JP2004318045A - Positive resist composition and method for forming pattern using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist composition showing sufficient transmitting property when a light source at ≤160 nm, specifically, F<SB>2</SB>excimer laser light (at 157 nm) is used, showing a favorable pattern profile, critical resolution, and dry etching durability, and having a favorable surface profile of the film after etching. <P>SOLUTION: The positive resist composition contains: a resin (A1) having a specified repeating unit; a resin (A2) having a specified repeating unit; and a compound (B) which generates an acid by the effect of active rays or radiation. At least one of the resin (A1) and the resin (A2) increases the solubility with an alkaline developing solution by the effect of an acid. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a positive resist composition suitably used in microlithography processes such as the production of VLSI and high-capacity microchips, and other photofabrication processes. More specifically, the present invention relates to a positive resist composition capable of forming a highly refined pattern using vacuum ultraviolet light of 160 nm or less.

  Integrated circuits have been increasingly integrated, and in manufacturing semiconductor substrates such as VLSI, processing of ultrafine patterns having a line width of less than a quarter micron has been required. As one of means for miniaturizing a pattern, it is known to shorten the wavelength of an exposure light source used in forming a resist pattern.

For example, in the manufacture of a semiconductor device having a degree of integration of up to 64 Mbits, i-line (365 nm) of a high-pressure mercury lamp has been used as a light source until now. As a positive resist corresponding to this light source, a number of compositions containing a novolak resin and a naphthoquinonediazide compound as a photosensitive material have been developed, and have achieved sufficient results in processing line widths of up to about 0.3 μm. . Further, in the manufacture of a semiconductor device having an integration degree of 256 Mbit or more, KrF excimer laser light (248 nm) has been adopted as an exposure light source instead of i-line.
In addition, for the purpose of manufacturing semiconductors with a degree of integration of 1 Gbit or more, the use of ArF excimer laser light (193 nm), which is a light source with a shorter wavelength in recent years, and F2 excimer laser light ( 157 nm) is under consideration.

In accordance with the shortening of the wavelength of these light sources, the constituent components of the resist material and the compound structure thereof have also changed greatly.
As a resist composition for exposure with KrF excimer laser light, a resin mainly composed of poly (hydroxystyrene) having a low absorption in the 248 nm region and protected with an acid-decomposable group is used as a main component. Compositions combining so-called generated compounds (photoacid generators), so-called chemically amplified resists, have been developed.

  Further, as a resist composition for ArF excimer laser light (193 nm) exposure, there is a chemically amplified resist using an acid-decomposable resin in which an alicyclic structure having no absorption at 193 nm is introduced into the main chain or side chain of a polymer. It has been developed.

For F ₂ excimer laser light (157 nm), the above alicyclic resin also has a large absorption in the 157 nm region, and it has been found that this is insufficient to obtain the desired pattern of 0.1 μm or less. In contrast, non-patent document 1 (Proc.SPIE.Vol.3678.13 (1999)) reports that a resin having a fluorine atom (perfluoro structure) introduced has sufficient transparency at 157 nm, and effective fluorine. Non-Patent Document 2 (Proc. SPIE. Vol. 3999. 330 (2000)), Non-Patent Document 3 (Proc. SPIE. Vol. 3999.357 (2000)), Non-Patent Document 4 (Proc. SPIE Vol. 3999.365 (2000)), Patent Document 1 (International Publication No. WO 00/17712 pamphlet), etc., and studies on resist compositions containing fluorine-containing resins have been made.

International Optical Engineering Bulletin (Proc.SPIE.) Vol.3678. P.13. (1999) International Optical Engineering Bulletin (Proc.SPIE.) Vol.3999. 330. (2000) International Optical Engineering Bulletin (Proc.SPIE.) Vol.3999. 357. (2000) International Optical Engineering Bulletin (Proc.SPIE.) Vol.3999. 365. (2000) WO-00 / 17712 pamphlet

  However, the resist composition containing a fluororesin for F2 excimer laser light exposure has problems in resolution, pattern profile, etc., and these solutions have been desired.

Accordingly, an object of the present invention is to provide a positive resist composition suitable for use as an exposure light source of 160 nm or less, particularly F ₂ excimer laser light (157 nm). Specifically, when a light source of 157 nm is used, An object is to provide a positive resist composition that exhibits a good pattern profile, critical resolution, and dry etching resistance, and also has a good surface shape after etching.

As a result of intensive investigations while paying attention to the above characteristics, the present inventors have found that the object of the present invention can be achieved brilliantly by using the following specific composition, and have reached the present invention.
That is, the present invention has the following configuration.

(1)
(A1) a resin containing a repeating unit having at least two groups represented by the following general formula (Z);
(A2) a resin containing at least one repeating unit among the repeating units represented by the following general formulas (I) to (III), and (B) a compound that generates an acid by the action of actinic rays or radiation,
And a positive resist composition characterized in that at least one of the resin (A1) or the resin (A2) is a resin whose solubility in an alkaline developer is increased by the action of an acid.

In general formula (Z),
A plurality of R ⁵⁰ to R ⁵⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R ^{50 to} R ⁵⁵ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
A plurality of Y each independently represents a hydrogen atom or an organic group.

In general formulas (I) to (III),
R ₀ and R ₁ may be the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl group or an aryl group.
R _{2 to} R ₄ may be the same or different and each represents an alkyl group, a cycloalkyl group, or an aryl group.
R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ may combine to form a ring.

(2) The repeating unit having at least two groups represented by the general formula (Z) is a repeating unit represented by the following general formulas (A), (A ′), (A ″) The positive resist composition as described in (1) above.

In the general formulas (A), (A ′), (A ″),
Several R _{< a1} > -R _<a6> represents a hydrogen atom, a fluorine atom, or an alkyl group each independently. However, at least one of R _{a1 to} R _a6 is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R _a7 represents a halogen atom, a cyano group or an alkyl group.
R _a8 and R _a9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an acyl group, an alkyl group, an alkenyl group, an aralkyl group or an aryl group.
When there are a plurality of R _{a10 s} , they may be different and each independently represents a halogen atom, an alkyl group or an alkoxy group.
R _a11 may be different when there are a plurality of R _a11 and each independently represents a halogen atom, an alkyl group or an alkoxy group.
R _{a12 to} R _a14 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Y _{a1 to} Y _a3 each independently represents a hydrogen atom or an organic group.
p, m1, and m ′ each independently represents an integer of 2 to 5.
n ′ represents an integer of 0 to 7.
n represents 0 or 1.
m2 represents an integer of 0 to 7.
A ₁ , A ₂ , and La ₁ each independently represent a single bond or a divalent linking group.

(3) The group of which solubility in an alkali developer is increased by the action of the acid of the resin (A1) and / or the resin (A2) protected the group represented by the formula (B) or the carboxyl group with an acid-decomposable group. The positive resist composition as described in (1) or (2), which comprises a group.

In general formula (B),
Zb represents an acid-decomposable group.
R _{31 to} R ₃₆ are each independently a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{31 to} R ₃₆ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
At least one of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.

(4) A resin whose solubility in an alkaline developer is increased by the action of the acid of the resin (A1) and / or the resin (A2),
The positive resist composition according to any one of (1) to (3), comprising a group represented by the formula (B ′) or a group obtained by protecting a carboxyl group with an acid-decomposable group .

In general formula (B ′),
Zc represents a hydrogen atom or a non-acid-decomposable group.
R _{31 to} R ₃₆ are each independently a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{31 to} R ₃₆ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
At least one of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.

(5) The resin (A1) and / or the resin (A2) further contains at least one repeating unit selected from the following formulas (IV) to (XII): (1) to (4) The positive resist composition as described in any one of (1).

In general formulas (IV) to (V),
R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or an acid-decomposable group.
R ₆ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or an acid-decomposable group.
R _7a may be different when there are a plurality of R _{7a s} and represents a halogen atom, an alkyl group or an alkoxy group. R _7a is preferably a halogen atom or a perfluoroalkyl group, more preferably a halogen atom. The halogen atom is preferably a fluorine atom.
n represents 0 or 1.
n ′ represents an integer of 0 to 7.
A ₁ is a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₂₂ —, —CO—O—R ₂₃ —, —CO—N (R ₂₄ ). -R ₂₅ - represents a.
R ₂₂ , R ₂₃ and R _{25 each} have a single bond or an ether group, ester group, amide group, urethane group or ureido group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group. Represents.
R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.

In general formula (VI),
Rx ₁ to Rx ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or at least one alkyl group wherein a hydrogen atom is substituted with a fluorine atom.
R _{61 to} R ₆₆ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{61 to} R ₆₆ is a fluorine atom.
R _{67 to} R ₇₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{67 to} R ₇₂ is a fluorine atom.
Z ₁ represents a phenylene group, a cyclohexylene group, an adamantane residue or a norbornane residue.
L ₁ represents a single bond or a divalent linking group.
q is 0 or 1.
Y ₁ represents a hydrogen atom or an organic group.

In general formula (VII),
R ₄₁ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
R ^{50 to} R ⁵⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R ^{50 to} R ⁵⁵ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Y ₂ represents a hydrogen atom or an organic group.
In general formula (VIII),
Ry _{1 to} Ry ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Y ₃ represents a hydrogen atom or an organic group.

In general formulas (IV) to (X),
R ₁₅ is a hydrogen atom, a hydroxyalkyl group, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, an alkenyl group having a fluorine atom, an aralkyl group having a fluorine atom, an aryl group having a fluorine atom, or an acid-decomposable group. Represents a group.
Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with a carbon atom.
R ₁₆ , R ₁₇ and R ₁₈ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group or —CO—O—R ₁₅ .
R ₁₉ , R ₂₀ and R ₂₁ may be the same or different and have a hydrogen atom, a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, an alkenyl group having a fluorine atom, or a fluorine atom. An aralkyl group, an aryl group having a fluorine atom, an alkoxy group having a fluorine atom, or a hydroxyalkyl group is represented. However, at least one of R ₁₉ , R ₂₀ and R ₂₁ is a group other than a hydrogen atom.
n represents 0 or 1, and x, y, z represents an integer of 0 to 4.

In general formula (XI),
Ra _{1 to} Ra ₃ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an aryl group, an alkoxy group or an aralkyl group.
Y ₄ represents a hydrogen atom or an organic group.
m represents 1 or 2.
In general formula (XII),
Ra _{4 to} Ra ₆ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an aryl group, an alkoxy group or an aralkyl group.
Y ₅ represents a hydrogen atom or an organic group.
m represents 1 or 2.

(6) The positive resist according to any one of (1) to (5), wherein k is 2 in the repeating unit represented by the formula (A) contained in the resin (A1) Composition.
(7) At least one of Rx ₁ to Rx ₃ in the repeating unit represented by the formula (VI) and at least one of Ry ₁ to Ry ₃ in the repeating unit represented by the formula (VIII) is a fluorine atom or at least The positive resist composition as described in (5) or (6), wherein one hydrogen atom is an alkyl substituted with a fluorine atom.

(8) The positive resist composition as described in any one of (1) to (6), further comprising (E) an organic basic compound.
(9) The positive resist composition according to any one of (1) to (8), further comprising (D) a surfactant.
(10) As described in any one of (1) to (9), the component (B) contains (B1) a compound that generates an organic sulfonic acid by the action of actinic rays or radiation. A positive resist composition.

(11) As the component (B1), a compound that generates an organic sulfonic acid containing at least one fluorine atom by the action of actinic rays or radiation, and an organic sulfonic acid that does not contain a fluorine atom by the action of actinic rays or radiation The positive resist composition as described in (10) above, which contains one or more kinds of generated compounds.
(12) The positive resist composition as described in (10) or (11), further comprising (B2) a compound that generates carboxylic acid by the action of actinic rays or radiation.

(13) The positive electrode according to any one of (1) to (12), wherein the resin (A1) and / or the resin (A2) further has a partial structure represented by the formula (D) Type resist composition

In general formula (D),
AR represents a monocyclic or polycyclic alicyclic hydrocarbon group.
L ₃ represents a single bond or a divalent linking group.
When there are a plurality of Xd, each independently represents a hydroxyl group, a cyano group, an alkoxy group or an alkyl group. However, at least one of Xd is not an alkyl group.
p represents an integer of 1 to 4.

(14) The positive resist composition as described in (13), wherein at least one of Xd in the repeating unit having the partial structure represented by the formula (D) is a hydroxyl group.

(15) The repeating unit having a partial structure represented by the formula (D) is at least one repeating unit selected from the formulas (D1) to (D4), (13) or (14 ) Positive resist composition.

In formula (D1),
Two Rb and Rb ′ each independently represents a hydrogen atom, a halogen atom or an organic group.
L ₃ represents a single bond or a divalent linking group.
D represents the partial structure represented by the general formula (D).
r represents 0 or 1;
In formula (D2),
Rc ₁ to Rc ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or at least one alkyl group wherein a hydrogen atom is substituted with a fluorine atom. However, at least one of Rc _{1 to} Rc ₃ is not a hydrogen atom.
D represents the partial structure represented by the general formula (D).

In general formula (D3),
Rd _{1 to} Rd ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. However, at least one of Rd _{1 to} Rd ₃ is not a hydrogen atom.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
D represents the partial structure represented by the general formula (D).
In general formula (D4),
Re _{1 to} Re ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
L ₄ represents a single bond, —O— or —N (Ra) —. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
D represents the partial structure represented by the general formula (D).

(16) In any one of (13) to (15), AR in the repeating unit represented by formula (D) is an adamantane residue, norbornane residue or tetracyclododecane residue The positive resist composition as described.

(17) The positive resist composition as described in any one of (1) to (16), further comprising a solvent.

(18) The positive resist composition as described in (17) above, which contains propylene glycol monomethyl ether acetate as the solvent.

(19) The positive resist composition as described in (18), further containing propylene glycol monomethyl ether as the solvent.

(20) A pattern forming method comprising: forming a resist film from the resist composition according to any one of (1) to (19) above; and exposing and developing the resist film.

  The positive resist composition of the present invention is excellent in pattern profile, limit resolution and dry etching resistance.

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).

[1] Resin (A1)
In the present invention, the resin (A1) is a resin containing a repeating unit containing at least two groups represented by the following formula (Z).

In general formula (Z),
A plurality of R ⁵⁰ to R ⁵⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R ^{50 to} R ⁵⁵ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
A plurality of Y each independently represents a hydrogen atom or an organic group.

A plurality of R ⁵⁰ to R ⁵⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R ^{50 to} R ⁵⁵ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Several Y independently represents a hydrogen atom or an organic group.
k represents an integer of 2 ≦ k ≦ 5.

The alkyl group of R ^{50 to} R ⁵⁵ may have a substituent, and examples thereof include linear and branched alkyl groups. For example, the alkyl group has 1 to 8 carbon atoms, Preferred examples include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group and octyl group. Examples of the substituent which may be included include a halogen atom, a hydroxyl group, a cyano group, and a carboxyl group, and a fluorine atom is preferable.
k is preferably 2 or 3, particularly preferably 2.

  Y represents hydrogen or an organic group, and the organic group may be an acid-decomposable organic group (acid-decomposable group) or a non-acid-decomposable organic group.

The acid-decomposable group is not limited as long as it is decomposed by the action of an acid to form a hydrophilic group such as a hydroxyl group or a carboxyl group and the solubility in an alkali developer is increased, but -C (R _11a ) (R _{A group represented by 12a} ) ( _R13a ), -C ( _R14a ) ( _R15a ) ( _OR16a ), -CO-O ( _R11a ) ( _R12a ) ( _R13a ) is preferred.

R _{11a to} R _13a each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. R _14a and R _15a each independently represents a hydrogen atom or an alkyl group. R _16a represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. Two of R _11a , R _12a and R _13a , or two of R _14a , R _15a and R _16a may combine to form a ring. As the alkyl group for R _{11a to} R _13a , R _14a , R _15a and R _16a , an alkyl group having 1 to 8 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- A butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, etc. can be mentioned.

The cycloalkyl group for R _{11a to} R _13a and R _16a may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclo A dodecyl group, an androstanyl group, etc. can be mentioned. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
The aryl group of R _{11a to} R _13a and R _16a is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group. , Anthryl group, 9,10-dimethoxyanthryl group and the like.

The aralkyl group of R _{11a to} R _13a and R _16a is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkenyl group of R _{11a to} R _13a and R _16a is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The substituents that R _{11a to} R _13a , R _14a , R _15a , and R _16a may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, and a hydroxy group. Carboxy group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like.

  Preferable specific examples of the acid-decomposable group include t-butyl group, t-amyl group, 1-alkyl-1-cyclohexyl group, 2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- Tertiary alkyl groups such as (4-methylcyclohexyl) -2-propyl group, 1-alkoxy-1-ethoxy group, 1-alkoxy-1-methoxy group, acetal group such as tetrahydropyranyl group, t-alkylcarbonyl group And t-alkylcarbonylmethyl group and the like are preferable.

  A non-acid-decomposable organic group is an organic group that does not decompose by the action of an acid. For example, an alkyl group, aryl group, aralkyl group, alkoxy group, alkoxycarbonyl that does not decompose by the action of an acid Group, amide group, cyano group and the like. The alkyl group is preferably a linear, branched or cycloalkyl group having 1 to 10 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, 2- Examples thereof include an ethylhexyl group, an octyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. The aralkyl group is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a cumyl group. The alkoxy group in the alkoxy group and the alkoxycarbonyl group is preferably an alkoxy group having 1 to 5 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, and an isobutoxy group. The alkyl group, aryl group, aralkyl group, alkoxy group, and alkoxycarbonyl group of Za may have a substituent such as a hydroxyl group.

  The repeating unit containing a group represented by the general formula (Z) is preferably a repeating unit represented by the following general formula (A), (A ′) or (A ″).

In the general formulas (A), (A ′), (A ″),
Several R _{< a1} > -R _<a6> represents a hydrogen atom, a fluorine atom, or an alkyl group each independently. However, at least one of R _{a1 to} R _a6 is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R _a7 represents a halogen atom, a cyano group or an alkyl group.
R _a8 and R _a9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an acyl group, an alkyl group, an alkenyl group, an aralkyl group or an aryl group.
When there are a plurality of R _{a10 s} , they may be different and each independently represents a halogen atom, an alkyl group or an alkoxy group. R _a10 is preferably a halogen atom or a perfluoroalkyl group, more preferably a halogen atom. As the halogen atom, a fluorine atom is preferable.
R _a11 may be different when there are a plurality of R _a11 and each independently represents a halogen atom, an alkyl group or an alkoxy group. R _a11 is preferably a halogen atom or a perfluoroalkyl group, more preferably a halogen atom. As the halogen atom, a fluorine atom is preferable.
R _{a12 to} R _a14 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Y _{a1 to} Y _a3 each independently represents a hydrogen atom or an organic group.
p, m1, and m ′ each independently represents an integer of 2 to 5.
n ′ represents an integer of 0 to 7. n ′ is preferably an integer of 0 to 5, more preferably an integer of 0 to 3.
n represents 0 or 1.
m2 represents an integer of 0 to 7. m2 is preferably an integer of 0 to 5, more preferably an integer of 0 to 3.
A ₁ , A ₂ , and La ₁ each independently represent a single bond or a divalent linking group.

_{Examples of} each group represented by R _{a1 to} R _a17 and Y _a1 and Y _a2 include the same groups as those in the general formula (Z).

As the divalent linking group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group Represents a single group or a combination of two or more groups selected from the group consisting of Examples of the alkylene group in A include groups represented by the following formulas.
− [C (Rb) (Rc)] r −
In the formula, Rb and Rc each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and they may be the same or different. 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, and more preferably selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).
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. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.
A ₁ , A ₂ , and La ₁ are particularly preferably a single bond or a methylene group.

  The resin (A1) preferably contains a group obtained by protecting the group represented by the formula (B) or the carboxyl group with an acid-decomposable group. This group may be contained in the repeating unit containing the group represented by the general formula (Z), or may be contained in another repeating unit.

In general formula (B),
Zb represents an acid-decomposable group.
R _{31 to} R ₃₆ are each independently a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{31 to} R ₃₆ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.

Examples of the acid-decomposable group for Zb in formula (B) include the same examples as the acid-decomposable group for Y in formula (Z).
The alkyl group in general formula (B) may have a substituent. Examples of the alkyl group and the substituent that may be present include those similar to R ^{50 to} R ⁵⁵ in formula (Z).
In addition, the structure of general formula (B) may be contained in the structure of general formula (IV)-(VI) of resin (A2), for example. In that case, R ₅ in the general formulas (IV) and (V), Y ₁ in the general formula (VI), and the like become Zb in the general formula (B).

  The resin (A1) preferably contains a group represented by the formula (B ′). This group may be contained in the repeating unit containing the group represented by the general formula (Z), or may be contained in another repeating unit.

In general formula (B ′),
Zc represents a hydrogen atom or a non-acid-decomposable group.
R _{31 to} R ₃₆ are each independently a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{31 to} R ₃₆ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
At least one of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.

Examples of the non-acid-decomposable group for Zc in formula (B ′) include the same examples as the non-acid-decomposable group for Y in formula (Z).
The alkyl group in the general formula (B ′) may have a substituent. Examples of the alkyl group and the substituent that may be present include those similar to R ^{50 to} R ⁵⁵ in formula (Z).

  Although the specific example of the repeating unit containing group represented by general formula (Z) below is shown, this invention is not limited to this.

  Resin (A1) may contain another repeating unit in addition to the repeating unit containing the group represented by formula (Z). As another repeating unit, it is preferable that the repeating unit represented by the following general formula (VI)-(XII), (D), (E), (F) is included. Among these, it is particularly preferable that the repeating unit described in the general formulas (VI) to (VIII) is included.

In general formulas (IV) to (V),
R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or an acid-decomposable group.
R ₆ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or an acid-decomposable group.
R _7a may be different when there are a plurality of R _{7a s} and represents a halogen atom, an alkyl group or an alkoxy group. R _7a is preferably a halogen atom or a perfluoroalkyl group, more preferably a halogen atom. The halogen atom is preferably a fluorine atom.
n represents 0 or 1.
n ′ represents an integer of 0 to 7. n ′ is preferably an integer of 0 to 5, more preferably an integer of 0 to 3.
A ₁ is a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₂₂ —, —CO—O—R ₂₃ —, —CO—N (R ₂₄ ). -R ₂₅ - represents a.
R ₂₂ , R ₂₃ and R _{25 each} have a single bond or an ether group, ester group, amide group, urethane group or ureido group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group. Represents.
R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.
In the formula (V), the group represented by R _7a may be located at any position of the carbocyclic structure.

In general formula (VI),
Rx ₁ to Rx ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or at least one alkyl group wherein a hydrogen atom is substituted with a fluorine atom.
R _{61 to} R ₆₆ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{61 to} R ₆₆ is a fluorine atom.
R _{67 to} R ₇₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{67 to} R ₇₂ is a fluorine atom.
Z ₁ represents a phenylene group, a cyclohexylene group, an adamantane residue or a norbornane residue.
L ₁ represents a single bond or a divalent linking group.
q is 0 or 1.
Y ₁ represents a hydrogen atom or an organic group.

In the case where the phenylene group, cyclohexylene group, adamantane residue or norbornane residue of Z ₁ in the general formula (VI) has a substituent, preferred substituents are a halogen atom, a hydroxyl group, an alkoxy group and a cyano group. More preferred are a fluorine atom and a hydroxyl group, and even more preferred is a fluorine atom. If Z ₁ is a fluorine atom as the value ventilation, the number of fluorine atoms is 1 to 5, and more preferably from 1 to 3.

In general formula (VII),
R ₄₁ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
R ^{50 to} R ⁵⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R ^{50 to} R ⁵⁵ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Y ₂ represents a hydrogen atom or an organic group.
In general formula (VIII),
Ry _{1 to} Ry ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Y ₃ represents a hydrogen atom or an organic group.

In general formulas (IX) to (X),
R ₁₅ is hydrogen atom, hydroxyalkyl group, alkyl group having fluorine atom, cycloalkyl group having fluorine atom, alkenyl group having fluorine atom, aralkyl group having fluorine atom, aryl group having fluorine atom, or acid-decomposable Represents a group.
Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with a carbon atom.
R ₁₆ , R ₁₇ and R ₁₈ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group or —CO—O—R ₁₅ .
R ₁₉ , R ₂₀ and R ₂₁ may be the same or different and have a hydrogen atom, a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, an alkenyl group having a fluorine atom, or a fluorine atom. An aralkyl group, an aryl group having a fluorine atom, an alkoxy group having a fluorine atom, or a hydroxyalkyl group is represented. However, at least one of R ₁₉ , R ₂₀ and R ₂₁ is a group other than a hydrogen atom.
n represents 0 or 1, and x, y, z represents an integer of 0 to 4.

In general formula (XI),
Ra _{1 to} Ra ₃ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an aryl group, an alkoxy group or an aralkyl group.
Y ₄ represents a hydrogen atom or an organic group.
m represents 1 or 2.
In general formula (XII),
Ra _{4 to} Ra ₆ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an aryl group, an alkoxy group or an aralkyl group. Ra _{4 to} Ra ₆ are preferably a hydrogen atom or a halogen atom, and the halogen atom is preferably a fluorine atom. In particular, Ra ₄ is preferably a fluorine atom.
Y ₅ represents a hydrogen atom or an organic group.
L ₂ represents a single bond or a divalent linking group.
m represents 1 or 2.

In general formula (D),
AR represents a monocyclic or polycyclic alicyclic hydrocarbon group.
L ₃ represents a single bond or a divalent linking group.
When there are a plurality of Xd, each independently represents a hydroxyl group, a cyano group, an alkoxy group or an alkyl group. However, at least one of X is any one of a hydroxyl group, a cyano group, and an alkoxy group.
p represents an integer of 1 to 4.

In general formula (E),
R ₄₂ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group.
However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Y ₆ represents a hydrogen atom or an organic group.
When there are a plurality of Y _{6 and} R _{50 to} R ₅₅ , they may be the same or different.
t represents an integer of 1 to 5.

In general formula (F),
R _{1 to} R ₃ each independently represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
R _{21 to} R ₂₆ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{21 to} R ₂₆ is a fluorine atom.
R ₂₇ to R ₃₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{27 to} R ₃₂ is a fluorine atom.
L _f1 and L _f2 each independently represent a single bond or a divalent linking group.
Y ₇ represents a hydrogen atom or an organic group.
n represents 0 or 1.

In general formulas (IV) to (XII), (D), (E), (F),
Examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, and specifically include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and a hexyl group. , 2-ethylhexyl group, octyl group and haloalkyl group can be preferably exemplified. As the haloalkyl group, for example, a haloalkyl group having 1 to 4 carbon atoms, specifically, a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, a bromoethyl group, a perfluoroalkyl group and the like are preferable. Can be mentioned. Examples of the perfluoroalkyl group include those having 4 to 12 carbon atoms, specifically, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorooctylethyl group, a perfluorododecyl group, and the like. Can be preferably given.

  The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferred examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The polycyclic type has 6 to 20 carbon atoms, such as an adamantyl group, norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, a-pinel group, tricyclodecanyl group, tetocyclododecyl group, An androstanyl group etc. can be mentioned preferably. However, the carbon atom in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

As the aryl group, for example, an aryl group having 6 to 15 carbon atoms, specifically, phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, Preferable examples include 9,10-dimethoxyanthryl group.
As the aralkyl group, for example, an aralkyl group having 7 to 12 carbon atoms, specifically, a benzyl group, a phenethyl group, a naphthylmethyl group, and the like can be preferably exemplified.
As an alkenyl group, it is a C2-C8 alkenyl group, for example, Specifically, a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group can be mentioned preferably.

Examples of the alkoxy group include an alkoxy group having 1 to 8 carbon atoms, and specifically include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group, and an octoxy group. Preferred examples include groups.
As the acyl group, for example, an acyl group having 1 to 10 carbon atoms, specifically, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, an octanoyl group, a benzoyl group and the like can be preferably exemplified. it can.
The alkynyl group is preferably an alkynyl group having 2 to 5 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a butynyl group.
Examples of the alkoxycarbonyl group include i-propoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, 1-methyl-1-cyclohexyloxycarbonyl group and the like, preferably secondary, more preferably tertiary alkoxycarbonyl. Groups.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkylene group preferably include those having 1 to 8 carbon atoms such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group, which may have a substituent.
The alkenylene group is preferably an alkenylene group having 2 to 6 carbon atoms such as an optionally substituted ethenylene group, propenylene group or butenylene group.
Preferred examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.
The arylene group is preferably an arylene group having 6 to 15 carbon atoms such as a phenylene group, a tolylene group and a naphthylene group which may have a substituent.
The divalent alicyclic group may be any polycyclic structure such as bicyclo, tricyclo, and tetracyclo. The carbon number is preferably 6-30, and more preferably 7-25. Preferred examples of the divalent alicyclic group include, for example, an adamantane residue (residue obtained by removing two hydrogen atoms from adamantane, the same shall apply hereinafter), a noradamantane residue, a decalin residue, a tricyclodecane residue, tetra A cyclododecane residue, a norbornane residue, etc. can be mentioned. More preferable examples of the divalent alicyclic group include an adamantane residue and a norbornane residue.

  The alicyclic group formed of the atomic group constituting the monocyclic or polycyclic alicyclic group is a monocyclic type having 3 to 8 carbon atoms, such as a cyclopropyl group or a cyclopentyl group. , A cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The polycyclic type has 6 to 20 carbon atoms, such as an adamantyl group, norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, a-pinel group, tricyclodecanyl group, tetocyclododecyl group, An androstanyl group etc. can be mentioned preferably.

  Examples of the acid-decomposable group include the same acid-decomposable groups as Y in formula (Z).

The above alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, alkoxy group, acyl group, alkynyl group, alkoxycarbonyl group, alkylene group, alkenylene group, cycloalkylene group, arylene group, etc. have a substituent. It may not be, and may have a substituent. An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, an acyl group, an alkynyl group, an alkoxycarbonyl group, an alkylene group, an alkenylene group, a cycloalkylene group, an arylene group, etc. Examples of the group include those having active hydrogen such as alkyl group, cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, and carboxyl group, and halogen atom (fluorine atom, chlorine atom). , Bromine atom, iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyl group) Oxy group, benzoyloxy group, etc.), alkoxy group Boniru group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group), a cyano group and a nitro group.
Here, examples of the alkyl group, cycloalkyl group, and aryl group include those described above. The alkyl group may be further substituted with a fluorine atom or a cycloalkyl group.

As the divalent linking group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group Represents a single group or a combination of two or more groups selected from the group consisting of Examples of the alkylene group in A include groups represented by the following formulas.
− [C (Rb) (Rc)] r −
In the formula, Rb and Rc each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and they may be the same or different. 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, and more preferably selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms). 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. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.
As the divalent linking group, a single bond or a methylene group is particularly preferable.

  Specific examples of the repeating structural units represented by the general formulas (IV) to (X) are shown below, but the present invention is not limited thereto.

  Preferred examples of the repeating unit represented by the general formula (V) are as follows.

  Preferred examples of the repeating unit represented by the general formula (VI) are as follows.

  Preferred examples of the repeating unit represented by formula (VIII) include the following.

  Preferred examples of the repeating unit represented by the general formula (IX) are as follows.

  Preferred examples of the repeating unit represented by the general formula (X) are as follows.

  Preferred examples of the repeating unit represented by formula (XI) include the following.

  Preferred examples of the repeating unit represented by formula (XII) include the following.

In formula (D), the alkyl group for Xd may be linear or branched.
The linear or branched alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, 2-ethylhexyl group, octyl group, more preferably alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), particularly preferably having 1 to 3 carbon atoms. An alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group) can be mentioned.

The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferred examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The polycyclic type has 6 to 20 carbon atoms, such as an adamantyl group, norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group, An androstanyl group etc. can be mentioned preferably. The cycloalkyl group includes a group in which a part of carbon atoms constituting the ring is substituted with a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom.
The alkoxy group for Xd may be linear, branched or cyclic, preferably an alkoxy group having 1 to 8 carbon atoms, and specifically includes a methoxy group, an ethoxy group, and n-propoxy. Group, iso-propoxy group, butoxy group, pentoxy group, allyloxy group, octoxy group, etc., more preferably, an alkoxy group having 1 to 4 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, etc.) ).
The alkyl group and alkoxy group of Xd may have further substituents such as a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 5 carbon atoms).

  Xd is preferably a hydroxyl group, an alkoxy group, or a cyano group from the viewpoint of developability and sensitivity. More preferred are a hydroxyl group and an alkoxy group, and particularly preferred is a hydroxyl group. At least one of Xd is preferably a hydroxyl group.

Examples of the divalent linking group for L ₃ include the same as L ₁ in the above formula (VI).

  The repeating unit having a partial structure represented by the formula (D) is preferably included in the repeating units represented by the following formulas (D1) to (D4).

In formula (D1),
Two Rb and Rb ′ each independently represents a hydrogen atom, a halogen atom or an organic group.
L ₃ represents a single bond or a divalent linking group.
D represents the partial structure represented by the general formula (D).
r represents 0 or 1;

In formula (D2),
Rc ₁ to Rc ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or at least one alkyl group wherein a hydrogen atom is substituted with a fluorine atom. However, at least one of Rc _{1 to} Rc ₃ is not a hydrogen atom.
D represents the partial structure represented by the general formula (D).

In general formula (D3),
Rd _{1 to} Rd ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. However, at least one of Rd _{1 to} Rd ₃ is not a hydrogen atom.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
D represents the partial structure represented by the general formula (D).

In general formula (D4),
Re _{1 to} Re ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
L ₄ represents a single bond, —O— or —N (Ra) —. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
D represents the partial structure represented by the general formula (D).

In formula (E),
The alkyl group of R ₄₂ and R _{50 to} R ₅₅ may have a substituent, may be linear or branched, and preferably has 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group). Group, isopropyl group, butyl group, etc.), more preferably an alkyl group having 1 to 3 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group). Examples of the substituent include a halogen atom such as a fluorine atom, a hydroxyl group, a carboxyl group, and a cyano group.

Y ₅ represents a hydrogen atom or an organic group. The organic group may be an acid-decomposable organic group (acid-decomposable group) or a non-acid-decomposable organic group. Examples of the acid-decomposable group and non-acid-decomposable group include the same groups as those represented by Y in formula (Z).

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

In the general formula (F), examples of the halogen atom represented by R _{1 to} R ₃ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group for R _{1 to} R ₃ , R _{21 to} R ₂₆ , and R _{27 to} R ₃₂ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, and propyl. Group, n-butyl group, sec-butyl group and the like.
The alkyl group of R < ₁ > -R < ₃ >, R < ₂₁ > -R < ₂₆ >, R < ₂₇ > -R < ₃₂ > may have further substituents, such as a halogen atom.

R _{21 to} R ₂₆ and R _{27 to} R ₃₂ are preferably fluorine atoms.

Examples of the divalent linking group of L ₁ and L ₂ include an alkylene group, a cycloalkylene group, an arylene group, and an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, The combination with a urea group etc. can be mentioned. The alkylene group is preferably an alkylene group having 1 to 8 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. The cycloalkylene group is preferably a cycloalkylene group having 5 to 15 carbon atoms, such as a cyclopentylene group, a cyclohexylene group, a norbornane residue, an adamantane residue, a tricyclodecane residue, a tetracyclododecane residue, etc. Can be mentioned. The arylene group is preferably an arylene group having 6 to 15 carbon atoms, and examples thereof include a phenylene group, a tolylene group, and a naphthylene group.

L ₁ is preferably a single bond or an alkylene group such as an ethylene group.
L ₂ is preferably a cyclohexylene group, a norbornane residue, or an adamantane residue, and more preferably a cyclohexylene group or an adamantane residue.

Y ₆ represents a hydrogen atom or an organic group. The organic group may be an acid-decomposable organic group (acid-decomposable group) or a non-acid-decomposable organic group. Examples of the acid-decomposable group and non-acid-decomposable group include the same groups as those represented by Y in formula (Z).

  Hereinafter, although the specific example of the repeating unit represented by general formula (F) is given, this invention is not limited to this.

The resin as the component (A1) may further be copolymerized with other copolymerization monomers.
Examples of the copolymerizable monomer that can be used include acrylic esters other than the above, acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and crotonic esters. The compound which has one addition polymerizable unsaturated bond chosen from these etc. can be mentioned.

In the resin of component (A1), the content of the repeating unit containing a group represented by formula (Z) is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol. %.
In the resin of component (A1), the content of the repeating units represented by general formulas (IV) to (XII) is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol. %.
In the resin of the component (A1), the content of the repeating unit represented by the general formulas (D), (E), and (F) is usually 1 to 80 mol%, preferably 3 to 65 mol%, more preferably 5 to 50 mol%.
In the resin of the component (A1), the content of the repeating unit containing a group represented by the general formula (B) is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol%. It is.
In the resin (A1), the content of the repeating unit containing a group represented by the general formula (B ′) is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol. %.

The preferred molecular weight of the resin (A1) is 1,000 to 200,000 in terms of mass average, and more preferably 3,000 to 200,000. Most preferably, it is 3,000 to 50,000. The molecular weight distribution (dispersion degree) is 1 to 10, preferably 1 to 3, more preferably 1 to 2.
Most preferably, it is 1-1.7. The smaller the molecular weight distribution, the better the coatability, sensitivity, and contrast. In the present invention, the proportion of the resin having a molecular weight of 1000 or less is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. Further, the ratio of the residual monomer in the resin (A1) is preferably 10% or less, more preferably 7% or less, and still more preferably 5% or less.

The resin (A1) used in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, monomer species are charged into a reaction vessel in a batch or in the course of reaction, and if necessary, a reaction solvent such as ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, methyl ethyl ketone, Dissolve in a solvent that can dissolve various monomers, such as ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, and propylene glycol monomethyl ether acetate described later, and then use nitrogen, argon, etc. Polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.) as necessary under an active gas atmosphere. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more. The reaction temperature is 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 50-100 ° C. Some monomers can be synthesized more suitably when anionic polymerization is used. The polymerization method is described in “Chemical Chemistry Course 28, Polymer Synthesis” (Maruzen) edited by the Chemical Society of Japan and “New Experimental Chemistry Course 19, Polymer Chemistry” (Maruzen) edited by the Chemical Society of Japan.
In addition, when the reactivity of a polymerization reaction is low, or when a monomer is gas at normal temperature and normal pressure, it may be able to synthesize | combine more suitably by sealing a reaction container and performing on pressurization conditions. Some monomers can be synthesized more suitably when polymerized using a transition metal catalyst such as palladium.

It is preferable that a small amount of metal components such as Na, K, Ca, Fe, and Mg contained in the resin (A1). Specifically, the metal species content contained in the resin is preferably 300 ppb or less, more preferably 200 ppb or less, and still more preferably 100 ppb or less.
In the resin (A1), the content of the repeating unit having an acid-decomposable group is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol%.

  Hereinafter, although the specific example of resin (A1) of this invention is shown, this invention is not limited to this.

[2] Resin (A2)
The resin (A2) in the present invention is a resin having a structure in which a fluorine atom is substituted in the main chain of the polymer, and is at least one selected from the group of repeating units represented by the following general formulas (I) to (III) including.

In general formulas (I) to (III),
R ₀ and R ₁ may be the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl group or an aryl group.
R _{2 to} R ₄ may be the same or different and each represents an alkyl group, a cycloalkyl group, or an aryl group.
R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ may combine to form a ring.

  In the general formulas (I) to (III), the alkyl group is, for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, sec Preferred examples include -butyl group, t-butyl group, hexyl group, 2-ethylhexyl group, octyl group and perfluoroalkyl group. Examples of the perfluoroalkyl group include those having 4 to 12 carbon atoms, specifically, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorooctylethyl group, a perfluorododecyl group, and the like. Can be preferably given.

  The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferred examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The polycyclic type has 6 to 20 carbon atoms, such as an adamantyl group, norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, a-pinel group, tricyclodecanyl group, tetocyclododecyl group, An androstanyl group etc. can be mentioned preferably. However, the carbon atom in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

  As the aryl group, for example, an aryl group having 6 to 15 carbon atoms, specifically, phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, Preferable examples include 9,10-dimethoxyanthryl group.

The ring formed by combining R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ is, for example, a 5- to 7-membered ring, specifically, a pentane ring substituted with fluorine, a hexane ring, Examples include a furan ring, a dioxonol ring, and a 1,3-dioxolane ring.
The ring formed by combining two of R _{36 to} R ₃₈ or two of R _{36 to} R ₃₇ and R ₃₉ is, for example, a 3- to 8-membered ring, specifically a cyclopropane ring. , Cyclopentane ring, cyclohexane ring, furan ring, pyran ring and the like.

The alkyl group, cycloalkyl group, aryl group and the like may not have a substituent or may have a substituent. Examples of the substituent which may be present include those having active hydrogen such as alkyl group, cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group and carboxyl group, halogen Atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy Groups (acetoxy group, propanoyloxy group, benzoyloxy group, etc.), alkoxycarbonyl groups (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), cyano group, nitro group and the like.
Here, examples of the alkyl group, cycloalkyl group, and aryl group include those described above. The alkyl group may be further substituted with a fluorine atom or a cycloalkyl group.

  The resin (A2) preferably contains a group obtained by protecting the group represented by the formula (B) or the carboxyl group with an acid-decomposable group. This group may be contained in the repeating units represented by the general formulas (I) to (III) or may be contained in other repeating units.

In general formula (B),
Zb represents an acid-decomposable group.
R _{31 to} R ₃₆ are each independently a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{31 to} R ₃₆ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
At least one of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.

Examples of the acid-decomposable group for Zb in formula (B) include the same examples as the acid-decomposable group for Y in formula (Z).
The alkyl group in general formula (B) may have a substituent. Examples of the alkyl group and the substituent which may be included are the same as those of R ₄₁ and R ^{50 to} R ⁵⁵ in formula (Z).

  The resin (A2) preferably contains a group represented by the formula (B ′). This group may be contained in the repeating unit containing the group represented by the general formula (Z), or may be contained in another repeating unit.

In general formula (B ′),
Zc represents a hydrogen atom or a non-acid-decomposable group. R _{31 to} R ₃₆ are each independently a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{31 to} R ₃₆ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
At least one of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.

Examples of the non-acid-decomposable group for Zc in formula (B ′) include the same examples as the non-acid-decomposable group for Y in formula (Z).
The alkyl group in the general formula (B ′) may have a substituent. Examples of the alkyl group and the substituent that may be present include those similar to R ^{50 to} R ⁵⁵ in formula (Z).

  Although the specific example of the repeating unit represented by general formula (I)-(III) below is shown, this invention is not limited to this.

The resin (A2) may contain other repeating units in addition to the repeating units represented by the general formulas (I) to (III). In particular, the resin (A1) preferably contains a repeating unit represented by the general formulas (VI) to (XII), (D), (E), and (F). Among these, it is particularly preferable that the repeating unit described in the general formulas (V) and (IX) to (XII) is included.
Examples of the repeating units represented by the general formulas (VI) to (XII), (D), (E), and (F) are the same as those in the resin (A1).

The resin as component (A2) may further be copolymerized with other copolymerization monomers.
Examples of the copolymerizable monomer that can be used include acrylic esters other than the above, acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and crotonic esters. The compound which has one addition polymerizable unsaturated bond chosen from these etc. can be mentioned.

In the resin as the component (A2), the content of the repeating unit represented by the general formulas (I) to (III) is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol. %.
In the resin of component (A2), the content of the repeating units represented by general formulas (IV) to (XII) is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol. %.
In the resin of the component (A2), the content of the repeating unit represented by the general formulas (D), (E), and (F) is usually 1 to 80 mol%, preferably 3 to 65 mol%, more preferably 5 to 50 mol%.
In the resin of the component (A2), the content of the repeating unit containing a group represented by the general formula (B) is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol%. It is.
In the resin of component (A2), the content of the repeating unit containing a group represented by the general formula (B ′) is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol. %.

The preferred molecular weight of the resin (A2) is 1,000 to 200,000 on a mass average, and more preferably 3,000 to 200,000. Most preferably, it is 3,000 to 50,000. The molecular weight distribution (dispersion degree) is 1 to 10, preferably 1 to 3, more preferably 1 to 2.
Most preferably, it is 1-1.7. The smaller the molecular weight distribution, the better the coatability, sensitivity, and contrast. In the present invention, the proportion of the resin having a molecular weight of 1000 or less is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. Further, the ratio of the residual monomer in the resin (A2) is preferably 10% or less, more preferably 7% or less, and still more preferably 5% or less.

Resin (A2) used for this invention is compoundable according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, monomer species are charged into a reaction vessel in a batch or in the course of reaction, and if necessary, a reaction solvent such as ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, methyl ethyl ketone, Dissolve in a solvent that can dissolve various monomers, such as ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, and propylene glycol monomethyl ether acetate described later, and then use nitrogen, argon, etc. Polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.) as necessary under an active gas atmosphere. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more. The reaction temperature is 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 50-100 ° C. Some monomers can be synthesized more suitably when anionic polymerization is used. The polymerization method is described in “Chemical Chemistry Course 28, Polymer Synthesis” (Maruzen) edited by the Chemical Society of Japan and “New Experimental Chemistry Course 19, Polymer Chemistry” (Maruzen) edited by the Chemical Society of Japan.
In addition, when the reactivity of a polymerization reaction is low, or when a monomer is gas at normal temperature and normal pressure, it may be able to synthesize | combine more suitably by sealing a reaction container and performing on pressurization conditions. Some monomers can be synthesized more suitably when polymerized using a transition metal catalyst such as palladium.

It is preferable that a small amount of metal components such as Na, K, Ca, Fe, and Mg contained in the resin (A2). Specifically, the metal species content contained in the resin is preferably 300 ppb or less, more preferably 200 ppb or less, and still more preferably 100 ppb or less.
Content of the repeating unit which has an acid-decomposable group in resin (A2) is 3-95 mol% normally, Preferably it is 5-80 mol%, More preferably, it is 7-70 mol%.

  Hereinafter, although the specific example of resin (A2) of this invention is shown, this invention is not limited to this.

  In the present invention, at least one of the resin (A1) and the resin (A2) is a resin whose solubility in an alkaline developer is increased by the action of an acid.

The total addition amount of the resin (A1) and the resin (A2) is generally 50 to 99.5% by mass, preferably 60 to 98% by mass, more preferably 65 to 95% by mass, based on the total solid content of the composition. Used in the range of%.
The addition ratio of the resin (A1) and the resin (A2) is mass ratio and is usually (A1) :( A2) = 3: 97 to 97: 3, preferably (A1) :( A2) = 5: 95. To 95: 5, more preferably (A1) :( A2) = 7: 93 to 93: 7.

[2] (B) Compound that generates acid by the action of actinic rays or radiation The positive resist composition of the present invention is a compound that generates acid upon irradiation with actinic rays or radiation, particularly F ₂ excimer laser light (B ). The compound (B) that generates an acid contains a compound (B1 component) that generates an organic sulfonic acid, and in particular, the component (B1) contains at least one fluorine atom by the action of actinic rays or radiation. It is preferable that each compound contains at least one compound that generates an organic sulfonic acid that does not contain a fluorine atom by the action of actinic rays or radiation.

  Furthermore, it is also preferable to contain a compound that generates a carboxylic acid by the action of component (B2) actinic rays or radiation. By combining the component (B2) with the component (B1), the coating property and contrast can be improved.

The organic sulfonic acid and carboxylic acid in the above (B1) and (B2) may be either aliphatic or aromatic.
The sulfonic acid of the component (B1) preferably has 1 to 20 carbon atoms, more preferably 2 to 16 and still more preferably 3 to 12.

Compounds (B1 component) and (B2 component) that generate acid upon irradiation with actinic rays or radiation are generally used as compounds (photoacid generators) that decompose upon irradiation with actinic rays or radiation to generate acid. You can choose from what you have.
That is, known light (400 to 200 nm ultraviolet light, far-off light used for photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photodecolorants of dyes, photochromic agents, or micro-resists. A compound capable of generating an acid by ultraviolet rays, particularly preferably g-line, h-line, i-line, KrF excimer laser beam), ArF excimer laser beam, F ₂ excimer laser beam, electron beam, X-ray, molecular beam or ion beam; Those mixtures can be appropriately selected and used.

  Examples of such compounds include diazonium salts described in, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), TSBaletal, Polymer, 21, 423 (1980), U.S. Pat.No. 4,069,055, 4,069,056, Re27,992, ammonium salts described in JP-A-3-140140, DCNecker et al, Macromolecules, 17, 2468 (1984), CS Wen et al, Teh, Proc. Conf. Rad. CuringASIA, p478Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056, etc., phosphonium salts, JVCrivelloetal, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng. (1988), European Patent Nos. 104,143, 339,049, 410,201, JP-A-2-150848, JP-A-2-96514 and the like, JVCrivelloetal, Polymer J. 17, 73 (1985) ), JV Crivello etal., J. Org. Chem., 43, 3055 (1978), WR Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JV Crivello etal, Polymer Bull ., 14, 279 (1985), JV Crivelloetal, Macromorecules, 14 (5), 1141 (1981), JV Crivello et al, J. PolymerSci., Polymer Chem. Ed., 17, 2877 (1979), European Patent Nos. 370,693, 161,811, 410,201, 339,049, 233,567, 297,443 No. 297,442, U.S. Pat.Nos. Selenonium salts described in Crivelloetal, Macromorecules, 10 (6), 1307 (1977), JV Crivello et al, J. PolymerSci., Polymer Chem. Ed., 17, 1047 (1979), etc., CS Wen et al, Teh, Proc .Conf.Rad. CuringASIA, p478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B 46-4605, JP-A 48-36281, JP-A 55 -32070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63-70243 Organic halogen compounds described in JP-A-63-298339 K. Meieretal, J. Rad. Curing, 13 (4), 26 (1986), TP Gill et al, Inorg. Chem., 19, 3007 (1980), D. Astruc, Acc. Chem. Res., 19 ( 12), 377 (1896), and organic metal / organic halides described in JP-A-2-16145, S. Hayasetal, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al, J. Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhuetal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit et al, Tetrahedron Lett., (24) 2205 (1973), DHR Bartonetal, J. Chem Soc., 3571 (1965), PM Collins et al, J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedron Lett., (17), 1445 (1975) ), JWWalkeret al, J. Am. Chem. Soc., 110,7170 (1988), SC Busmanetal, J. ImagingTechnol., 11 (4), 191 (1985), HM Houlihanet al, Macromolecules, 21, 2001 ( 1988), PMCollins et al, J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayaset al, Macromolecules, 18, 1799 (1985), E. Reichmanis etal, J. Electrochem. Soc. , SolidState Sci. Technol., 130 (6), FM Houlihan etal, Macromolcules, 21, 2001 (1988), European Patent 0290,750, 0-nitrobenzyl type protection described in 046,083, 156,535, 271,851, 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, JP-A-53-133022, etc. Photoacid generator having a group, M.TUNOOKAetal, PolymerPreprints Japan, 35 (8), G. Berner et al, J. Rad. Curing, 13 (4), WJMijset al, CoatingTechnol., 55 (697), 45 ( 1983), Akzo, H. Adachi etal, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 044,115, 618,564, 0101,122, U.S. Patent No. 4,371,605 No. 4,431,774, JP-A-64-18143, JP-A-2-245756, JP-A-3-140109, and the like, compounds that generate sulfonic acid by photolysis, such as the iminosulfonates, etc. Examples thereof include disulfone compounds described in JP-A-61-166544.

  Preferred combinations of the B1 component and the B2 component include the following combinations.

As the B1 component, a compound that generates an aliphatic or aromatic sulfonic acid substituted with at least one fluorine atom upon irradiation with actinic rays or radiation, and an aliphatic or aromatic sulfonic acid that does not contain a fluorine atom as an anion A compound that generates
A combination which is an ionic compound having an aliphatic or aromatic carboxylic acid which may have a fluorine atom as the B2 component.

[A] A compound that generates fluorine-containing sulfonic acid upon irradiation with actinic rays or radiation (and an ionic compound having fluorine-containing sulfonic acid as an anion) will be described.

  For example, an iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the general formula (PAG4) can be given.

In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group.
Z ⁻ represents a sulfonate anion having at least one fluorine atom.
Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

The aryl group as Ar ¹ , Ar ² , R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ is preferably an aryl group having 6 to 14 carbon atoms, and the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms. .
Preferred substituents are aryl groups having 1 to 8 carbon atoms, alkyl groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 9 carbon atoms, and alkylcarbonylamino groups having 2 to 9 carbon atoms. , A nitro group, a carboxyl group, a hydroxy group, a halogen atom and a phenylthio group, with respect to the alkyl group, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 5 to 14 carbon atoms, and an arylcarbonyl having 6 to 15 carbon atoms Groups, carboxyl groups and halogen atoms.

Preferred examples of the Z ⁻ sulfonate anion include an aliphatic hydrocarbon having 1 to 20 carbon atoms and an aromatic hydrocarbon having 5 to 20 carbon atoms having at least one fluorine atom. These may have a substituent. Examples of the substituent include an alkoxy group which may be substituted with fluorine having 1 to 10 carbon atoms and an alkoxycarbonyl which may be substituted with fluorine having 2 to 11 carbon atoms. Group, phenylamino group, phenylcarbonyl group, halogen atom and hydroxyl group. For aromatic hydrocarbons, there can be further mentioned alkyl groups having 1 to 15 carbon atoms.

  Although a specific example is given below, it is not limited to these.

[B] As a compound that generates a fluorine-free sulfonic acid upon irradiation with actinic rays or radiation and an ionic compound having a fluorine-free sulfonic acid as an anion, for example, in the general formulas (PAG3) and (PAG4), Z ^- it can be mentioned iodonium salts and sulfonium salts are sulfonate anion having no fluorine atom.

  Specific examples include the following compounds, but are not limited thereto.

  Moreover, the disulfone derivative represented by the following general formula (PAG5) or the imino sulfonate derivative represented by general formula (PAG6) can also be mentioned.

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.

  Specific examples include the following compounds, but are not limited thereto.

  Moreover, the diazo disulfone derivative represented by the following general formula (PAG7) can be mentioned.

  In the formula, R represents a linear, branched or cyclic alkyl group, or an optionally substituted aryl group.

  Specific examples include the following compounds, but are not limited thereto.

The compounds described in the above [a] and [b] can be synthesized by reacting an aromatic compound with periodate and exchanging the obtained iodonium salt with the corresponding sulfonic acid.
Alternatively, it can be synthesized by reacting an aryl Grignard reagent such as arylmagnesium bromide with a substituted or unsubstituted phenyl sulfoxide, and subjecting the resulting triarylsulfonium halide to salt exchange with the corresponding sulfonic acid. Also, a method in which a substituted or unsubstituted phenyl sulfoxide and a corresponding aromatic compound are condensed and salt exchanged using an acid catalyst such as methanesulfonic acid / phosphorus pentoxide or aluminum chloride, and a diaryl iodonium salt and a diaryl sulfide are mixed with copper acetate. It can be synthesized by a method such as condensation or salt exchange using a catalyst such as
Salt exchange can also be performed by once converting to a halide salt and then converting it to a sulfonate using a silver reagent such as silver oxide, or by using an ion exchange resin. The sulfonic acid or sulfonate used for salt exchange can be obtained by using a commercially available product or by hydrolysis of a commercially available sulfonic acid halide.

[C] A compound that generates a fluorine-containing carboxylic acid upon irradiation with actinic rays or radiation and an ionic compound having a fluorine-containing carboxylic acid as an anion will be described.

  Examples of the fluorine-substituted aliphatic carboxylic acid include acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, trimethylacetic acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, Examples include fluorine-substituted products of aliphatic carboxylic acids such as palmitic acid, stearic acid, undecanoic acid, dodecanoic acid, and tridecanoic acid. These may have a hydroxyl group, an alkoxy group, or a halogen atom as a substituent. In addition, the aliphatic chain preferably contains a linking group such as an oxygen atom, a sulfur atom, a carbonyl group, a carboxyl group, or a sulfonyl group.

Preferred fluorine-substituted aliphatic carboxylic acids include those represented by the following general formula.
_{L- (CH 2) p (CF} 2) q (CH 2) r -COOH

In the general formula, L represents a hydrogen atom or a fluorine atom. p and r each independently represents an integer of 0 to 15, and q represents an integer of 1 to 15. The hydrogen atom or fluorine atom of the alkyl chain in this general formula is an alkyl group (preferably having 1 to 5 carbon atoms) which may be substituted with a fluorine atom, or an alkoxy group (preferably carbon atom) which may be substituted with a fluorine atom. Formula 1-5) or may be substituted with a hydroxyl group.
The fluorine-substituted aliphatic carboxylic acid is preferably a fluorine-substituted product of a saturated aliphatic carboxylic acid having 2 to 20 carbon atoms, more preferably 4 to 20 carbon atoms. By setting the number of carbon atoms to 4 or more, the generated carboxylic acid-decomposable diffusibility is reduced, and the change in line width over time from exposure to post-heating can be further suppressed. Of these, a fluorine-substituted product of a linear or branched saturated aliphatic carboxylic acid having 4 to 18 carbon atoms is preferable.

  The fluorine-substituted aromatic carboxylic acid is a fluorine-substituted aromatic carboxylic acid having 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, and further preferably 7 to 11 carbon atoms. Is preferred. Specifically, benzoic acid, substituted benzoic acid, naphthoic acid, substituted naphthoic acid, anthracene carboxylic acid, substituted anthracene carboxylic acid (wherein the substituents are alkyl groups, alkoxy groups, hydroxyl groups, halogen atoms, aryl groups, acyls) A fluorine-substituted product of an aromatic carboxylic acid such as a group, an acyloxy group, a nitro group, an alkylthio group, and an arylthio group. Of these, fluorine-substituted products of benzoic acid and substituted benzoic acid are preferable.

  The aliphatic or aromatic carboxylic acid substituted with a fluorine atom is one in which one or more hydrogen atoms existing in the skeleton other than the carboxyl group are substituted with a fluorine atom, and particularly preferably a skeleton other than the carboxyl group. Is an aliphatic or aromatic carboxylic acid (perfluoro-saturated aliphatic carboxylic acid or perfluoroaromatic carboxylic acid) in which all hydrogen atoms present in are substituted with fluorine atoms. As a result, the sensitivity is further improved.

Preferably, an onium salt compound (sulfonium salt, iodonium salt, etc.) having an anion of an aliphatic or aromatic carboxylic acid substituted with a fluorine atom as described above as a counter anion, and an imidocarboxylate compound having a carboxylic acid ester group Or a nitrobenzyl ester compound etc. are mentioned.
More preferred are compounds represented by the following general formulas (I ′) to (III ′). As a result, sensitivity, resolution, and exposure margin are further improved. By irradiating this compound with actinic rays or radiation, a saturated aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom corresponding to X ⁻ in the following general formulas (I ′) to (III ′) is obtained. And functions as a photoacid generator.

(In the above formula, R ₁ To R ₃₇ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, hydroxy group, a halogen atom or -S-R ₃₈ group,. Here, R ₃₈ represents a linear, branched, cyclic alkyl group or aryl group. X ⁻ is an anion of an aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom. )
X ⁻ is preferably an anion of a perfluoroaliphatic carboxylic acid or a perfluoroaromatic carboxylic acid, and particularly preferably an anion of a fluorine-substituted alkylcarboxylic acid having 4 or more carbon atoms.

In the above general formulas (I ′) to (III ′), the linear and branched alkyl groups of R _{1 to} R ₃₈ may have a substituent, methyl group, ethyl group, propyl group, n-butyl. And those having 1 to 4 carbon atoms such as a group, sec-butyl group and t-butyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
Examples of the alkoxy group of R _{1 to} R ₃₇ include 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a t-butoxy group. Can be mentioned.
Examples of the halogen atom represented by R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
_Examples of the aryl group for R ₃₈ include those having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. The aryl group may have a substituent.
These substituents are preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, iodine atom), an aryl group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. , Cyano group, hydroxy group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The iodonium compound or sulfonium compound represented by the general formulas (I ′) to (III ′) used in the present invention is a saturated aliphatic or aromatic group substituted with at least one fluorine atom as its counter anion X ^−. Having an anion of carboxylic acid. These anions are anions (—COO ⁻ ) from which a hydrogen atom of the carboxylic acid (—COOH) has been removed.

Specific examples are shown below, but the present invention is not limited thereto.
Specific examples (I-1f) to (I-6f) of the photoacid generator represented by the general formula (I ′):

  Specific examples (II-1f) to (II-13f) of the photoacid generator represented by the general formula (II ′):

  Specific examples (III-1f) to (III-3f) of the photoacid generator represented by the general formula (III ′):

  Specific examples (IV-1f) to (V to 4f) of other photoacid generators:

The compound represented by the above general formula (I ′) can be synthesized by reacting an aromatic compound using periodate and exchanging the obtained iodonium salt with the corresponding carboxylic acid.
The compound represented by general formula (II ′) or general formula (III ′) is obtained by reacting an aryl Grignard reagent such as arylmagnesium bromide with a substituted or unsubstituted phenyl sulfoxide, and reacting the resulting triarylsulfonium halide with the compound. It can be synthesized by a method of salt exchange with the corresponding carboxylic acid. Also, a method in which a substituted or unsubstituted phenyl sulfoxide and a corresponding aromatic compound are condensed and salt exchanged using an acid catalyst such as methanesulfonic acid / phosphorus pentoxide or aluminum chloride, and a diaryl iodonium salt and a diaryl sulfide are mixed with copper acetate. It can be synthesized by a method such as condensation or salt exchange using a catalyst such as
The salt exchange can also be performed by once converting to a halide salt and then converting to a carboxylate using a silver reagent such as silver oxide, or by using an ion exchange resin. The carboxylic acid or carboxylate used for salt exchange can be obtained by using a commercially available product or by hydrolysis of a commercially available carboxylic acid halide.

  Fluoro-substituted carboxylic acids as anionic moieties may be those derived from fluoroaliphatic compounds produced by the telomerization method (also called telomer method) or the oligomerization method (also called oligomer method). preferable. With respect to the production method of these fluoroaliphatic compounds, for example, “Synthesis and Function of Fluorine Compounds” (Supervision: Nobuo Ishikawa, published by CMC Co., 1987), “Chemistry of Organic Fluorine Compounds II” (Monograph 187 Ed by Milos Hudlicky and Attila E. Pavlath, American Chemical Society 1995), pages 747-752. The telomerization method is a method of synthesizing a telomer by radical polymerization of a fluorine-containing vinyl compound such as tetrafluoroethylene using an alkyl halide having a large chain transfer constant such as iodide as a telogen (example in Scheme-1). showed that). In the synthesis by the telomer method, a mixture of a plurality of compounds having different carbon chain lengths is obtained, but this may be used as a mixture or may be used after purification.

[D] Specific examples of the compound that generates a fluorine-free carboxylic acid upon irradiation with actinic rays or radiation and the ionic compound having a fluorine-free carboxylic acid as an anion are given, but the invention is not limited thereto.

  Examples thereof include compounds represented by the following general formulas (AI) to (AV).

In the above formula, R _{301 to} R ₃₃₇ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxy group, a halogen atom, or a —S—R ₀ group. . R ₀ represents a linear, branched, cyclic alkyl group or an aryl group.
Ra and Rb in the above formula (AV) each independently represent a hydrogen atom, a nitro group, a halogen atom, or an alkyl group or an alkoxy group which may have a substituent. In the above formula (AIV), Rc and Rd each independently represents a halogen atom or an alkyl group or an aryl group which may have a substituent. Rc and Rd may combine to form an aromatic ring, monocyclic or polycyclic hydrocarbon (which may contain an oxygen atom or a nitrogen atom). Y ₁ and Y _{2 each} represent a carbon atom, and the Y ₁ -Y ₂ bond may be a single bond or a double bond. X ⁻ represents an anion of a carboxylic acid compound represented by the following formula. X ₁ and X ₂ each independently represent a carboxylic acid compound represented by the following formula, which has become an ester group at the carboxyl group portion.

In the above formula, R ₃₃₈ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (wherein the chain of the alkyl group may contain an oxygen atom or a nitrogen atom), carbon number 1 to 20 linear, branched or cyclic alkenyl groups, 1 to 20 carbon straight, branched or cyclic alkynyl groups, 1 to 20 linear, branched or cyclic alkoxyl A group wherein at least part of the hydrogen atoms of the alkyl group are substituted with halogen atoms and / or hydroxyl groups, a group wherein at least part of the hydrogen atoms of the alkenyl group are substituted with halogen atoms and / or hydroxyl groups, or carbon The substituted or unsubstituted aryl group of Formula 6-20 is shown. Here, examples of the substituent of the aryl group include an alkyl group, a nitro group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, and a halogen atom.

R ₃₃₉ is a single bond or a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms (wherein the chain of the alkylene group may contain an oxygen atom or a nitrogen atom), carbon number 1-20 linear, branched or cyclic alkenylene groups, groups in which at least some of the hydrogen atoms of the alkylene group are substituted with halogen atoms and / or hydroxyl groups, and at least some of the hydrogen atoms of the alkenylene group A group substituted with a halogen atom or an alkoxyalkylene group having 2 to 20 carbon atoms, and a plurality of R ₃₃₈ and R ₃₃₉ may be the same or different from each other.

R ₃₄₀ represents a hydroxyl group or a halogen atom, and a plurality of R ₃₄₀ may be the same or different from each other. m, n, p and q are each independently an integer of 0 to 3, and m + n ≦ 5 and p + q ≦ 5. z is 0 or 1.

As the linear or branched alkyl group in R _{301 to} R ₃₃₇ , Ra, Rb, Rc, Rd, R ₀ in the general formulas (AI) to (AV), a methyl group which may have a substituent, Examples thereof include those having 1 to 4 carbon atoms such as ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
Examples of the alkoxy group of R _{301 to} R ₃₃₇ , Ra and Rb include carbon numbers such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. 1-4 may be mentioned.
Examples of the halogen atom for R _{301 to} R ₃₃₇ , Ra, Rb, Rc, and Rd include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the aryl group for R ₀ , Rc, and Rd include those having 6 to 14 carbon atoms that may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group.
These substituents are preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, iodine atom), an aryl group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. , Cyano group, hydroxy group, carboxy group, alkoxycarbonyl group, nitro group and the like.

  Aromatic, monocyclic or polycyclic hydrocarbons formed by combining Rc and Rd (which may contain oxygen and nitrogen atoms) include benzene and naphthalene structures. , Cyclohexane structure, norbornene structure, oxabicyclo structure and the like.

The sulfonium and iodonium compounds represented by the general formulas (AI) to (AIII) that can be used in the present invention include at least the carboxylic acid compounds represented by the above formulas (C1) to (C10) as the counter anion X ^−. It includes those in which the carboxyl group (—COOH) of one compound is an anion (—COO ⁻ ).
The compounds represented by the general formulas (AIV) to (AV) used in the present invention are at least one of the carboxylic acid compounds represented by the above formulas (C1) to (C10) as substituents X ₁ and X _2. It includes a substituent in which the carboxyl group (—COOH) of the seed compound is an ester group (—COO—).

As R ₃₃₈ , a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (wherein the alkyl group chain may contain an oxygen atom or a nitrogen atom) includes methyl, ethyl, Examples include propyl, butyl, pentyl, hexyl, cyclohexyl, dodecyl, 1-ethoxyethyl, adamantyl and the like.
Examples of the linear, branched or cyclic alkenyl group having 1 to 20 carbon atoms include ethenyl, propenyl, isopropenyl, cyclohexene and the like.
Examples of the linear, branched or cyclic alkynyl group having 1 to 20 carbon atoms include acetylene and propenylene.
Examples of the linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, propyloxy, butoxy, cyclohexyloxy, isobutoxy, dodecyloxy and the like.
Examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, anthranyl and the like.
Examples of the substituent for the aryl group include an alkyl group, a nitro group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, and a halogen atom.

As R ₃₃₉ , a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms (wherein the chain of the alkylene group may contain an oxygen atom or a nitrogen atom), methylene, ethylene , Propylene, butylene, isobutylene, ethoxyethylene, cyclohexylene and the like.
Examples of the linear, branched or cyclic alkenylene group having 1 to 20 carbon atoms include vinylene and arylene.

  Although a specific example is shown, this invention is not limited to these.

  The photoacid generator, that is, the compound represented by the general formula (AI), the general formula (AII), or the general formula (AIII) is prepared by the method described in US Pat. No. 3,734,928, Macromolecules, vol. .10, 1307 (1977), Journal of Organic Chemistry, vol. 55, 4222 (1990), J. Radiat.Curing, vol. 5 (1), 2 (1978) It can be synthesized by exchanging. The compounds represented by formulas (AIV) and (AV) are prepared by reacting an N-hydroxyimide compound and carboxylic acid chloride under basic conditions, or reacting nitrobenzyl alcohol and carboxylic acid chloride under basic conditions. Can be obtained.

The mass ratio of the added amount of the B1 component and the B2 component is usually 1/1 to 50/1, preferably 1/1 to 10/1, particularly preferably 2/1 to 5/1.
The total amount of the B1 component and the B2 component is usually in the range of 0.5 to 20% by mass, preferably 0.75 to 15% by mass, and more preferably 1 to 10% by mass with respect to the total solid content of the composition.
A plurality of B1 components and B2 components may be contained.

[3] Solvent (component C)
The composition of the present invention is preferably dissolved in a solvent that dissolves each of the above components and coated on a support. Examples of the solvent used here include 1-methoxy-2-propanol acetate (propylene glycol monomethyl ether acetate), 1-methoxy-2-propanol (propylene glycol monomethyl ether), ethylene dichloride, cyclohexanone, cyclopentanone, and 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 monoethyl ether, propylene glycol monomethyl ether acetate, toluene, Ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, 1-methoxy-2-propanol acetate, 1-methoxy- 2-propanol is particularly preferred. These solvents are used alone or in combination. When mixed and used, those containing 1-methoxy-2-propanol acetate or those containing 1-methoxy-2-propanol are preferred.

[4] Surfactant (component D)
The positive resist composition of the present invention further comprises (D) a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant, a surfactant containing both fluorine atoms and silicon atoms) It is preferable to contain any one of 2) or 2 types or more.
When the positive resist composition of the present invention contains the surfactant (D), when using an exposure light source of 250 nm or less, particularly 220 nm or less, good sensitivity and resolution, and less adhesion and development defects. A resist pattern can be provided.
As these (D) surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-62-170950 are disclosed. No. 63-34540, 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. 5,436,098, 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, the 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 Copolymer) of (ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or copolymerizing copolymers of methacrylate), acrylate having a C ₈ F ₁₇ group (with or methacrylate) (poly (oxyethylene) (or methacrylate) and (poly (oxypropylene)) acrylate and) acrylate (or methacrylate) Body, and the like.

  (D) 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).

[5] Acid diffusion inhibitor (E)
In the composition of the present invention, performance fluctuations due to aging after irradiation with actinic rays or radiation and heat treatment (pattern T-top shape formation, sensitivity fluctuations, pattern line width fluctuations, etc.) and performance fluctuations with time after application Furthermore, it is preferable to add an acid diffusion inhibitor for the purpose of preventing excessive diffusion (degradation of resolution) of the acid during the heat treatment after irradiation with actinic rays or radiation. The acid diffusion inhibitor is an organic basic compound, for example, an organic basic compound containing basic nitrogen, and a compound having a pKa value of the conjugate acid of 4 or more is preferably used.
Specifically, the structures of the following formulas (A) to (E) can be exemplified.

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, Here, R ²⁵¹ and R ²⁵² may combine with 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.

  Preferred examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, imidazole, substituted or unsubstituted Substituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted Aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. Preferred substituents are 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 It is.

  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, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl)- Examples include 5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine. However, the present invention is not limited to this.
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. The molar ratio is preferably from the standpoint of thickening the resist pattern over time from resolution to post-exposure heat treatment. (Acid generator) / (organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

[6] Non-polymer type dissolution inhibitor (X)
The positive resist composition of the present invention particularly preferably further contains a non-polymer type dissolution inhibitor. Here, the non-polymer type dissolution inhibitor is a compound in which at least two or more acid-decomposable groups are present in a compound having a molecular weight of 3000 or less, and the solubility in an alkali developer is increased by the action of an acid. is there. In particular, it is preferable from the viewpoint of transparency that a fluorine atom is substituted in the mother nucleus.
3-50 mass% is preferable with respect to the polymer in a composition, More preferably, 5-40 mass%, More preferably, it is 7-30 mass% with respect to the polymer in a composition. By adding the component (X), sensitivity and contrast are further improved.

  Specific examples of the component (X) are shown below, but the present invention is not limited to these specific examples.

  In the manufacture of precision integrated circuit elements, the pattern formation process on the resist film is performed on the substrate (eg, transparent substrate such as silicon / silicon dioxide cover, glass substrate, ITO substrate, etc.). A good resist pattern can be formed by applying an object, then irradiating with an actinic ray or radiation drawing apparatus, heating, developing, rinsing and drying.

Examples of the developer for the positive resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, n-propylamine and the like. Monoamines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethyl Aqueous solutions of alkalis such as quaternary ammonium salts such as ammonium hydroxide and choline, cyclic amines such as pyrrole and piperidine, and the like 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.

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

Synthesis example (1) Synthesis of resin (A1-1)

43.62 g of monomer (A) and 22.47 g of the protected methoxymethyl monomer (A) were dissolved in 100 g of tetrahydrofuran, and the reaction system was purged with nitrogen, and then polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries) 1 .42 g was added and heated at 65 ° C. for 8 hours while flowing nitrogen through the reaction system. Thereafter, the mixture was cooled to room temperature, and the reaction solution was dropped into 1.5 L of hexane. The powder was taken out by filtration and dried under reduced pressure at 100 ° C. to obtain 50.23 g of powder (yield 76%). The obtained powder had a weight average molecular weight of 11,400 and a dispersity of 1.53 as determined by gel permeation chromatography (GPC). Further, the composition ratio of the protected methoxymethyl monomer (A) / monomer (A) by ¹ H-NMR and ¹³ C-NMR analysis was 72/28.
Resins (A1-2) to (A1-10) were obtained in the same manner except that the monomer to be added was changed.

(2) Synthesis of Resin (A2-1) 9.42 g of norbornene, 19.23 g of t-butyl acrylate, 50 g of tetrahydrofuran and 4.96 g of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) were added to the autoclave. The inside was deaerated and purged with nitrogen, and then sealed. Tetrafluoroethylene was introduced into the reaction system and pressurized while the reactor was cooled with dry ice. Then, it heated up at 60 degree | times and made it react for 12 hours. The reactor was allowed to cool to room temperature to obtain a polymer solution with high viscosity. The polymer solution was dropped into methanol, and the powder was taken out and dried under reduced pressure to obtain 34.33 g of powder (yield 64%). The obtained powder had a weight average molecular weight of 8,900 and a dispersity of 1.51 as determined by gel permeation chromatography (GPC). The composition ratio of tetrafluoroethylene / norbornene / t-butyl acrylate by ¹ H-NMR and ¹⁹ F-NMR analysis was 53/20/27.
Resins (A2-2) to (A2-9) were obtained in the same manner except that the monomer to be added was changed.

Resist Solution Preparation 1.2 g of the polymer shown in Table 2 below, 0.030 g of acid generator, 100 ppm of surfactant with respect to the polymer solution, and polymer solution of 0.0012 g of organic basic compound dissolved in 19.6 g of solvent. Was filtered through a 0.1 μm Teflon filter to prepare a positive resist solution.

Exposure Evaluation The positive resist solution prepared as described above is uniformly applied on a silicon wafer coated with an antireflection film (manufactured by DUV42-6 BrewerScience. Inc.) using a spin coater, and is heated and dried at 120 ° C. for 60 seconds. Then, a positive resist film having a thickness of 0.1 μm was formed. The resist film was subjected to pattern exposure using a KrF microstepper using a line and space mask (line / space = 1: 1), and immediately after the exposure, it was heated on a hot plate at 130 ° C. for 90 seconds. Further, the resist film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed pure for 30 seconds, and then dried. The resist performance of the pattern on the silicon wafer thus obtained was evaluated by the following method.
(Pattern profile)
Observe the cross section of the line width 150nm (line / space = 1: 1) with SEM (S-8840, manufactured by Hitachi, Ltd.), and the line pattern is vertical, ○, T-top, round top or hem A case where slight pulling was observed was evaluated as Δ, and a T-top, a round top or a case where the degree of tailing was large was evaluated as x. For the case where the line width of 150 nm (line / space = 1: 1) was not resolved, the evaluation was performed using the minimum line width that can be resolved.
[Limit resolution]
The minimum line width that can be resolved at line / space = 1: 1 was confirmed by cross-sectional SEM observation, and the line width at that time was evaluated as the critical resolution. A smaller value indicates better performance.
The results are shown in Table 2.

[Dry etching resistance]
3.2 g of each of the resins (A1-1) to (A1-7) and (A2-1) to (A2-6) of the present invention was dissolved in 25 g of propylene glycol monomethyl ether acetate and filtered through a 0.1 μm Teflon filter. did. Each sample solution was applied onto a silicon wafer subjected to hexamethyldisilazane treatment using a spin coater, and dried by heating at 120 ° C. for 60 seconds to form a 0.5 μm resist film. The resist film was etched using an etching apparatus with an etching gas of CHF ₃ / O ₂ = 16/4, a pressure of 20 mTorr, and an applied power of 100 mW / cm ³ . The etching rate of the resist film was determined from the change in film thickness of the resist. Ratio with etching rate when using cresol novolak (m / p ratio = 4/6, weight average molecular weight 5000) under the same conditions (etching rate of film of example or comparative example / etching rate of cresol novolak film) Was calculated. Moreover, the cross section and surface of the obtained sample were observed and evaluated as follows.
○: Almost no irregularities on the resist surface are observed. Δ: Some irregularities are seen on the resist surface. X: Unevenness on the resist surface is noticeable. Table 2 shows the results.

In the table, each abbreviation represents one described in the specific examples of each component described above and the following.
N-1: Hexamethylenetetramine N-2: 1,5-diazabicyclo [4.3.0] -5-nonene N-3: 1,8-diazabicyclo [5.4.0] -7-undecene W-1 : Megafuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
S-1: Methyl lactate S-2: Propylene glycol monomethyl ether acetate S-3: Propylene glycol monomethyl ether

  It can be seen that the coating film using the composition of the present invention exhibits a good pattern profile, limit resolution, and dry etching resistance, and the surface shape of the film after etching is also good.

Claims (6)

(A1) a resin containing a repeating unit having at least two groups represented by the following general formula (Z);
(A2) a resin containing at least one repeating unit among the repeating units represented by the following general formulas (I) to (III), and (B) a compound that generates an acid by the action of actinic rays or radiation,
Containing
A positive resist composition, wherein at least one of the resin (A1) and the resin (A2) is a resin whose solubility in an alkaline developer is increased by the action of an acid.

In general formula (Z),
A plurality of R ⁵⁰ to R ⁵⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R ^{50 to} R ⁵⁵ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
A plurality of Y each independently represents a hydrogen atom or an organic group.

In general formulas (I) to (III),
R ₀ and R ₁ may be the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl group or an aryl group.
R _{2 to} R ₄ may be the same or different and each represents an alkyl group, a cycloalkyl group, or an aryl group.
R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ may combine to form a ring. The repeating unit having at least two groups represented by the general formula (Z) in the resin (A1) is a repeating unit represented by any one of the following general formulas (A), (A ′), and (A ″). The positive resist composition according to claim 1, wherein:

In the general formulas (A), (A ′), (A ″),
Several R _{< a1} > -R _<a6> represents a hydrogen atom, a fluorine atom, or an alkyl group each independently. However, at least one of R _{a1 to} R _a6 is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R _a7 represents a halogen atom, a cyano group or an alkyl group.
R _a8 and R _a9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an acyl group, an alkyl group, an alkenyl group, an aralkyl group or an aryl group.
When there are a plurality of R _{a10 s} , they may be different and each independently represents a halogen atom, an alkyl group or an alkoxy group.
R _a11 may be different when there are a plurality of R _a11 and each independently represents a halogen atom, an alkyl group or an alkoxy group.
R _{a12 to} R _a14 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Y _{a1 to} Y _a3 each independently represents a hydrogen atom or an organic group.
p, m1, and m ′ each independently represents an integer of 2 to 5.
n ′ represents an integer of 0 to 7.
n represents 0 or 1.
m2 represents an integer of 0 to 7.
A ₁ , A ₂ , and La ₁ each independently represent a single bond or a divalent linking group. The resin whose solubility in an alkaline developer is increased by the action of the acid of the resin (A1) and / or the resin (A2) contains a group represented by the formula (B) or a group obtained by protecting the carboxyl group with an acid-decomposable group. The positive resist composition according to claim 1, wherein the resist composition is a positive resist composition.

In general formula (B),
Zb represents an acid-decomposable group.
R _{31 to} R ₃₆ are each independently a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{31 to} R ₃₆ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain. Resin (A1) and / or resin (A2) resin whose solubility in an alkaline developer is increased by the action of an acid contains a group represented by formula (B '). The positive resist composition according to any one of the above.

In general formula (B ′),
Zc represents a hydrogen atom or a non-acid-decomposable group.
R _{31 to} R ₃₆ are each independently a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{31 to} R ₃₆ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain. The resin (A1) and / or the resin (A2) further contains at least one repeating unit selected from the following formulas (IV) to (XII): The positive resist composition according to Item.

In general formulas (IV) to (V),
R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or an acid-decomposable group.
R ₆ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or an acid-decomposable group.
R _7a may be different when there are a plurality of R _{7a s} and represents a halogen atom, an alkyl group or an alkoxy group.
n represents 0 or 1.
n ′ represents an integer of 0 to 7.
A ₁ is a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₂₂ —, —CO—O—R ₂₃ —, —CO—N (R ₂₄ ). -R ₂₅ - represents a.
R ₂₂ , R ₂₃ and R _{25 each} have a single bond or an ether group, ester group, amide group, urethane group or ureido group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group. Represents.
R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.

In general formula (VI),
Rx ₁ to Rx ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or at least one alkyl group wherein a hydrogen atom is substituted with a fluorine atom.
R _{61 to} R ₆₆ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{61 to} R ₆₆ is a fluorine atom.
R _{67 to} R ₇₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{67 to} R ₇₂ is a fluorine atom.
Z ₁ represents a phenylene group, a cyclohexylene group, an adamantane residue or a norbornane residue.
L ₁ represents a single bond or a divalent linking group.
q is 0 or 1.
Y ₁ represents a hydrogen atom or an organic group.
In general formula (VII),
R ₄₁ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
R ^{50 to} R ⁵⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R ^{50 to} R ⁵⁵ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Y ₂ represents a hydrogen atom or an organic group.
In general formula (VIII),
Ry _{1 to} Ry ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Y ₃ represents a hydrogen atom or an organic group.

In general formulas (IV) to (X),
R ₁₅ is hydrogen atom, hydroxyalkyl group, alkyl group having fluorine atom, cycloalkyl group having fluorine atom, alkenyl group having fluorine atom, aralkyl group having fluorine atom, aryl group having fluorine atom, or acid-decomposable Represents a group.
Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with a carbon atom.
R ₁₆ , R ₁₇ and R ₁₈ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group or —CO—O—R ₁₅ .
R ₁₉ , R ₂₀ and R ₂₁ may be the same or different and have a hydrogen atom, a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, an alkenyl group having a fluorine atom, or a fluorine atom. An aralkyl group, an aryl group having a fluorine atom, an alkoxy group having a fluorine atom, or a hydroxyalkyl group is represented. However, at least one of R ₁₉ , R ₂₀ and R ₂₁ is a group other than a hydrogen atom.
n represents 0 or 1, and x, y, z represents an integer of 0 to 4.

In general formula (XI),
Ra _{1 to} Ra ₃ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an aryl group, an alkoxy group or an aralkyl group.
Y ₄ represents a hydrogen atom or an organic group.
m represents 1 or 2.
In general formula (XII),
Ra _{4 to} Ra ₆ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an aryl group, an alkoxy group or an aralkyl group.
Y ₅ represents a hydrogen atom or an organic group.
L ₂ represents a single bond or a divalent linking group.
m represents 1 or 2. A pattern forming method comprising: forming a resist film from the resist composition according to claim 1; and exposing and developing the resist film.