JP2005070327A - Positive resist composition and pattern forming method using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide positive resist compositions suitable for use under an exposure light source of ≤160 nm, particularly F<SB>2</SB>excimer laser light (157 nm). <P>SOLUTION: One of the positive resist compositions contains (A1) a fluorine-containing resin having a fluorine substituted structure in a principal chain and/or a side chain of a polymer skeleton and having solubility in an alkali developer increased by the action of an acid, and (B) a compound which generates an acid under the action of an actinic ray or a radiation, wherein a water content of the composition is <0.3 mass%. The other of the positive resist compositions contains (A2) an alkali-soluble fluorine-containing resin having a fluorine substituted structure in a principal chain and/or a side chain of a polymer skeleton, (B) a compound which generates an acid under the action of an actinic ray or a radiation, and (X) a non-polymer type dissolution inhibitor, wherein a water content of the composition is <0.3 mass%. <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 having excellent line edge roughness and storage stability.

  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.
Resist composition for exposure with KrF excimer laser light, using poly (hydroxystyrene) basic skeleton with low absorption in the 248 nm region as a main component and acid-decomposable group as the main component, generating acid upon irradiation with far ultraviolet light A so-called chemically amplified resist has been developed in which a compound (photoacid generator) is combined.

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.
In Patent Document 1 (Japanese Patent Application Laid-Open No. 9-22115), an attempt is made to limit the amount of water applied to the resist composition to suppress variation in performance of the resist solution over time.

For the 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 2 (International Publication No. WO00 / 17712 pamphlet), etc., and studies on resist compositions containing fluorine-containing resins have been made.

However, resist compositions containing fluorine-containing resins for F ₂ excimer laser light exposure and other fluorine-containing compounds have fluorine atoms in the vicinity of an alkali-soluble group protected with an acid-decomposable group. Due to electron withdrawing properties, hydrolysis and other deprotection reactions tend to proceed. Therefore, the resist composition has poor storage stability in a solution state as compared with a resist composition containing a fluorine-free resin or other fluorine-containing compound, and has a problem that performance variation between lots is large. Had.
Further, the resist composition for F ₂ excimer laser light exposure has a problem that the uniformity of line pattern edges (line edge roughness) is poor.

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) JP-A-9-22115 WO-00 / 17712 pamphlet

An object of the present invention is to provide a positive resist composition suitable for use with an exposure light source of 160 nm or less, particularly F ₂ excimer laser light (157 nm), specifically, sufficient transmission when using a light source of 157 nm. It is an object of the present invention to provide a positive resist composition that exhibits the properties and has excellent line edge roughness and storage stability.

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 by using the following specific composition, and have reached the present invention.
That is, the present invention has the following configuration.

(1) (A1) a fluorine group-containing resin having a structure in which a fluorine atom is substituted on the main chain and / or side chain of the polymer skeleton, and having increased solubility in an alkali developer by the action of an acid;
(B) A positive resist composition containing a compound that generates an acid by the action of actinic rays or radiation, wherein the water content in the composition is 0.3% by mass or less. Resist composition.
(2) (A2) an alkali-soluble fluorine-containing resin having a structure in which a fluorine atom is substituted on the main chain and / or side chain of the polymer skeleton,
(B) a compound that generates an acid by the action of actinic rays or radiation, and
(X) A positive resist composition containing a non-polymer type dissolution inhibitor, wherein the moisture content in the composition is 0.3% by mass or less.

(3) The positive resist composition as described in (1) above, wherein the resin (A1) is a resin having a repeating unit containing a group represented by the following general formula (a).

In general formula (a),
R _{31 to} R ₃₆ each independently represent 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.
One of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.
Y ₀ represents a hydrogen atom or an organic group.

一般式（ｂ）中、
Ｒ₃₁〜Ｒ₃₆はそれぞれ 独立して、水素原子、フッ素原子、またはアルキル基を表す。ただし、Ｒ₃₁〜Ｒ₃₆うち少なくとも１つはフッ素原子または少なくとも１つの水素原子がフッ素原子で置換されたアルキル基である。
Ｒ₃₁〜Ｒ₃₆のうちの１つは炭素鎖を介して樹脂の主鎖につながっていてもよい。
Ｙ_0bは、水素原子または酸非分解性の有機基を表す。 (4) The positive resist composition as described in (2), wherein the resin (A2) is a resin having a repeating unit containing a group represented by the following general formula (b).

In general formula (b),
R _{31 to} R ₃₆ each independently represent 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.
One of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.
Y _0b represents a hydrogen atom or an acid non-decomposable organic group.

(5) The positive resist composition as described in (1) or (3) above, wherein the resin (A1) contains a repeating unit containing a group in which a carboxyl group is protected with an acid-decomposable group. .

The preferred embodiments of the present invention will be further described below.
(6) The above-mentioned (1) to (5), wherein the resin (A1) or (A2) contains at least one repeating unit selected from the following general formulas (I) to (XII): The positive resist composition according to any one of the above.

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 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 ₇ each independently represents a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group.
n represents 0 or 1.
n ′ represents an integer of 0 to 7.
m ′ represents an integer of 1 to 5.
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 ₃ represents a benzene residue, a cyclohexane residue, an adamantane residue or a norbornane residue.
L ₁ represents a single bond or a divalent linking group.
q is 0 or 1.
q ′ is an integer of 1 to 5.
Y ₂ 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 ₄₂ and R ₄₃ 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.
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.
k represents an integer of 1 to 5.
Y ₃ 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 ₄ 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),
Each Ra ₄ 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 ₄ represents a single bond or a divalent linking group.
m represents 1 or 2.
m1 represents an integer of 1 to 5.
m2 represents an integer of 0 to 7.

(7) The resin (A1) or (A2) is at least one repeating unit selected from the general formulas (I) to (III) described in the above (6) and the general structure described in the above (6) The positive resist composition as described in any one of (1) to (5) above, which contains at least one repeating unit selected from formulas (IV) to (XII).
(8) The resin (A1) or (A2) is represented by the repeating unit represented by the general formula (I) described in the above (6) and the general formula (V) described in the above (6). The positive resist composition as described in (7) above, wherein at least one repeating unit is contained.

(9) The resin (A1) or (A2) is at least one selected from the general formulas (IV), (V), (VII), and (IX) to (XII) described in (6) above Any one of (1) to (5) above, comprising one repeating unit and at least one repeating unit selected from the general formulas (VI) and (VIII) described in (6) above A positive resist composition as described above.
(10) The resin (A1) or (A2) is at least one repeating unit selected from the general formulas (V) and (VII) described in the above (6), and the above described (6) The positive resist composition as described in (8) above, which contains at least one repeating unit selected from the general formulas (VI) and (VIII).

(11) The positive resist composition as described in any one of (1) to (10) above, further comprising (E) an organic basic compound.
(12) The positive resist composition as described in any one of (1) to (11) above, further comprising (D) a surfactant.

(13) As the component (B),
(B1) The positive resist composition as described in any one of (1) to (12) above, which comprises a compound that generates an organic sulfonic acid by the action of actinic rays or radiation.
(14) 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 that does not contain at least one fluorine atom by the action of actinic rays or radiation The positive resist composition as described in (13) above, which contains at least one compound that generates sulfonic acid.
(15) The positive resist composition as described in (13) or (14) above, further comprising (B2) a compound that generates carboxylic acid by the action of actinic rays or radiation.

(16) The positive resist composition according to any one of (1) to (15), further comprising a solvent (17) characterized in that propylene glycol monomethyl ether acetate is contained as the solvent. The positive resist composition (18) according to (16), further containing propylene glycol monomethyl ether as the solvent, (19) The positive resist composition according to (17), wherein (1) to (18) A pattern forming method comprising: forming a resist film from the resist composition according to any one of the above); and exposing and developing the resist film.

  According to the present invention, it is possible to provide a positive resist composition exhibiting sufficient transparency even at a wavelength of 160 nm or less, particularly at a short wavelength of F2 excimer laser light (157 nm), and having excellent line edge roughness and storage stability.

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] (A1 or A2) Fluorine-containing resin The fluorine-containing resin in the present invention has (A1) a structure in which a fluorine atom is substituted in the main chain and / or side chain of the polymer, and is decomposed by the action of an acid. Fluorine group-containing resin having a group that increases the solubility in an alkali developer, the solubility in an alkali developer being increased by the action of an acid, or (A2) a structure in which a fluorine atom is substituted on the main chain and / or side of the polymer An alkali-soluble fluorine-containing resin having a chain and an alkali-soluble group, and each resin preferably has at least a site selected from a perfluoroalkylene group and a perfluoroarylene group in the main chain of the polymer skeleton. Perfluoroalkyl group, perfluoroaryl group, hexafluoro-2-propanol group, and hexafluoro group. It is a fluorine atom-containing resin having at least one site selected from a group in which the OH group of the ro-2-propanol group is protected in the side chain of the polymer backbone.

The fluorine-containing resins (A1) and (A2) in the present invention are preferably resins containing a repeating unit having a group represented by the general formula (a), and particularly in the resin (A2), A resin having a repeating unit containing a group in which Y ₀ in general formula (a) is a hydrogen atom is preferable.

In general formula (a),
R _{31 to} R ₃₆ each independently represent 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.
One of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.
Y ₀ represents a hydrogen atom, an acid-decomposable group or a non-acid-decomposable group.

In the general formula (a), the alkyl group of R _{31 to} R ₃₆ may have a substituent, for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group And ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, hexyl group, 2-ethylhexyl group and octyl group.
One of R _{31 to} R ₃₆ may be connected to the main chain of the fluorine atom-containing resin through a carbon chain. Such a carbon chain is preferably an alkylene group having 1 to 10 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.

Y ₀ represents a hydrogen atom 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.
The alkyl group of R _{11a to} R _13a , R _14a , R _15a , and R _16a may have a substituent, and is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, and propyl Group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and the like.

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 cyclic alkyl 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 group represented by the general formula (a) can be provided, for example, in the repeating units represented by the general formulas (IV) to (VII).

  The fluorine atom-containing resin in the present invention preferably further has a repeating unit having a group obtained by protecting a carboxyl group with an acid-decomposable group.

As the group a in carboxyl groups present invention has been protected with an acid decomposable group, for _{example, -COO-C (R 36)} (R 37) (R 38), - COO-C (R 36) (R 37) (OR ₃₉ ), —O—COO—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —O—C (R ₀₁ ) (R ₀₂ ) COO—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) And the like.
A group in which a carboxyl group is protected with an acid-decomposable group can be given, for example, in a repeating unit represented by formulas (IV) to (IX).

  The fluorine atom-containing resins (A1) and (A2) in the present invention are preferably resins containing at least one repeating unit selected from the above general formulas (I) to (XII), more preferably. Is a resin containing at least one repeating unit selected from the above general formulas (I) to (III) and at least one repeating unit selected from the above general formulas (IV) to (XII), Or at least one repeating unit selected from the above general formulas (IV), (V), (VII), and (IX) to (XII), and the above general formulas (VI), (VIII) to ( IX). A resin containing at least one repeating unit selected from IX).

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 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 ₇ each independently represents a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group.
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.
m ′ represents an integer of 1 to 5. m ′ is preferably an integer of 1 to 4, more preferably an integer of 1 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 ₇ and the group represented by A ₁ (CF ₃ ) ₂ OR ₆ may be substituted 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 benzene residue, a cyclohexane residue, an adamantane residue or a norbornane residue. These residues may have a substituent, and preferred substituents include a halogen atom, a hydroxyl group, an alkoxy group, and a cyano group. When Z ₃ has a substituent, the substituent is more preferably a fluorine atom or a hydroxyl group, and particularly preferably a fluorine atom. If Z ₃ is a fluorine as a substituent, the number of fluorine atoms in each repeating unit is preferably from 1 to 5, more preferably 1-3.
L ₁ represents a single bond or a divalent linking group.
q is 0 or 1.
q ′ is an integer of 1 to 5. q ′ is preferably an integer of 1 to 4, more preferably 1 or 2.
Y ₂ 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 ₄₂ and R ₄₃ 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.
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.
k represents an integer of 1 to 5.
Y ₃ 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 ₄ represents a hydrogen atom or an organic group.

一般式（ＩＸ）〜（Ｘ）中、
Ｒ₁₅は、水素原子、ヒドロキシアルキル基、フッ素原子を有するアルキル基、フッ素原子を有するシクロアルキル基、フッ素原子を有するアルケニル基、フッ素原子を有するアラルキル基、フッ素原子を有するアリール基または酸分解性基を表す。
Ｚは、炭素原子とともに単環又は多環の脂環式基を構成する原子団を表す。
Ｒ₁₆、Ｒ₁₇、Ｒ₁₈は、同じでも異なっていても良く、水素原子、ハロゲン原子、シアノ基、アルキル基、アルコキシ基、−ＣＯ−Ｏ−Ｒ₁₅を表す。
Ｒ₁₉、Ｒ₂₀、Ｒ₂₁は、同じでも異なっていても良く、水素原子、フッ素原子、フッ素原子を有するアルキル基、フッ素原子を有するシクロアルキル基、フッ素原子を有するアルケニル基、フッ素原子を有するアラルキル基、フッ素原子を有するアリール基、フッ素原子を有するアルコキシ基又はヒドロキシアルキル基を表す。但しＲ₁₉、Ｒ₂₀、Ｒ₂₁の少なくとも一つは水素原子以外の基である。
ｎは０又は１を表し、ｘ、ｙ、ｚは０〜４の整数を表す。

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. Ra _{1 to} Ra ₃ are preferably a hydrogen atom or a halogen atom, and the halogen atom is preferably a fluorine atom. In particular, Ra ₁ is preferably a fluorine atom.
Y ₄ represents a hydrogen atom or an organic group.
m represents 1 or 2.
In general formula (XII),
Each Ra ₄ 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 ₄ represents a single bond or a divalent linking group.
m represents 1 or 2.
m1 represents an integer of 1 to 5. m1 is preferably an integer of 1 to 4, more preferably 1 or 2.
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.
In the formula (XII), the group represented by R _a4 and the group represented by L ₄ (CF ₃ ) ₂ OY ₅ may be substituted at any position of the carbocyclic structure.

In general formulas (I) to (XII),
The alkyl group may have a substituent, for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group. Preferred examples include a group, t-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and haloalkyl group. 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 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.

  Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group, and the formed alicyclic group is a monocyclic type having 3 to 8 carbon atoms, for example, 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.

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.

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

  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 (VII) include the following.

  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 the present invention, R ₅ in the general formulas (IV) and (V) and R _{15 in} (IX) may be an acid-decomposable group.

  In the present invention, the resin (A1) and the resin (A2) may further contain other repeating units. The other repeating unit that can be contained is not particularly limited, but is preferably a repeating unit represented by the following formula (D), (E) or (F).

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 ₄₃ and R ₄₄ each independently represents 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.
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 ₅ represents a hydrogen atom or an organic group.
When there are a plurality of Y _{5 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 formula (D),
AR represents an alicyclic hydrocarbon group. The alicyclic hydrocarbon group is bonded from the main chain of the resin via a linking group, or the carbon atoms constituting the ring of the alicyclic hydrocarbon itself form the main chain of the resin.
L ₂ represents a single bond or a divalent linking group.
When X is plural, each X independently represents a hydroxyl group, a cyano group, an alkoxy group or an alkyl group. However, at least one of X is not an alkyl group.
p represents an integer of 1 to 4.

The alicyclic hydrocarbon group of AR may be monocyclic or polycyclic, and specific examples thereof include those having an alicyclic structure such as monocyclo, bicyclo, tricyclo, and tetracyclo having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25.
Below, the specific example of an alicyclic structure is shown.

Examples of the alicyclic hydrocarbon group for AR include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cycloheptyl group, and the like. Examples include residues obtained by further removing some hydrogen atoms from an octyl group, a cyclodecanyl group, a cyclododecanyl group, and the like. A group selected from a norbornane residue, an adamantane residue, a tricyclodecane residue, and a tetracyclododecane residue is preferable, and an adamantane residue is more preferable.
The alicyclic hydrocarbon group of AR may have other substituents such as a carboxyl group and an alkoxycarbonyl group.

The alkyl group of X may have a substituent. Further, the alkyl group may be linear, branched or cyclic.
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 cyclic alkyl 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 X may be linear, branched or cyclic, and is preferably an alkoxy group having 1 to 8 carbon atoms, specifically, a methoxy group, an ethoxy group, or 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 X may have further substituents such as a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 5 carbon atoms).

X 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 a cyano group, and particularly preferred is a hydroxyl group.
X may be bonded to the carbon forming the alicyclic hydrocarbon group of AR or bonded to the carbon of the substituent bonded to the alicyclic hydrocarbon group of AR. It may be.

L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an ether group, a thioether group, a carbonyl group, and an ester. A single group selected from the group consisting of a group, an amide group, a sulfonamide group, a urethane group, or a urea group, or a combination of two or more groups. Examples of the alkylene group in the above include groups represented by the following formulas.
− [C (R _b ) (R _c )] _r −
In the formula, R _b and R _c represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and both 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.
L ₂ is particularly preferably a single bond or a methylene group.
p represents an integer of 1 to 4, and is preferably 2 or 3.

  In the present invention, the repeating unit having a partial structure represented by the general formula (D) is not particularly limited, but is preferably a repeating unit represented by the following general formulas (A1) to (A5).

In general formulas (A-1) to (A-5),
R _{1 to} R ₁₄ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group.
L ₁ represents a single bond or a linking group.
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.
m represents 0 or 1.
Y ₁ 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.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
Examples of the divalent linking group for L ₃ include the same groups as those described above for L ₂ .
Examples of the alkyl group, cycloalkyl group, and aryl group are the same as those in the general formulas (I) to (III).
As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms is preferable, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

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

  In the formula (E), the alkyl group may have a substituent, may be linear or branched, and is preferably an alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group). 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 those similar to Y ₀ in formula (a).

  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 Y ₀ in the general formula (a).

  The general formula (F) is preferably represented by the following general formula (F-1).

In general formula (F-1),
L ₁ represents a single bond or a divalent linking group.
Za 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. The acid-decomposable group and non-acid-decomposable group include the same as those of Y ₅ in Zb or formula (E) in the general formula (A).
That, L ₁ and Za are the general formula (F) the same meaning as in L ₁ and Za.

  Monomers (vinyl ethers) corresponding to the repeating units represented by the general formula (F) include, for example, a condensation reaction between commercially available chloroethyl vinyl ether and various alcohols, vinyl ethers and various alcohols that are readily available, and Hg, Pd. , And Ir can be synthesized by an exchange reaction using a catalyst such as Ir.

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

  In the present invention, the resins (A1) and (A2) may be copolymerized with other polymerizable monomers for the purpose of further improving the performance of the positive resist of the present invention in addition to the above repeating structural units. Also good.

  Examples of copolymerizable monomers that can be used include those shown below. For example, an addition polymerizable unsaturated bond selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters other than the above. A compound having one.

  Specifically, for example, acrylic acid esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate) , Amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylol Propane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) Rate (e.g., phenyl acrylate);

Methacrylic acid esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, amyl methacrylate, hexyl methacrylate) Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, Pentaerythritol monomethacrylate, glycidyl methacrylate, Le furyl methacrylate, tetrahydrofurfuryl methacrylate), aryl methacrylates (e.g., phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkyl acrylamide, (the alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl Group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (as aryl group, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, cyanophenyl group, hydroxyphenyl) Group, carboxyphenyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl) Group, etc.), N, N-diaryla (Examples of the aryl group include phenyl group.) Riruamido, N- methyl -N- phenyl acrylamide, N- hydroxyethyl -N- methylacrylamide, etc. N-2- acetamidoethyl -N- acetyl acrylamide;

Methacrylamide, for example, methacrylamide, N-alkylmethacrylamide (the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl Group, etc.), N-aryl methacrylamide (the aryl group includes phenyl group), N, N-dialkyl methacrylamide (the alkyl group includes ethyl group, propyl group, butyl group, etc.) ), N, N-diarylmethacrylamide (the aryl group includes phenyl group), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N -Phenylmethacrylamide and the like; allyl compounds such as allyl este Class (e.g., allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), and allyl oxyethanol;

Vinyl ethers such as alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl Vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc., vinyl aryl ethers (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chloropheny) Ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinylphenyl Acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .;

Styrenes such as styrene, alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoro Dimethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (for example, methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.), halogen styrene (for example, chloro styrene, dichloro styrene, trichloro styrene). , Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, tri Ruorusuchiren, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.), carboxy styrene, vinyl naphthalene;

Crotonic esters such as alkyl crotonic acid (eg butyl crotonate, hexyl crotonate, glycerol monocrotonate); dialkyl itaconates (eg dimethyl itaconate, diethyl itaconate, dibutyl itaconate); Examples thereof include dialkyl esters of acid or fumaric acid (for example, dimethyl maleate and dibutyl fumarate), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilonitrile and the like. In addition, any addition-polymerizable unsaturated compound that is generally copolymerizable may be used.

The content of the repeating unit containing the partial structure represented by the general formula (Ia) is generally 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 in the total polymer composition. Mol%.
The total content of the repeating units represented by the general formulas (I) to (III) is generally 3 to 90 mol%, preferably 5 to 80 mol%, more preferably 7 in the total polymer composition. -70 mol%.
The total content of the repeating units represented by the general formulas (IV) to (XII) is generally 1 to 80 mol%, preferably 3 to 65 mol%, more preferably 5 in the total polymer composition. ˜50 mol%.
The total content of the repeating units represented by the general formulas (D), (E) and (F) is generally 1 to 80 mol%, preferably 3 to 65 mol% in the total polymer composition, More preferably, it is 5-50 mol%.

  The content of the repeating unit having a group that decomposes by the action of an acid and increases the solubility in an alkali developer is generally 5 to 70 mol%, preferably 10 to 65 mol% in the total polymer composition, More preferably, it is 15-50 mol%.

  The acid-decomposable resin 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 this invention, it is preferable that metal components, such as Na, K, Ca, Fe, Mg, contained in the resin of (A1) and (A2) are a small amount. 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.

  The preferred molecular weights of the resins (A1) and (A2) of the present invention having the above repeating structural units are 1,000 to 200,000 on a weight average, and more preferably 3,000 to 20,000. Is done. The molecular weight distribution is usually from 1 to 10, preferably from 1 to 3, more preferably from 1 to 2. The smaller the molecular weight distribution, the smoother the resolution, the resist shape, and the side wall of the resist pattern, and the better the line edge roughness.

  The addition amount of the resins (A1) and (A2) of the present invention is generally 50% by mass or more, 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

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

［２］（Ｂ）活性光線の照射により、酸を発生する化合物 本発明のポジ型レジスト組成物に用いられる、活性光線又は放射線の照射により酸を発生する化合物（以下、「酸発生剤」と呼ぶ場合がある。）について以下に説明する。
本発明に於いて使用可能な酸発生剤としては、光カチオン重合の光開始剤、光ラジカル重合の光開始剤、色素類の光消色剤、光変色剤、あるいはマイクロレジスト等に使用されている活性光線又は放射線の照射により酸を発生する公知の化合物及びそれらの混合物を適宜に選択して使用することができる。

[2] (B) Compound that generates an acid upon irradiation with actinic rays The compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter referred to as “acid generator”) used in the positive resist composition of the present invention. Will be described below.
Acid generators that can be used in the present invention include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and microresists. Known compounds that generate an acid upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used.

  For example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, onium salts such as arsonium salts, organic halogen compounds, organic metal / organic halides, acid generators having o-nitrobenzyl type protecting groups And compounds capable of generating sulfonic acid by photolysis represented by imino sulfonate and the like, and disulfone compounds.

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

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

(B) As a compound of a component, the compound which generate | occur | produces organic sulfonic acid by the effect | action of actinic light or a radiation is preferable. (B) The compound of a component can be used individually by 1 type or in combination of 2 or more types. When using in combination of 2 or more types, the following combinations (a) to (d) may be mentioned.

(A)
(B1a) a compound that generates an organic sulfonic acid containing at least one fluorine atom by the action of actinic rays or radiation, and (B1b) a compound that generates an organic sulfonic acid that does not contain a fluorine atom by the action of actinic rays or radiation. combination

(B)
A combination of (B1a) and (B2) a compound that generates a carboxylic acid by the action of actinic rays or radiation (c)
Combination (d) of (B1b) and (B2)
Combination of (B1a)

  Of these combinations, (a), (b) and (d) are preferred, and (a) and (b) are more preferred.

  Of the compounds that can be decomposed by irradiation with actinic rays or radiation that can be used, those that are particularly effective are described below.

  (1) An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the general formula (PAG4).

Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferable substituents include an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group. Preferred are aryl groups having 6 to 14 carbon atoms, alkyl groups having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents are an aryl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group, and a halogen atom. An alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group;

Z ⁻ represents a counter anion, such as perfluoroalkanesulfonic acid anion such as BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , pentafluoro Examples include, but are not limited to, condensed polynuclear aromatic sulfonate anions such as benzenesulfonate anion and naphthalene-1-sulfonate anion, anthraquinone sulfonate anion, and sulfonate group-containing dyes.

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.

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

  Diphenyl iodonium dodecyl benzene sulfonate, diphenyl iodonium trifluoromethane sulfonate, bis (4-trifluoromethylphenyl) iodonium trifluoromethane sulfonate, bis (4-t-butylphenyl) iodonium camphor sulfonate.

  Triphenylsulfonium dodecylbenzenesulfonate, triphenylsulfonium-2,4,6-trimethylbenzenesulfonate, triphenylsulfonium-2,4,6-triisopropylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorooctanesulfonate , Triphenylsulfonium perfluorononane sulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium perfluorobenzene sulfonate, triphenylsulfonium-3,4-bis (trifluoromethyl) benzene sulfonate.

  The above onium salts represented by the general formulas (PAG3) and (PAG4) are known and can be synthesized, for example, by the methods described in U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

  (2) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

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.

  Bis (tolyl) disulfone, bis (4-methoxyphenyl) disulfone, bis (4-trifluoromethylphenyl) disulfone, phenyl-4-isopropylphenyldisulfone.

  (3) A diazodisulfone derivative represented by the following general formula (PAG7).

Here, R represents a linear, branched or cyclic alkyl group, or an aryl group which may be substituted.
Specific examples include the following compounds, but are not limited thereto.

  Bis (phenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (tolylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane.

  (4) As the acid generator (A), a phenacylsulfonium derivative represented by the following general formula (I) can also be used.

In general formula (I),
R _{1 to} R ₅ represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, an alkyloxycarbonyl group or an aryl group, and at least two of R _{1 to} R ₅ are bonded to form a ring structure. It may be formed.
R ₆ and R ₇ represent a hydrogen atom, an alkyl group, a cyano group, or an aryl group.
Y ₁ and Y ₂ represent an alkyl group, an aryl group, an aralkyl group or an aromatic group containing a hetero atom, and Y ₁ and Y ₂ may be bonded to form a ring.
Y ₃ represents a single bond or a divalent linking group.
X ⁻ represents a non-nucleophilic anion.
At least one of R ₁ to R ₅ and at least one of Y ₁ or Y ₂ may be bonded to form a ring, or at least one of R ₁ to R ₅ and at least one of R ₆ or R ₇ may be bonded. To form a ring.
It may be bonded via a linking group at any position of R ₁ to R ₇ or at any position of Y ₁ or Y ₂ and may have two or more structures of formula (I).

  Specific examples of the compound represented by the above formula (I) are shown below, but the present invention is not limited thereto.

  Among the above-mentioned compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, examples of particularly preferable compounds are listed below.

  (B) The compound of a component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (B) compound in the positive resist composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the solid content of the composition. More preferably, it is 1-7 mass%.

[3] Non-polymer type dissolution inhibitor (X)
The positive resist composition of the present invention may contain a non-polymer type dissolution inhibitor (X component). When the resin is an alkali-soluble resin, the resist composition of the present invention contains a non-polymer type dissolution inhibitor. When the resin is an acid-decomposable resin, the resist composition of the present invention may or may not contain a non-polymer type dissolution inhibitor. Non-polymer type dissolution inhibitors are compounds whose solubility in an alkaline developer is increased by the action of an acid. The non-polymer type dissolution inhibitor in the present invention is preferably a compound having a molecular weight of 3000 or less, more preferably 200 to 2000, and more preferably 400 to 1500. The non-polymer type dissolution inhibitor in the present invention preferably contains two or more acid-decomposable groups.
The non-polymer type dissolution inhibitor is particularly preferably a compound represented by the formula (XA) or the formula (XB).

In formula (XA) and formula (XB),
AR represents a monocyclic or polycyclic cycloalkane residue or an aromatic ring residue.
R _{81 to} R ₈₆ independently represent a hydrogen atom fluorine atom or an alkyl group. However, at least one of R _{81 to} R ₈₆ is a fluorine atom.
R ₈₇ and R ₈₈ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, a cyano group or an alkyl group.
L ₃ and L ₄ each independently represents a single bond or a divalent linking group.
Z ₁ and Z ₂ each independently represent a hydrogen atom, an acid-decomposable group or a non-acid-decomposable group.
M ₁ represents a single bond or a divalent linking group.
M ₂ represents a (g + h) -valent linking group.
a and b each independently represent an integer of 0 or more and 5 or less. However, 2 ≦ a + b ≦ 10 is satisfied.
c represents an integer satisfying 0 ≦ c ≦ 5.
d and e each independently represent an integer of 0 or more and 5 or less. However, 1 ≦ d + e ≦ 10 is satisfied.
f represents an integer satisfying 0 ≦ f ≦ 5.
g represents an integer satisfying 2 ≦ g ≦ 6.
h represents an integer satisfying 0 ≦ h ≦ 5.
The compound represented by the formula (XA) or the formula (XB) contains at least two acid-decomposable groups.

  The alkyl group may have a substituent, for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group. Preferred examples include a group, t-butyl group, hexyl group, 2-ethylhexyl group, and octyl group.

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

  The alkoxy group may be linear, branched or cyclic, preferably an alkoxy group having 1 to 8 carbon atoms, specifically, a methoxy group, an ethoxy group, an n-propoxy group, An iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group, an octoxy group, etc. can be mentioned, More preferably, a C1-C4 alkoxy group (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) is mentioned. Can be mentioned.

Examples of the acid-decomposable group and the non-acid-decomposable group include those similar to Y ₀ in the formula (a) in the resin (A).

  Examples of the divalent linking group include an alkylene group, a cycloalkylene group, an arylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, a urea group, and combinations thereof. be able to. 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. The alkylene group, cycloalkylene group, and arylene group may have a substituent such as a fluorine atom.

The (g + h) -valent linking group is preferably a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms, or an aromatic ring residue having 6 to 20 carbon atoms. These groups may have a substituent, and may have —O—, —CO ₂ —, —CO—, —SO ₂ —, —SO— or the like between carbon-carbon bonds. .

  The alicyclic group or aromatic ring group of AR may be monocyclic or polycyclic. Specific examples include those having an alicyclic structure such as monocyclo, bicyclo, tricyclo, and tetracyclo having 5 or more carbon atoms. The carbon number is preferably 6 to 30, and particularly preferably 6 to 25.

The compound represented by the formula (XA) or (XB) preferably contains two or more acid-decomposable groups.
Examples of the acid-decomposable group and non-acid-decomposable group include the same acid-decomposable groups as Y ₀ in the general formula (a) of the resin (A).

  Although the specific example of an alicyclic structure is shown below, it is not limited to this.

  Of these alicyclic structures, (23), (35), (40), (51) are preferred, and (23), (40) are more preferred.

  The aromatic group represented by AR may be monocyclic or polycyclic, and is an aromatic ring residue having 6 to 30 carbon atoms, preferably 6 to 25 carbon atoms, and more preferably 6 to 20 carbon atoms. Specific examples include benzene, naphthalene, phenanthrene, and pyrene residues. Each aromatic ring may have a substituent. Examples of the substituent include the same substituents that may be substituted on the alkyl group.

  3-50 mass% is preferable with respect to the polymer in a composition, and, as for the addition amount of X component, More preferably, it is 5-40 mass%, More preferably, it is 7-30 mass%.

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

  The non-polymeric dissolution inhibitor (X) preferably contains a fluorine atom in the molecule. The number of fluorine atoms contained in one molecule is preferably 1 to 40, more preferably 3 to 35, and still more preferably 5 to 30.

  The non-polymer type dissolution inhibitor (X) can be synthesized by protecting a readily available compound containing a plurality of alkali-soluble groups in one molecule with an acid-decomposable group by a conventional method. Alternatively, it can be synthesized by linking a plurality of readily available compounds containing at least one alkali-soluble group in one molecule by a conventional method to synthesize a mother nucleus molecule and then protecting with an acid-decomposable group by a conventional method. It can also be synthesized by linking a plurality of compounds in which alkali-soluble groups are previously protected with an acid-decomposable machine.

[4] Solvent (component C)
The composition of the present invention is 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.

In the present invention, the resin (A1) and the (B) component positive resist composition containing a compound that generates an acid by the action of actinic rays or radiation, and the resin (A2) and (B) components. And (X) the water content in the positive resist composition containing the non-polymer type dissolution inhibitor is 0.3% by mass or less.
When the acid-decomposable group is an acetal group, the deprotection reaction proceeds due to the moisture in the composition, so it is preferable that a slight amount of moisture remains in the composition. That is, the moisture content is preferably 0 or more and 0.3% by mass or less. More preferably, it is 0.005-0.25 mass%, Most preferably, it is 0.01-0.2 mass%.
By setting the moisture content to 0.3% by mass or less, the storage stability can be improved, the performance variation between lots can be reduced, and the object of the present invention can be achieved.
The water content is a value obtained by measuring 50 to 100 μl of a chemically amplified positive resist composition solution by a conventional method using a Karl Fischer moisture meter (MKC-210 manufactured by KYOTO ELECTRONICS).

  In order to obtain a chemically amplified positive resist composition in which the moisture content of the present invention is 0.3% by mass or less in the composition, each component constituting the composition of the present invention and each component to be added as necessary are added. , A method of heating to such an extent that they do not decompose, and drying under reduced pressure conditions for a long time (at least 10 hours or more), each component constituting the composition, and (C) solvent solution of each component added as necessary under reduced pressure A method of heating under conditions to distill water off, each component constituting the composition, and each component added as necessary are dehydrated by, for example, a molecular sieve known as molecular sieve (manufactured by Union Showa Co., Ltd.) There are a method of adjusting, a method of directly treating each component constituting the composition of the present invention and (C) the solvent solution of each component added as necessary with a molecular sieve, etc., but the water content in the resist composition is adjusted. If a method which can lower, but is not limited thereto.

[5] Fluorine-based and / or silicon-based surfactant (component D)
The positive resist composition of the present invention further comprises a surfactant (D), particularly (D) a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant, fluorine atom and silicon). It is preferable to contain any one or two or more of surfactants containing both atoms.
When the positive resist composition of the present invention contains the above-mentioned (D) surfactant, 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 EFTOP EF301 and EF30.
3, (made by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (Sumitomo 3M Co., Ltd.)
Manufactured), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Fluorosurfactants or silicon surfactants such as Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

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

  (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).

[6] Organic basic compound (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 over time after application Furthermore, it is preferable to add an organic basic compound as an acid diffusion inhibitor for the purpose of preventing excessive diffusion (degradation of resolution) of the acid during heat treatment after irradiation with actinic rays or radiation. The organic basic compound is, for example, an organic basic compound containing basic nitrogen, and a compound having a pKa value of 4 or more of the conjugate acid 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 are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. Wherein 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. If the molar ratio is less than 2.5, the sensitivity may be low and the resolution may be reduced. If the molar ratio is more than 300, the resist pattern may increase in thickness over time until post-exposure heat treatment, and the resolution may also be reduced. . (Acid generator) / (organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

  In the manufacture of precision integrated circuit elements, the pattern forming process on the resist film is carried out by applying the positive resist composition of the present invention on a substrate (eg, a transparent substrate such as a silicon / silicon dioxide covering, a glass substrate, an ITO substrate). 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 alkaline developer of 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, and n-propylamine. Primary amines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, An aqueous solution of alkalis such as quaternary ammonium salts such as tetraethylammonium 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 alkaline developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and an aqueous solution of 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 (F-1)]
5- [2,2-bis (trifluoromethyl) -2-hydroxyethyl] bicyclo [2.2.1] hept-2-ene 10.97 g (0.04 mol), 2-trifluoromethylacrylic acid t- After charging 11.77 g (0.06 mol) of butyl ester into the reaction vessel and replacing the inside of the reaction system with nitrogen, 0.248 g (1.43 mmol) of polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries) was added. The mixture was heated and stirred at 65 ° C. while flowing nitrogen through the reaction system.
The obtained powder had a weight average molecular weight of 15,200 and a dispersity of 1.45 as determined by gel permeation chromatography (GPC). Moreover, 5- [2,2-bis (trifluoromethyl) -2-hydroxyethyl] bicyclo [2.2.1] hept-2-ene / 2- by 1H-NMR, 13C-NMR, and 19F-NMR analysis. The composition ratio of trifluoromethyl acrylic acid t-butyl ester was 30/70.
2 hours later, 4 hours later, 6 hours later, and 8 hours later, 0.248 g of V-65 was added, and the mixture was heated and stirred for a total of 20 hours. 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 50 ° C. to obtain 14.33 g of powder (yield 63%).
Resins (F-2) to (F-3), (F-5), (F-11) to (F-12), (F-15), (F) F-18) to (F-19), (F-21), (F-25), (F-36), (F-37), (F-44), (F-46), (F- 47) was obtained.

[Synthesis Example 2 Synthesis of Resin (F-32)]
In a 200 mL pressure vessel, 13.71 g (0.05 mol) of 5- [2,2-bis (trifluoromethyl) -2-hydroxyethyl] bicyclo [2.2.1] hept-2-ene, t-acrylate 9.61 g (0.075 mol) of butyl ester, 50 ml of 1,1,2-trichloro-trifluoroethylene, and 0.996 g (2.5 mmol) of di (4-t-butylcyclohexyl) peroxydicarbonate were added.
The container was closed, cooled in dry ice, evacuated, charged with 18.8 g (0.188 mol) of tetrafluoroethylene and pressurized. The inside of the container was heated to 60 ° C. with stirring, and the heating and stirring were continued for 12 hours. Thereafter, the container was allowed to cool to room temperature to obtain a polymer solution having a high viscosity. The polymer solution was dropped into methanol to remove the powder, and dried under reduced pressure to obtain 12.19 g of polymer (F-32).
The weight average molecular weight of the obtained powder as measured by gel permeation chromatography (GPC) was 4700, and the degree of dispersion was 1.51. Further, tetrafluoroethylene / 5- [2,2-bis (trifluoromethyl) -2-hydroxyethyl] bicyclo [2.2.1] hept-2-ene / acrylic acid by 1H-NMR and 13C-NMR analysis The molar composition ratio of t-butyl ester was 50/20/30.
Resins (F-29), (F-32), (F-35), (F-40) to (F-43), and (F-45) are obtained in the same manner except that the monomer to be added is changed. It was.
The structure and the like of the synthesized resin (A) are shown below.

Preparation of resist composition (1)
10 g of the resin (F-1) was dissolved in 30 g of PGMEA (propylene glycol monomethyl ether acetate). To this solution, 0.5 g of molecular sieves 3A (in the form of pellets) was added and stirred for 24 hours, and the molecular sieves were filtered off under a dry nitrogen atmosphere.
The same treatment was performed on the resins shown in Table 1 other than the resin (F-1). A resist composition was prepared using the materials subjected to the above treatment in the following quantitative relationship, and the solid content concentration was adjusted to 6% by mass with PGMEA dehydrated by the same treatment as described above. This solution was filtered through a 0.1 μm Teflon filter in a dry nitrogen atmosphere to prepare a resist solution of Example 1.
Resin: 1.2 g, acid generator: 0.030 g, surfactant: 100 ppm with respect to the resin solution, organic basic compound: 0.0012 g, non-polymer type dissolution inhibitor: 0.24 g
50 μL of this resist composition was taken out and measured with a Karl Fischer moisture meter MKC-120 (manufactured by KYOTOELECTRONICS). The water content was 0.12% by mass.

Preparation of resist composition (2)
Resin (F-2) was used instead of resin (F-1), and the compound described in Example 2 in the following table was mixed in the same amount relationship as described above. Commercially available PGMEA and propylene glycol monomethyl ether were added to adjust the solid content concentration to 6% by mass. Molecular sieves 4A (in the form of pellets) was added at a rate of 1 g per 10 g and stirred for 12 hours. From this solution, molecular sieves were filtered off under a dry nitrogen atmosphere to obtain a resist composition of Example 2. The moisture content of this resist composition was measured in the same manner as described above.
Resist compositions of Examples 3 to 25 were obtained in the same manner except that the resin, acid generator, surfactant, organic basic compound, non-polymer type dissolution inhibitor, and solvent to be added were changed. Further, the water content was measured in the same manner as described above.

Preparation of resist composition (3)
Resist compositions of Comparative Examples 1 and 2 were prepared in the same manner as in the preparation of the resist composition (1) except that the resin used was changed and the treatment with molecular sieves was not performed. Further, the water content was measured in the same manner as described above.

Preparation of resist composition (4)
A resist composition was prepared in the same manner as in the preparation of the resist composition (3), and pure water was added and stirred well so that the water content shown in Table 1 was obtained. This solution was filtered through a 0.1 μm Teflon filter under a dry nitrogen atmosphere to obtain resist compositions of Comparative Examples 3 and 4. Further, the water content was measured in the same manner as described above.

Exposure Evaluation (ArF) (1)
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. A positive resist film having a thickness of 0.1 μm was formed. The resist film was subjected to pattern exposure using an ArF 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 film was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried. The pattern on the silicon wafer thus obtained was observed, and the minimum exposure amount for reproducing the mask pattern having a line width of 150 nm (line / space = 1: 1) was evaluated as sensitivity. Moreover, LER (line edge roughness) was evaluated by the following method.

LER (Line Edge Roughness) Evaluation Using a length-measuring scanning electron microscope (CD-SEM), an edge of a 0.15 micron line and space pattern (line / space = 1: 1) was measured. Within the measurement monitor, pattern edges were detected at a plurality of positions, and the variance (3σ) of variations in the detected positions was used as an index of edge roughness. The smaller the value, the better.

Relative sensitivity evaluation The resist composition was aged at 5 days, 15 days, and 30 days in a constant temperature room at 30 ° C., and the sensitivity was determined by the same method as described above on each elapsed time, and the relative sensitivity was determined according to the following formula: Asked.
Relative sensitivity = (sensitivity at time 0) / (sensitivity at time)

Transmittance with respect to light having a wavelength of 157 nm The positive resist composition prepared above was applied onto a calcium fluoride disk by a spin coater and dried by heating at 120 ° C. for 5 minutes to obtain a film having a thickness of 0.1 μm. These coatings were measured for absorption by a resist film using an Acton CAMS-507 spectrometer, and the transmittance of the resist film at a wavelength of 157 nm was calculated.

  Table 1 shows the composition of each sample and each evaluation result.

  In Table 1, the reference number of the photoacid generator refers to the number given to the specific examples described above in the specification. The resin has the structure described in the synthesis example. The other components refer to 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 D-1 : Megafuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
D-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

Non-polymeric dissolution inhibitor XA-1

Non-polymeric dissolution inhibitor XB-1

  From the results in Table 1, it can be seen that the composition of the present invention exhibits sufficient permeability and is excellent in line edge roughness and storage stability.

Claims (6)

(A1) a fluorine group-containing resin having a structure in which a fluorine atom is substituted on the main chain and / or side chain of the polymer skeleton, and having increased solubility in an alkali developer by the action of an acid;
(B) A positive resist composition containing a compound that generates an acid by the action of actinic rays or radiation, wherein the water content in the composition is 0.3% by mass or less. Resist composition. (A2) an alkali-soluble fluorine-containing resin having a structure in which a fluorine atom is substituted on the main chain and / or side chain of the polymer skeleton,
(B) a compound that generates an acid by the action of actinic rays or radiation, and
(X) A positive resist composition containing a non-polymer type dissolution inhibitor, wherein the moisture content in the composition is 0.3% by mass or less. 2. The positive resist composition according to claim 1, wherein the resin (A1) is a resin having a repeating unit containing a group represented by the following general formula (a).

In general formula (a),
R _{31 to} R ₃₆ each independently represent 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.
One of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.
Y ₀ represents a hydrogen atom or an organic group. 3. The positive resist composition according to claim 2, wherein the resin (A2) is a resin having a repeating unit containing a group represented by the following general formula (b).

In general formula (b),
R _{31 to} R ₃₆ each independently represent 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.
One of R _{31 to} R ₃₆ may be connected to the main chain of the resin via a carbon chain.
Y _0b represents a hydrogen atom or an acid non-decomposable organic group. The positive resist composition according to claim 1 or 3, wherein the resin (A1) contains a repeating unit containing a group in which a carboxyl group is protected with an acid-decomposable group. A pattern forming method comprising: forming a resist film from the resist composition according to claim 1, and exposing and developing the resist film.