (A2 ′) is more preferable.

In general formula (A2 ′),
AR represents a benzene ring, a naphthalene ring, or an anthracene ring.
Rn represents an alkyl group or an aryl group.
AR and Rn may combine to form a ring.
A represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group.

  AR represents a benzene ring, a naphthalene ring, or an anthracene ring, and each may have one or more substituents. Preferred substituents include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl and the like. Is a linear or branched alkyl group having 1 to 20 carbon atoms, or an alkoxy group, a hydroxyl group, a halogen atom, an aryl group, a cyano group, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an alkylthio group, Examples include arylthio groups, aralkylthio groups, thiophenecarbonyloxy groups, thiophenemethylcarbonyloxy groups, heterocyclic residues such as pyrrolidone residues, etc., but linear or branched alkyl groups having 1 to 5 carbon atoms, or alkoxy groups Is preferable from the viewpoint of resolving power. More preferred is benzene, paramethylbenzene or paramethoxybenzene.

As the alkyl group in Rn, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc. , Preferably a linear or branched alkyl group having 1 to 20 carbon atoms is used.
As the aryl group in Rn, those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group, and anthracenyl group are preferable.
Preferred substituents that the above-mentioned group as Rn may have include alkoxy groups, hydroxyl groups, halogen atoms, nitro groups, acyl groups, acyloxy groups, acylamino groups, sulfonylamino groups, alkylthio groups, arylthio groups, Heterocyclic residues such as aralkylthio group, thiophenecarbonyloxy group, thiophenemethylcarbonyloxy group, pyrrolidone residue, etc. are mentioned, among them alkoxy group, hydroxyl group, halogen atom, nitro group, acyl group, acyloxy group, acylamino group, A sulfonylamino group is preferred.

Examples of the alkyl group in A include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc. , Preferably a linear or branched alkyl group having 1 to 20 carbon atoms is used. These groups may have a substituent, and preferred substituents that may be included 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, an alkylthio group, Examples include arylthio groups, aralkylthio groups, thiophenecarbonyloxy groups, thiophenemethylcarbonyloxy groups, and heterocyclic residues such as pyrrolidone residues. Among them, CF ₃ groups, alkyloxycarbonylmethyl groups, alkylcarbonyloxymethyl groups, hydroxy groups, etc. A methyl group, an alkoxymethyl group and the like are preferable.
Examples of the halogen atom in A include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the alkyl contained in the alkyloxycarbonyl group in A include the same alkyl groups as in A above.

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

  The resin (A) may further have a repeating unit represented by the general formula (A4), which is preferable from the viewpoints of improving the film quality and suppressing the decrease in film thickness of the unexposed area.

In general formula (A4),
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 halogen atom, an aryl group, an alkoxy group or an acyl group.
q represents an integer of 0 to 4.
W represents a group that is not decomposed by the action of an acid.

  W represents a group that is not decomposed by the action of an acid (also referred to as an acid stabilizing group). Specifically, a hydrogen atom, 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.

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

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

The resin (A) is preferably a resin (acid-decomposable resin) whose solubility in an alkaline developer is increased by the action of an acid, and is decomposed by the action of an acid in an arbitrary repeating unit. It preferably contains a group (acid-decomposable group) that generates a soluble group.
As described above, the repeating unit represented by the general formula (A1) or (A2) may have an acid-decomposable group, or may be included in another repeating unit.
Examples of the acid-decomposable group include those represented by —C (═O) —X ₁ —R ₀ other than those described above.
In the formula, R ₀ is a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy. 1-alkoxyethyl group such as ethyl group, 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- An oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue and the like can be mentioned. X ₁ represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or -NHSO ₂
NH- is represented.

The content of the repeating unit having an acid-decomposable group in the resin (A) is preferably 5 to 95 mol%, more preferably 10 to 60 mol%, and particularly preferably 10 to 50 mol% in all repeating units. It is.
The content of the repeating unit represented by the general formula (A1) in the resin (A) is preferably 40 to 100 mol%, more preferably 45 to 100 mol%, and particularly preferably 50 to 50% in all repeating units. 100 mol%.
The content of the repeating unit represented by the general formula (A2) or (A2 ′) in the resin (A) is preferably 5 to 60 mol%, more preferably 10 to 50 mol% in all repeating units. Most preferably, it is 10-40 mol%.
The content of the repeating unit represented by the general formula (A4) in the resin (A) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, particularly preferably in all repeating units. Is 0-30 mol%.

  The resin (A) 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 weight average molecular weight (Mw) of the resin (A) 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 (A) having a dispersity of 1.5 to 2.0 can be synthesized by radical polymerization using an azo polymerization initiator. Further preferred resin (A) having a dispersity of 1.0 to 1.5 can be synthesized by living radical polymerization.

Moreover, you may use resin (A) in combination of 2 or more types.
The total amount of the resin (A) added is generally 10 to 96% by mass, preferably 15 to 96% by mass, and particularly preferably 20 to 95% by mass with respect to the total solid content of the positive resist composition. %.

  Specific examples of the repeating unit of the main chain of the resin (A) are shown below, but are not limited thereto.

  Specific examples (M-1) to (M-31) of the main chain terminal and specific examples (A-1) to (A-135) of the repeating units of the main chain of the resin (A) may be in any combination.

[2] Compound that generates acid upon irradiation with actinic ray or radiation The resist composition of the present invention contains a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter also referred to as “acid generator”).
Examples of the acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, a microresist, and the like, KrF excimer laser light, electron Known compounds that generate acid upon irradiation with actinic rays or radiation such as rays and EUV, and mixtures thereof can be appropriately selected and used.
Examples of such an acid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, o-nitrobenzyl sulfonates, and the like.

  Further, a group that generates an acid upon irradiation with actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. 3914407, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A 62-153853, JP-A The compounds described in 63-146029 and the like can be used.

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

  Preferred compounds among the acid generators 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 generally 1 to 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. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Z ⁻ represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

  Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.

  Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

  The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms such as methyl. Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group and the like.

The aromatic group in the aromatic sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (Preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), aryl Ruoxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.

  Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylmethyl group.

  The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include, for example, the same halogen atom and alkyl as in the aromatic sulfonate anion Group, cycloalkyl group, alkoxy group, alkylthio group and the like.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Alkyl groups substituted with fluorine atoms are preferred.

  Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Examples of the non-nucleophilic anion of Z ⁻ include an aliphatic sulfonate anion in which the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group. A bis (alkylsulfonyl) imide anion substituted with a fluorine atom and a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include a compound (ZI-1) described later.
), (ZI-2) and (ZI-3).

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or R ₂₀₁
Some of to R ₂₀₃ is an aryl group and the remainder may be an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include 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.

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 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 substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. These are 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 all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group having no 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 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, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R _203, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

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

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

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

  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 general formula (ZI-3),
R _{1c to} R _5c each independently represents 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.

Any 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, and this ring structure includes an oxygen atom and a sulfur atom. , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.

Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 8 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c , such as a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxy group. A carbonylmethyl group is more preferred.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .

Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as in R _{1c to} R _5c .

R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like.

The alkyl group and cycloalkyl group in R ₂₀₄ to R _207, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

  Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₆ , R ₂₀₇ and R ₂₀₈ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.
Further, the acid generator is preferably a compound that generates an acid having one sulfonic acid group or imide group, more preferably a compound that generates monovalent perfluoroalkanesulfonic acid, or a monovalent fluorine atom or fluorine atom. A compound that generates an aromatic sulfonic acid substituted with a group containing fluorinated acid, or a compound that generates a monovalent fluorine atom or imide acid substituted with a group containing a fluorine atom, and even more preferably, It is a sulfonium salt of a substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted imide acid or a fluorine-substituted methide acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid or a fluorinated substituted imido acid whose pKa of the generated acid is pKa = -1 or less, and the sensitivity is improved. .

<Sulfonic acid generator>
A compound that generates sulfonic acid upon irradiation with actinic rays or radiation, which is preferable as an acid generator (also referred to as a sulfonic acid generator), is a compound that generates sulfonic acid upon irradiation with actinic rays or radiation such as KrF excimer laser light, electron beam, EUV, etc. Examples of such compounds are diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

From the viewpoint of improving image performance such as resolution and pattern shape, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, and disulfones are preferable.
From the viewpoint of remaining low standing waves, more preferred are imide sulfonate, oxime sulfonate, diazodisulfone and disulfone, and still more preferred are oxime sulfonate and diazodisulfone.
The sulfonic acid generator can be synthesized by a known method such as a synthesis method described in JP-A-2002-27806.

  Examples of particularly preferred sulfonic acid generators are given below.

The content of the acid generator is generally 0.5 to 20% by mass, preferably 1 to 15% by mass, particularly preferably 1 to 10% by mass, based on the total solid content of the resist composition. It is. That is, 1% by mass or more is preferable in terms of sensitivity and line edge roughness, and 10% by mass or less is preferable in terms of resolution, pattern shape, and film quality.
In addition, one type of acid generator may be used, or two or more types may be mixed and used. For example, as the acid generator, a compound that generates aryl sulfonic acid upon irradiation with active light or radiation and a compound that generates alkyl sulfonic acid upon irradiation with active light or radiation may be used in combination.

<Carboxylic acid generator>
You may use the compound (it is also called a carboxylic acid generator) which generate | occur | produces carboxylic acid by irradiation of actinic light or a radiation.
As the carboxylic acid generator, a compound represented by the following general formula (C) is preferable.

In the general formula (C), R _{21 to} R ₂₃ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. Z represents a sulfur atom or an iodine atom. When Z is a sulfur atom, p is 1, and when Z is an iodine atom, p is 0.

In the general formula (C), R _{21 to} R ₂₃ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and these groups may have a substituent.
Examples of the substituent that the alkyl group, cycloalkyl group or alkenyl group may have include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), an aryl group (a phenyl group, a naphthyl group, etc.), a hydroxy group, An alkoxy group (methoxy group, ethoxy group, butoxy group, etc.) etc. can be mentioned.
Examples of the substituent that the aryl group may have include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), nitro group, cyano group, alkyl group (methyl group, ethyl group, t-butyl group, t -Amyl group, octyl group, etc.), hydroxy group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.) and the like.

R _{21 to} R ₂₃ are preferably each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms. And more preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 18 carbon atoms, and particularly preferably an aryl group having 6 to 15 carbon atoms. Each of these groups may have a substituent.

R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.
Examples of the substituent that the alkyl group, cycloalkyl group, and alkenyl group may have are the same as those described as examples of the substituent when R ₂₁ is an alkyl group. Examples of the substituent for the aryl group, the R ₂₁ may be the same as those mentioned as examples of the substituent when it is an aryl group.

R ₂₄ is preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 24 carbon atoms, and more Preferably, they are a C1-C18 alkyl group, a C3-C18 cycloalkyl group, and a C6-C18 aryl group, Most preferably, a C1-C12 alkyl group, C3-C3 A cycloalkyl group having 12 carbon atoms and an aryl group having 6 to 15 carbon atoms. Each of these groups may have a substituent.

Z represents a sulfur atom or an iodine atom. p is 1 when Z is a sulfur atom, and 0 when Z is an iodine atom.
Two or more cation moieties of formula (C) are bonded by a single bond or a linking group (for example, -S-, -O-, etc.) to form a cation structure having a plurality of cation moieties of formula (C). May be.

  Although the preferable specific example of a carboxylic acid generator is given to the following, of course, it is not limited to these.

Regarding the carboxylic acid generator, the content in the positive resist composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, based on the total solid content of the composition. %, Particularly preferably 0.05 to 3% by mass. One type of carboxylic acid generator may be used, or two or more types may be mixed and used.
The carboxylic acid generator can be synthesized by a known method such as the synthesis method described in JP-A-2002-27806.
When the sulfonic acid generator (B) and the carboxylic acid generator (C) are used in combination, the C / B (mass ratio) is usually 99.9 / 0.1-50 / 50, preferably 99 / 1-60. / 40, particularly preferably 98/2 to 70/30.

[3] A compound that has a proton acceptor functional group and generates a compound that is decomposed by irradiation with actinic rays or radiation to decrease, disappear, or change the proton acceptor property to acidic. The positive resist composition of the present invention has a proton acceptor functional group in terms of sensitivity, resolution, and line edge roughness, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease or disappearance of proton acceptor properties. Or a compound that generates a compound that has been changed from proton acceptor property to acidity (hereinafter also referred to as “compound (PA)”).

  A compound (PA) generated by decomposition by irradiation with actinic rays or radiation, wherein the proton acceptor property is lowered, disappears, or is changed from proton acceptor property to acid, is represented by the following general formula (PA-I) Mention may be made of the compounds represented.

In general formula (PA-I),
A represents a divalent linking group.
Q represents a sulfo group (—SO ₃ H) or a carboxyl group (—CO ₂ H).
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom or -N (Rx)-.
Rx represents a hydrogen atom or a monovalent organic group.
R represents a monovalent organic group having a proton acceptor functional group or a monovalent organic group having an ammonium group.

  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 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
The alkyl group 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. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And a branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group.
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. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
The aryl group in Rx may have a substituent and is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
The aralkyl group in Rx may have a substituent, preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.
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 a group capable of electrostatically interacting with protons or a functional group having electrons, such as a functional group having a macrocyclic structure such as a cyclic polyether. Or a functional group having a nitrogen atom with a lone electron pair that does not contribute to π conjugation. The nitrogen atom having a lone 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.

Preferable partial structures of the proton acceptor functional group include, for example, crown ether, azacrown ether, tertiary amine, secondary amine, primary amine, pyridine, imidazole, pyrazine structure and the like.
Preferred examples of the partial structure of the ammonium group include tertiary ammonium, secondary ammonium, primary ammonium, pyridinium, imidazolinium, and pyrazinium structures.
The group containing such a structure preferably has 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkyl group in the alkenyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group, which contain a proton acceptor functional group or an ammonium group in R, are represented by Rx. These are the same as the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group mentioned.

  Examples of the substituent that each group 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 having 3 to 10 carbon atoms), and an aryl group (preferably Has 6 to 14 carbon atoms, an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably C2-C20), an aminoacyl group (preferably C2-C20) etc. are mentioned. 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 20). As for the aminoacyl group, examples of the substituent further include 1 or 2 alkyl groups (preferably having 1 to 20 carbon atoms).

When B is -N (Rx)-, R and Rx are preferably bonded 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 1 to 15 carbon atoms). As for the aminoacyl group, examples of the substituent include 1 or 2 alkyl groups (preferably having 1 to 15 carbon atoms).

  Among the compounds represented by the general formula (PA-I), 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.

  Hereinafter, although the specific example of a compound represented by general formula (PA-I) is shown, this invention is not limited to this.

The compound represented by the following general formula (PA-II), which is generated by the decomposition of the compound (PA) upon irradiation with actinic rays or radiation and whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity, ) Can be mentioned.

In general formula (PA-II),
Q ₁ and Q ₂ each independently represents a monovalent organic group. However, either _one of Q ₁ and Q ₂ has a proton acceptor functional group. Q ₁ and Q ₂ may combine to form a ring, and the formed ring may have a proton acceptor functional group.
X ₁ and X ₂ each independently represent —CO— or —SO ₂ —.

The monovalent organic groups as Q ₁ and Q _{2 in} formula (PA-II) preferably have 1 to 40 carbon atoms, and examples thereof include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, An alkenyl group etc. can be mentioned.
The alkyl group in Q ₁ and Q ₂ may have a substituent, preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and an oxygen atom, sulfur atom, nitrogen atom in the alkyl chain You may have. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And a branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group.
The cycloalkyl group in Q ₁ and Q ₂ may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a nitrogen atom in the ring. Good. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
The aryl group in Q ₁ and Q ₂ may have a substituent, and preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group and a naphthyl group.
The aralkyl group in Q ₁ and Q ₂ may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, or a naphthylethyl group. Is mentioned.
The alkenyl group for Q ₁ and Q ₂ may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group.
Examples of the substituent that each group 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 having 3 to 10 carbon atoms), and an aryl group (preferably Has 6 to 14 carbon atoms, an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably C2-C20), an aminoacyl group (preferably C2-C10) etc. are mentioned. 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 1 to 10 carbon atoms). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 10). Examples of the alkyl group having a substituent include perfluoroalkyl groups such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

One of the monovalent organic groups of Q ₁ and Q ₂ has a proton acceptor functional group.
The proton acceptor functional group is a group that can electrostatically interact with a proton or a functional group having a lone pair of electrons, such as a functional group having a macrocyclic structure such as a cyclic polyether, or π A functional group having a nitrogen atom having a lone electron pair with little conjugation contribution can be given. Examples of the nitrogen atom having a lone electron pair with little contribution of π conjugation include a nitrogen atom having a partial structure represented by the following general formula.

  Preferable partial structures of the proton acceptor functional group include, for example, crown ether, azacrown ether, tertiary amine, secondary amine, primary amine, pyridine, imidazole, pyrazine, aniline structure and the like. The group containing such a structure preferably has 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. The alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group are the same as those mentioned above.

  Examples of the substituent that each group 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 having 3 to 10 carbon atoms), and an aryl group (preferably Has 6 to 14 carbon atoms, an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably C2-C20), an aminoacyl group (preferably C2-C20) etc. are mentioned. 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 20). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having 1 to 20 carbon atoms).

  The proton acceptor functional group may be substituted with an organic group having a bond that is cleaved by an acid. Examples of the organic group having a bond that can be cleaved by an acid include an amide group, an ester group (preferably a tertiary alkyloxycarbonyl group), an acetal group (preferably a 1-alkyloxy-alkyloxy group), and a carbamoyl group. Group, carbonate group and the like.

Examples of the structure in which Q ₁ and Q ₂ are bonded to form a ring and the formed ring has a proton acceptor functional group include, for example, an organic group of Q ₁ and Q ₂ is further an alkylene group, an oxy group And a structure bonded with an imino group or the like.

In the general formula (PA-II), at least one of X ₁ and X ₂ is preferably —SO ₂ —.

  The compound represented by the general formula (PA-II) is preferably a compound represented by the following general formula (PA-III).

In general formula (PA-III),
Q ₁ and Q ₃ each independently represents a monovalent organic group. However, _one of Q ₁ and Q ₃ has a proton acceptor functional group. Q ₁ and Q ₃ may combine to form a ring, and the formed ring may have a proton acceptor functional group.
X ₁ , X ₂ and X ₃ each independently represent —CO— or —SO ₂ —.
A represents a divalent linking group.
B represents a single bond, an oxygen atom, or —N (Qx) —.
Qx represents a hydrogen atom or a monovalent organic group.
When B is —N (Qx) —, Q ₃ and Qx may combine to form a ring.
n represents 0 or 1.

Q ₁ has the same meaning as Q _{1 in} formula (PA-II).
Examples of the organic group of Q ₃ include the same organic groups as Q ₁ and Q ₂ in formula (PA-II).

  The divalent linking group in A is preferably a divalent linking group having 1 to 8 carbon atoms, for example, an alkylene group having 1 to 8 carbon atoms, a phenylene group having a fluorine atom. Etc. An alkylene group having a fluorine atom is more preferable, 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 preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, more preferably a perfluoroalkylene group, and particularly preferably a perfluoroethylene group, a perfluoropropylene group, or a perfluorobutylene group. .

  The monovalent organic group in Qx is preferably an organic group having 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group are the same as those described above.

In the general formula (PA-III), X ₁ , X ₂ and X ₃ are preferably —SO ₂ —.

  Hereinafter, although the specific example of a compound represented by general formula (PA-II) is shown, this invention is not limited to this.

  As the compound (PA), a sulfonium salt compound of the compound represented by the general formula (PA-I), (PA-II) or (PA-III), the general formula (PA-I), (PA-II) or The iodonium salt compound of the compound represented by (PA-III) is preferable, and the compound represented by the following general formula (PA1) or (PA2) is more preferable.

In general formula (PA1):
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a sulfonate anion or carboxylate anion from which a hydrogen atom of the —SO ₃ H site or —COOH site of the compound represented by the general formula (PA-I) is removed, or a general formula (PA-II) or (PA -III) represents an anion of the compound represented by

The carbon number of the organic group in R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
It is also possible to form the two members ring structure of the R ₂₀₁ to R _203, an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Specific examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the compound (A1a) described later.
, (A1b), and (A1c), the corresponding groups.
In addition, the compound which has two or more structures represented by general formula (PA1) may be sufficient. For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (PA1) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (PA1) It may be a compound.

  As more preferred (PA1) component, compounds (A1a), (A1b), and (A1c) described below can be exemplified.

Compound (A1a) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (PA1), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or R ₂₀₁
Part of the to R ₂₀₃ is an aryl group with the remaining being an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, diarylcycloalkylsulfonium compounds, aryldialkylsulfonium compounds, aryldicycloalkylsulfonium compounds, arylalkylcycloalkylsulfonium compounds, and the like.
The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Examples thereof include a butyl group and a t-butyl group.
The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 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 substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, most preferably They are a C1-C4 alkyl group and a C1-C4 alkoxy group. The substituent may be substituted on any one of three R ₂₀₁ to R _203, or may be substituted on all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (A1b) will be described.
The compound (A1b) is a compound in which R _{201 to} R ₂₀₃ in the general formula (PA1) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring having a hetero atom.
The organic group not having an aromatic ring in R ₂₀₁ to R _203, generally from 1 to 30 carbon atoms, preferably an organic group having 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, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, An alkoxycarbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.
The alkyl group in R _{201 to} R ₂₀₃ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group,
Propyl group, butyl group, pentyl group). The alkyl group as R ₂₀₁ to R ₂₀₃ is a straight-chain or branched 2-oxoalkyl group, an alkoxycarbonylmethyl group are preferred.
Preferred examples of the cycloalkyl group for R _{201 to} R ₂₀₃ include cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group). The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is a 2-oxocycloalkyl group is more preferable.
The linear or branched 2-oxoalkyl group in R _{201 to} R ₂₀₃ may have a double bond in the chain, and preferably has> C═O at the 2-position of the alkyl group. The group can be mentioned.
The 2-oxocycloalkyl group in R _{201 to} R ₂₀₃ may have a double bond in the chain, and preferably includes a group having> C═O at the 2-position of the cycloalkyl group. be able to.
The alkoxy group in the alkoxycarbonylmethyl group of R ₂₀₁ to R _203, preferably may be mentioned alkoxy groups having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), an alkoxycarbonyl group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. .

  The compound (A1c) is a compound represented by the following general formula (A1c), and is a compound having an arylacylsulfonium salt structure.

In general formula (A1c):
_R213 represents an aryl group which may have a substituent, and is preferably a phenyl group or a naphthyl group. Preferred substituents in R _213, an alkyl group, an alkoxy group, an acyl group, a nitro group, a hydroxyl group, an alkoxycarbonyl group and a carboxy group.
R ₂₁₄ and R ₂₁₅ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Y ₂₀₁ and Y ₂₀₂ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or a vinyl group.
X ⁻ represents a sulfonate anion or carboxylate anion from which a hydrogen atom of the —SO ₃ H site or —COOH site of the compound represented by the general formula (PA-I) is removed, or a general formula (PA-II) or (PA -III) represents an anion of the compound represented by
R ₂₁₃ and R ₂₁₄ may be bonded to form a ring structure, R ₂₁₄ and R ₂₁₅ may be bonded to form a ring structure, and Y ₂₀₁ and Y ₂₀₂ are bonded to each other. To form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond. Examples of the group R ₂₁₃ and R _214, R ₂₁₄ and R _215, Y ₂₀₁ and Y ₂₀₂ are formed by combined include a butylene group and a pentylene group.

As the alkyl group for R ₂₁₄ , R ₂₁₅ , Y _201, and Y ₂₀₂ , a linear or branched alkyl group having 1 to 20 carbon atoms is preferable. Examples of the alkyl group for Y ₂₀₁ and Y ₂₀₂ include a 2-oxoalkyl group having> C═O at the 2-position of the alkyl group, an alkoxycarbonylalkyl group (preferably an alkoxy group having 2 to 20 carbon atoms), and a carboxyalkyl group. More preferred.
The cycloalkyl group for R ₂₁₄ , R ₂₁₅ , Y ₂₀₁ and Y ₂₀₂ is preferably a cycloalkyl group having 3 to 20 carbon atoms.

Y ₂₀₁ and Y ₂₀₂ are preferably an alkyl group having 4 or more carbon atoms, more preferably an alkyl group having 4 to 6, and further preferably 4 to 12.
In addition, at least one of R ₂₁₄ or R ₂₁₅ is preferably an alkyl group, and more preferably both R ₂₁₄ and R ₂₁₅ are alkyl groups.

In the general formula (PA2),
_R204 and _R205 each independently represents an aryl group, an alkyl group or a cycloalkyl group.
X ⁻ represents a sulfonate anion or carboxylate anion from which a hydrogen atom of the —SO ₃ H site or —COOH site of the compound represented by the general formula (PA-I) is removed, or a general formula (PA-II) or (PA -III) represents an anion of the compound represented by

The aryl group of R ₂₀₄ and R _205, a phenyl group, a naphthyl group, more preferably a phenyl group.
The alkyl group in R ₂₀₄ and R ₂₀₅ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group). Group, butyl group, pentyl group).
Preferred examples of the cycloalkyl group for R ₂₀₄ and R ₂₀₅ include cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
_R204 and _R205 may have a substituent. Examples of the substituent that R204 and R205 may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group (for example, 6 to 15 carbon atoms). , Alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups, and the like.

  The compound that generates the compound represented by the general formula (PA-I), (PA-II), or (PA-III) upon irradiation with actinic rays or radiation is preferably represented by the general formula (PA1). A compound, more preferably compounds (A1a) to (A1c).

Compound (PA) decomposes upon irradiation with actinic rays or radiation to generate, for example, a compound represented by general formula (PA-1) or (PA-2).
The compound represented by the general formula (PA-1) has a sulfo group or a carboxyl group together with a proton acceptor functional group, so that the proton acceptor property is lowered or disappeared compared to the compound (PA), or the proton acceptor. It is a compound that has changed from scepter to acidic.
The compound represented by the general formula (PA-2) has an organic sulfonylimino group or an organic carbonylimino group together with a proton acceptor functional group, so that the proton acceptor property decreases and disappears compared to the compound (PA). Or a compound that is changed from proton acceptor property to acidity.
In the present invention, the acceptor property is lowered when the non-covalent complex which is a proton adduct is formed from a compound having a proton acceptor functional group and a proton, and the equilibrium constant in the chemical equilibrium is reduced. Means.
Proton acceptor property can be confirmed by measuring pH.

  Hereinafter, although the specific example of the compound (PA) which generate | occur | produces the compound represented with general formula (PA-I) by irradiation of actinic light or a radiation is given, this invention is not limited to this.

  These compounds are synthesized from a compound represented by the general formula (PA-I) or a lithium, sodium or potassium salt thereof and a hydroxide, bromide or chloride of iodonium or sulfonium. Or a salt exchange method described in JP-A No. 2003-246786.

  Hereinafter, although the specific example of the compound (PA) which generate | occur | produces the compound represented by general formula (PA-II) by irradiation of actinic light or a radiation is given, this invention is not limited to this.

These compounds can be easily synthesized by using a general sulfonic acid esterification reaction or sulfonamidation reaction. For example, one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine or alcohol containing a partial structure represented by the general formula (PA-II) to form a sulfonamide bond or a sulfonate bond Then, the other sulfonyl halide moiety can be hydrolyzed, or the cyclic sulfonic acid anhydride can be opened by an amine or alcohol containing a partial structure represented by the general formula (PA-II). . An amine or alcohol containing a partial structure represented by the general formula (PA-II) is an amine, an alcohol such as (R′O ₂ C) ₂ O or an anhydride such as R′O ₂ CCl, acid It can be synthesized by reacting with a chloride compound.

  The content of the compound (PA) in the positive resist composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total solid content of the composition. .

[4] Organic basic compound (C)
The organic basic compound contained in the resist composition of the present invention is preferably a compound having a stronger basicity than phenol. The molecular weight of the organic basic compound is usually 100 to 900, preferably 150 to 800, more preferably 200 to 700. Further, nitrogen-containing basic compounds are particularly preferable.

  Preferred nitrogen-containing basic compounds are compounds having structures of the following formulas (A) to (E) as a preferred chemical environment. Formulas (B) to (E) may be part of a ring structure.

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group. (Preferably having 6 to 20 carbon atoms), wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

  The alkyl group may be unsubstituted or may have a substituent. Examples of the alkyl group having a substituent include an aminoalkyl group having 1 to 6 carbon atoms and a hydroxyalkyl group having 1 to 6 carbon atoms. preferable.

R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms.

  Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms of different chemical environments in one molecule, and particularly preferably both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. Or a compound having an alkylamino group.

Further, at least one nitrogen-containing compound selected from an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group can be exemplified. .
As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably C6-C12) may be bonded to a nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group. Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. As the halogen atom, 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 of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. 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 of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. 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 amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Etc. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be any in the range of 1 to 5.
It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

In the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group, the sulfonic acid ester group may be any of alkyl sulfonic acid ester, cycloalkyl group sulfonic acid ester, and aryl sulfonic acid ester. In the case of an alkyl sulfonate ester, the alkyl group has 1 to 20 carbon atoms, in the case of a cycloalkyl sulfonate ester, the cycloalkyl group has 3 to 20 carbon atoms, and in the case of an aryl sulfonate ester, the aryl group has 6 carbon atoms. ~ 12 are preferred. Alkyl sulfonic acid ester, cycloalkyl sulfonic acid ester, and aryl sulfonic acid ester may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, and a sulfonic acid. An ester group is preferred.
It is preferable to have at least one oxyalkylene group between the sulfonate group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  Preferred examples include guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and the like. These may have a substituent, and preferred substituents include 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, cyano group and the like.

  Particularly preferred compounds include 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-aminoethylpyridine, 4- Aminoethylpyridine, 3-aminopyrrolidine, Perazine, 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, but are not limited to, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine. It is not a thing.

A tetraalkylammonium salt type nitrogen-containing basic compound can also be used. Among these, tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (
n-butyl) ammonium hydroxide and the like are preferred. These nitrogen-containing basic compounds are used alone or in combination of two or more.

  The use ratio of the acid generator and the organic basic compound in the composition is preferably acid generator / organic basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / organic basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

[5] Surfactants In the present invention, surfactants can be used, which are preferable from the viewpoints of film-forming properties, pattern adhesion, development defect reduction, and the like.

  Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Sorbitan mono palmitate - door,

Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (Shin-Akita Kasei) (Made by Co., Ltd.), MegaFuck F171, F173 (Dainippon Ink Chemical Co., Ltd.), Florad FC430, FC431 (Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102 , SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), silicon surfactants, organosiloxane polymer KP341 Shin-Etsu Chemical Co., Ltd.) and acrylic or methacrylic acid-based (co) polymer Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.). The compounding amount of these surfactants is usually 2 parts by mass or less, preferably 1 part by mass or less per 100 parts by mass of the solid content in the composition of the present invention.
These surfactants may be added alone or in some combination.

The surfactant is any one of fluorine and / or silicon surfactants (fluorine surfactants and silicon surfactants, surfactants containing both fluorine atoms and silicon atoms), or It is preferable to contain 2 or more types.
As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540 No. 7, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A 2002-277862, US Pat. No. 5,405,720. No. 5,360,692, No. 5,529,881, No. 5,296,330, No. 5,543,098, No. 5,576,143, No. 5,294,511, No. 5,824,451. The following commercially available surfactants can also be used as they are.
Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block linked body) or a poly (block linked body of oxyethylene and oxypropylene) group, may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).
Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Coalesce, etc. Can.

  The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the positive resist composition (excluding the solvent).

[6] Other components The positive resist composition of the present invention may further contain a dye, a photobase generator and the like, if necessary.

1. Dye A dye can be used in the present invention.
Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (oriental chemical industry) Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI522015) and the like.

2. Photobase generator As photobase generators that can be added to the composition of the present invention, JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, JP-A-5-5995, JP-A-6-194835,
Examples thereof include compounds described in JP-A-8-146608, JP-A-10-83079 and European Patent No. 622682, specifically, 2-nitrobenzylcarbamate, 2,5-dinitrobenzylcyclohexylcarbamate, N-cyclohexyl-4- Methylphenylsulfonamide, 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate and the like can be suitably used. These photobase generators are added for the purpose of improving the resist shape and the like.

3. Solvents The resist composition of the present invention is dissolved in a solvent that dissolves each of the above components and coated on a support. The solid content concentration of all resist components is usually preferably 2 to 30% by mass, more preferably 3 to 25% by mass.
Solvents used here include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethyl Formamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable. Or mixed to use.

  The positive resist composition of the present invention is applied onto a substrate to form a thin film. The thickness of this coating film is preferably 0.05 to 4.0 μm.

  The composition of the present invention is excellent in that the generation of a standing wave is remarkably suppressed and a good pattern can be obtained even when it is directly applied to a substrate having a highly reflective surface without applying an antireflection film. Although effective, a good pattern can be formed even if an antireflection film is used.

  As the antireflection film used as the lower layer of the resist, either an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, or an organic film type made of a light absorber and a polymer material may be used. it can. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. Examples of the organic antireflection film include a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin, a light absorber, and maleic anhydride copolymer described in US Pat. No. 5,294,680. A reaction product of a coalescence and a diamine type light absorbing agent, a resin binder described in JP-A-6-186863 and a methylolmelamine thermal crosslinking agent, a carboxylic acid group, an epoxy group and a light-absorbing group described in JP-A-6-118656. An acrylic resin-type antireflection film in the same molecule, a composition comprising methylol melamine and a benzophenone-based light absorber described in JP-A-8-87115, and a low-molecular light absorber added to a polyvinyl alcohol resin described in JP-A-8-179509 And the like.

  In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

  Further, if necessary, an antireflection film can be used as an upper layer of the resist. Examples of the antireflection film include AQUATAR-II, AQUATAR-III, and AQUATAR-VII manufactured by AZ Electronic Materials.

In the manufacture of precision integrated circuit elements, the pattern forming process on the resist film is carried out on the substrate (eg, silicon / silicon dioxide coated substrate, glass substrate, ITO substrate, quartz / chromium oxide coated substrate, etc.). A resist pattern is formed by applying a resist composition, forming a resist film, and then irradiating actinic rays or radiation such as KrF excimer laser light, electron beam, EUV light, etc., heating, developing, rinsing and drying. Can be formed.

Examples of the alkaline developer used in development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, An aqueous solution (usually 0.1 to 20% by mass) of an alkali such as a quaternary ammonium salt such as choline or a cyclic amine such as pyrrole or piperidine can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution.
Among these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.
The pH of the alkali developer is usually 10-15.

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

(Synthesis Example 1) Synthesis of Resin (J-1) of Terminal (M-14) and Main Chain (A-2) 204 mL of (4-phenyl) phenylmagnesium bromide (0.5M tetrahydrofuran solution) was added to 50 mL of dry tetrahydrofuran. The mixture was stirred and cooled to 0 ° C. Maintaining 0 ° C., 7.77 g of carbon disulfide was added over 15 minutes. Thereafter, the mixture was stirred at 0 ° C. for 1 hour, and 15.86 g of benzyl bromide was added over 15 minutes. Then, it stirred at room temperature for 1 hour. Ice water (300 mL) was added, and the organic layer was extracted with ethyl acetate (500 mL). Furthermore, the organic layer was washed with 300 mL of brine and dried over anhydrous magnesium sulfate. After anhydrous magnesium sulfate was removed by filtration, the residual solvent was removed. Further, purification was performed with silica gel (ethyl acetate / hexane solvent) to obtain benzyl (4-phenyl) dithiobenzoate (28.4 g, yield 87%) (exchange transfer chain type RAFT agent).

  In a reaction vessel, 81.10 g of 4-acetoxystyrene, 5.76 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), and 16.02 g of benzyl (4-phenyl) dithiobenzoate were added to ethylene glycol mono It melt | dissolved in 460 g of ethyl ether acetate, and was dripped over 4 hours in the 80 degreeC type | system | group in nitrogen gas atmosphere. After dropping, the reaction solution was allowed to cool to room temperature after being heated and stirred for 2 hours, and dropped into 5 L of hexane to precipitate a polymer. The filtered solid was dissolved in 500 ml of acetone, dropped again into 5 L of hexane, and the filtered solid was dried under reduced pressure to obtain 64.78 g of 4-acetoxystyrene polymer (main chain terminal (M-14)). It was confirmed by NMR and absorption spectrum that (M-14) was introduced at the end of the main chain.

  40.00 g of the polymer obtained above, 40 ml of methanol, 100 ml of 1-methoxy-2-propanol and 1.5 ml of concentrated hydrochloric acid were added to the reaction vessel, heated to 80 ° C. and stirred for 5 hours. The reaction solution was allowed to cool to room temperature and dropped into 3 L of distilled water. The filtered solid was dissolved in 200 ml of acetone, dropped again into 3 L of distilled water, and the filtered solid was dried under reduced pressure to obtain 29.31 g of 4-hydroxystyrene polymer (main chain terminal (M-14)). The weight average molecular weight by GPC was 2000, and the molecular weight dispersity (Mw / Mn) was 1.10.

  20 g of the 4-hydroxystyrene polymer is dissolved in 100 g of propylene glycol monomethyl ether acetate (PGMEA), and the solution is decompressed to 60 mmHg at 60 ° C. to distill off about 50 g of the solvent together with water remaining in the system. did. The mixture was cooled to 20 ° C., 7.20 g of ethyl vinyl ether and 0.10 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 2 hours. Thereafter, 0.42 g of triethylamine was added for neutralization, and 300 g of ethyl acetate and 150 g of water were added for washing operation three times. Then, the amount of solvent was adjusted and the 30 mass% resin (J-1) solution was obtained. The weight average molecular weight by GPC was 2800, the molecular weight dispersity was 1.10, and from 1H and 13C-NMR analysis, the acetal protection rate of phenolic OH was 50%.

(Synthesis Example 2) Synthesis of terminal (M-30) and main chain (A-2) resin (J-5) In a reaction vessel, 81.10 g of 4-acetoxystyrene, polymerization initiator V-601 (Pure Wako) 5.76 g (manufactured by Yakuhin Kogyo Co., Ltd.) was dissolved in 460 g of ethylene glycol monoethyl ether acetate, and dropped into the system at 80 ° C. over 4 hours in a nitrogen gas atmosphere. After dropping, the reaction solution was allowed to cool to room temperature after being heated and stirred for 2 hours, and dropped into 5 L of hexane to precipitate a polymer. The filtered solid was dissolved in 500 ml of acetone, dropped again into 5 L of hexane, and the filtered solid was dried under reduced pressure to obtain 75.48 g of 4-acetoxystyrene polymer (main chain terminal is derived from V-601).

In a reaction vessel, 75.48 g of the 4-acetoxystyrene polymer obtained above (main chain terminal is derived from V-601), 3 L of aqueous sodium hydroxide (0.1 M), and 1 L of tetrahydrofuran were stirred at room temperature for 5 hours. Thereafter, 5 L of ethyl acetate was added, followed by 1000 g of sodium chloride. The organic layer was extracted and the residual solvent was removed. To this solution, 120 g of dicyclohexylcarbodiimide, 3 g of 4-dimethylaminopyridine, 39.4 g of 4-phenylphenol, and 5 L of dry tetrahydrofuran were added and stirred overnight at room temperature in an argon atmosphere.
Thereafter, the solvent was removed, 5 L of ethyl acetate was added, the organic layer was extracted, and dropped into 10 L of hexane to precipitate the polymer. The filtered solid was dissolved in 1 L of acetone, dropped again into 10 L of hexane, and the filtered solid was dried under reduced pressure to obtain 74.30 g of 4-acetoxystyrene polymer (main chain terminal (M-30)).

  Into the reaction vessel, 40.00 g of the 4-acetoxystyrene polymer (main chain terminal (M-30)) obtained above, 40 ml of methanol, 100 ml of 1-methoxy-2-propanol, and 1.5 ml of concentrated hydrochloric acid were added. The mixture was heated to 0 ° C. and stirred for 5 hours. The reaction solution was allowed to cool to room temperature and dropped into 3 L of distilled water. The filtered solid was dissolved in 200 ml of acetone, dropped again into 3 L of distilled water, and the filtered solid was dried under reduced pressure to obtain 29.31 g of 4-hydroxystyrene polymer (main chain terminal (M-14)). The weight average molecular weight by GPC was 15000, and the molecular weight dispersity (Mw / Mn) was 1.55.

20 g of the 4-hydroxystyrene polymer is dissolved in 100 g of propylene glycol monomethyl ether acetate (PGMEA), and the solution is decompressed to 60 mmHg at 60 ° C. to distill off about 50 g of the solvent together with water remaining in the system. did. The mixture was cooled to 20 ° C., 4.20 g of ethyl vinyl ether and 0.10 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 2 hours. Thereafter, 0.42 g of triethylamine was added for neutralization, and 300 g of ethyl acetate and 150 g of water were added for washing operation three times. Then, the amount of solvent was adjusted and the 30 mass% resin (J-5) solution was obtained. The weight average molecular weight by GPC was 16000, the molecular weight dispersity was 1.55, and the acetal protection rate of phenolic OH was 30% from 1H and 13C-NMR analysis.
When the absorption at 248 nm was measured for each synthesized resin, the absorption at 248 nm was confirmed, and the presence of the desired specific end group was confirmed.

  Polymers shown in Table 2 were synthesized in the same manner as in Synthesis Example 1 except that the monomers, polymers, terminal groups, vinyl ethers, and the like used were changed.

Resins exemplified in the structure shown in Table 1 were synthesized in the same manner as in Synthesis Example 1 above.
The resin composition ratio (molar ratio of repeating units) is the order of repeating units from the left of the structure shown above.

(Preparation of resist composition)
It is obtained after dissolving resin, acid generator, proton acceptor-containing compound, surfactant and basic compound (when used in combination) in propylene glycol monomethyl ether acetate to prepare a solution having a solid content concentration of 5.0% by mass. The resulting solution was microfiltered with a membrane filter having a 0.1 μm aperture to obtain a resist solution.

<Preparation of resist composition>
Resin: 17.1653g
Acid generator: 0.1479 g
Basic compound or proton acceptor group-containing compound: 0.0393 g
Surfactant: 0.4020 g
When the proton acceptor group-containing compound and the basic compound are used in combination, the proton acceptor group-containing compound is 0.0196 g and the basic compound is 0.0196 g.

[Pattern preparation and evaluation (KrF)]
Using a spin coater, the positive resist solution prepared as described above is uniformly coated on a silicon wafer that has been subjected to hexamethyldisilazane treatment, and is heated and dried at 120 ° C. for 90 seconds to form a positive film having a thickness of 0.4 μm. A mold resist film was formed. The resist film was subjected to pattern exposure using a KrF excimer laser stepper (FPA3000EX-5 manufactured by Canon Inc., wavelength 248 nm). After irradiation, it was baked at 110 ° C. for 90 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried. The obtained pattern was evaluated by the following method.

Resist performance was evaluated as follows. The results are shown in Table 2. However, Examples 2, 7, 16, 17, 25, 28, 29, 30, 32, 34 and 35 are reference examples.

[Remaining standing waves]
The side wall of the resist pattern obtained with a 0.30 μm line and space mask pattern was observed with a scanning electron microscope, and the following five-step evaluation was performed.
A: When there is no standing wave and the side wall of the pattern is very clean B: When the standing wave is slightly seen or irregularities are seen on the side wall of the pattern C: When the standing wave can be clearly confirmed D: Constant When standing waves can be confirmed slightly strongly E: When standing waves can be confirmed very strongly Note that B to D are not applicable in this embodiment.
[Profile]
The profile of the pattern obtained above was observed with a cross-sectional SEM, and the following three-stage evaluation was performed.
1: When it is rectangular 2: When taper is hardly recognized, when it is almost rectangular 3: When it is clearly tapered [sensitivity]
Scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.) was used for the cross-sectional shape of the obtained pattern.
Was observed. The minimum irradiation energy when resolving a 180 nm line (line: space = 1: 1) was defined as sensitivity.
[Resolution]
The resolving power was defined as the limiting resolving power (line and space were separated and resolving) at the irradiation dose showing the above sensitivity.

The component (c) used in the examples, other components, and the resins used in the comparative examples are shown below.
[Organic basic compounds]
D-1: Dicyclohexylmethylamine D-2: 2,4,6-triphenylimidazole D-3: Tetra- (n-butyl) ammonium hydroxide D-4: The following compound

[Other components (surfactant)]
W-1: Fluorosurfactant, PF6320 (manufactured by OMNOVA)
W-2: Fluorine / silicone surfactant, MegaFac R08 (manufactured by Dainippon Ink & Chemicals, Inc.)
W-3: Silicon-based surfactant, siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

C-1: molar composition ratio; 65/35, weight average molecular weight; 9500, dispersity; 1.15

C-2: molar composition ratio; 65/35, weight average molecular weight; 9000, dispersity; 1.20

From the results of Table 2, the resist composition of the present invention has a profile that significantly reduces the occurrence of standing waves even when it is directly coated on a substrate having a highly reflective surface without coating an antireflection film. It can be seen that the sensitivity and resolution are excellent.

Claims (11)

A positive resist composition comprising a resin (A) having a group represented by the following general formula (M′-2) at the main chain terminal.

In the above formula, Y ′ represents a group having at least absorption at 248 nm,
The group having at least absorption at 248 nm represents a group having one or more benzene rings and a conjugated double bond, a group having a biphenyl structure, or a group having a terphenyl structure. A positive resist composition comprising a resin (A) having a group represented by the following general formula (M′-1) at the end of the main chain.

  In the above formula, Y ″ represents a group having at least absorption at 248 nm,
  The group having at least absorption at 248 nm represents a group having one or more benzene rings and a conjugated double bond, a group having two or more benzene rings, or a group having a hetero ring.
  R ¹ And R ² Is a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group, a cycloalkyl group, an aryl group, a carboxyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group or an aralkyl group Represents. A positive resist composition comprising a resin (A) having a group represented by any one of the following general formulas (M'-3) to (M'-5) at the end of the main chain.

  In the above formula, Y represents a group having at least absorption at 248 nm.
  R ¹ Is a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group, a cycloalkyl group, an aryl group, a carboxyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group or an aralkyl group Represents.
  Met represents a metal atom. 4. The positive resist composition according to claim 3 , wherein the group having at least absorption at 248 nm has at least one benzene ring. 4. The positive resist composition according to claim 3 , wherein the group having at least absorption at 248 nm has at least two benzene rings. Resin (A), is decomposed by the action of an acid The positive resist composition according to any one of claims 1 to 5, characterized in that the solubility in an alkali developer is increased. Resin (A) contains at least 1 sort (s) of the repeating unit represented by general formula (A1), and (A2), The positive in any one of Claims 1-6 characterized by the above-mentioned. Type resist composition.

In general formula (A1),
n shows the integer of 0-5. m shows the integer of 0-5. However, m + n ≦ 5.
A ₁ represents a hydrogen atom or a group containing a group that decomposes under the action of an acid, and when there are a plurality of groups, they may be the same or different.
S ₁ represents an arbitrary substituent, and when there are a plurality of them, they may be the same or different.
In general formula (A2),
A ₂ represents a group containing a group that decomposes by the action of an acid.
In general formulas (A1) and (A2),
A ₃ 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 aralkyl. Represents a group. Furthermore, (B) The positive resist composition according to any one of claims 1 to 7, characterized in that it contains an actinic ray or a compound which generates an acid when exposed to radiation. It has a proton acceptor functional group and contains a compound that decomposes upon irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is reduced, disappeared, or changed from proton acceptor property to acidity. the positive resist composition according to any one of claims 1 to 8, wherein. A resist film formed from the positive resist composition according to claim 1. Pattern forming method characterized by having a resist film EXPOSURE, a step of developing of claim 10.