JP2005070329A - Positive resist composition and pattern forming method using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist composition suitable for use under an exposure light source of ≤160 nm, particularly F<SB>2</SB>excimer laser light (157 nm), and to specifically provide an excellent positive resist composition which exhibits satisfactory transmittance when a light source of 157 nm is used, ensures diminished line edge roughness, and has a wide defocus latitude. <P>SOLUTION: The positive resist composition contains (A) a resin having a fluorine substituted structure in a principal chain and/or a side chain of a polymer skeleton, (B) a specified structure compound which generates an acid under the action of an actinic ray or a radiation, and (X) a non-polymer type dissolution inhibitor. <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 LER (line edge roughness) and DOF (defocus latitude) characteristics.

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

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

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

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

For F ₂ excimer laser light (157 nm), the above alicyclic resin also has a large absorption in the 157 nm region, and it has been found that this is insufficient to obtain the desired pattern of 0.1 μm or less. In contrast, non-patent document 1 (Proc.SPIE.Vol.3678.13 (1999)) reports that a resin having a fluorine atom (perfluoro structure) introduced has sufficient transparency at 157 nm, and effective fluorine. Non-Patent Document 2 (Proc. SPIE. Vol. 3999. 330 (2000)), Non-Patent Document 3 (Proc. SPIE. Vol. 3999.357 (2000)), Non-Patent Document 4 (Proc. SPIE Vol. 3999.365 (2000)), Patent Document 1 (International Publication No. WO 00/17712 pamphlet), etc., and studies on resist compositions containing fluorine-containing resins have been made.
In addition, Patent Document 2 (European Patent Application Publication No. 1041442), Patent Document 3 (European Patent Application Publication No. 1113334), Patent Document 4 (European Patent Application Publication No. 1207423), respectively, It has been studied to improve various performances of the positive resist composition by using a specific acid generator or by combining a specific acid generator and a specific resin.

However, a resist composition containing a fluororesin for F ₂ excimer laser light exposure has been desired to be improved in terms of line edge roughness and defocus latitude.

International Optical Engineering Bulletin (Proc.SPIE.) Vol.3678. P.13. (1999) International Optical Engineering Bulletin (Proc.SPIE.) Vol.3999. 330. (2000) International Optical Engineering Bulletin (Proc.SPIE.) Vol.3999. 357. (2000) International Optical Engineering Bulletin (Proc.SPIE.) Vol.3999. 365. (2000) WO-00 / 17712 pamphlet European Patent Application No. 1041442 European Patent Application No. 1113334 European Patent Application No. 1207423

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) (A) a 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 at least one actinic ray or radiation selected from a compound represented by the following general formula (PA) and a compound represented by the general formula (PB); and
(X) A positive resist composition containing a non-polymer type dissolution inhibitor.

In general formula (PA),
R ^{1b to} R ^3b each independently represents an organic group containing no aromatic ring.
Xa ^- represents a sulfonic acid, carboxylic acid, or sulfonyl imide anions.

In general formula (PB),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an aryl group or an alkenyl group, and any two or more of R _{1c to} R _5c are bonded to form an aromatic ring. It may be formed.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, or an aryl group.
Rx and Ry each independently represents an alkyl group, an allyl group, or a vinyl group.
Any two or more of R _1c to R _7c, and Rx and Ry may combine with each other to form a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond You may go out.
Xb ^- represents a sulfonic acid, carboxylic acid, or sulfonyl imide anions.

(2) The positive resist composition as described in (1) above, wherein the resin (A) is an alkali-soluble resin.
(3) The positive resist composition as described in (1) above, wherein the resin (A) is a resin that decomposes by the action of an acid and increases the solubility in an alkali developer.
(4) The positive electrode according to any one of (1) to (3) above, wherein the resin (A) is a resin having a repeating unit containing a group represented by the following general formula (a): Type resist composition.

In general formula (a),
R _{31 to} R ₃₆ each independently represents 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 a single bond or a carbon chain and may be connected to the main chain of the resin as the component (A).
Y ₀ represents a hydrogen atom or an organic group.

(5) The resin (A) contains a repeating unit containing a carboxyl group or a group obtained by protecting a carboxyl group with an acid-decomposable group, according to any one of the above (1) to (4), A positive resist composition.

The preferred embodiments of the present invention will be further described below.
(6)
2. The positive resist composition according to claim 1, wherein the resin of component (A) has at least one selected from the group of repeating units represented by the following general formulas (I) to (XII). .

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.
A ₁ is a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₂₂ —, —CO—O—R ₂₃ —, —CO—N (R ₂₄ ). -R ₂₅ - represents a.
R ₂₂ , R ₂₃ and R _{25 each} have a single bond or an ether group, ester group, amide group, urethane group or ureido group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group. Represents.
R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.

In general formula (VI),
Rx ₁ to Rx ₃ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or at least one alkyl group wherein a hydrogen atom is substituted with a fluorine atom.
R _{61 to} R ₆₆ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{61 to} R ₆₆ is a fluorine atom.
R _{67 to} R ₇₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{67 to} R ₇₂ is a fluorine atom.
Z ₁ represents a 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.
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),
Ra _{4 to} Ra ₆ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an aryl group, an alkoxy group or an aralkyl group.
Y ₅ represents a hydrogen atom or an organic group.
L ₄ represents a single bond or a divalent linking group.
m represents 1 or 2.

(7) The (X) non-polymer type dissolution inhibitor is a compound represented by the following general formula (IA) or (IB), and is described in any one of (1) to (6) above A positive resist composition.

式（ＸＡ）および式（ＸＢ）中、
ＡＲは各々独立に脂環式炭化水素基を表す。
Ｒ₈₁〜Ｒ₈₆は各々独立に水素原子、フッ素原子またはアルキル基を表す。ただし、Ｒ₈₁〜Ｒ₈₆のうち少なくとも１つはフッ素原子である。
Ｒ₈₇およびＲ₈₈は、各々独立にハロゲン原子、ヒドロキシ基、アルコキシ基、シアノ基またはアルキル基を表す。
Ｌ₃およびＬ₄は、各々独立に単結合または２価の連結基を表す。
Ｚ₁およびＺ₂は、各々独立に水素原子または有機基を表す。
Ｍ₁は、単結合または２価の連結基を表す。
Ｍ₂は、（ｇ＋ｈ）価の連結基を表す。
ａおよびｂは、各々独立に０以上５以下の整数を表す。ただし、２≦ａ＋ｂ≦１０を満たす。
ｃは、０以上５以下の整数を表す。
ｄおよびｅは、各々独立に０以上５以下の整数を表す。ただし、１≦ｄ＋ｅ≦１０を満たす。
ｆは、各々独立に０以上５以下の整数を表す。
ｇは、２以上６以下の整数を表す。
ｈは、０以上５以下の整数を表す。
一般式（ＩＡ）又は（ＩＢ）で示される化合物中には、酸分解性基がそれぞれ少なくとも２つ以上含まれる。

In formula (XA) and formula (XB),
Each AR independently represents an alicyclic hydrocarbon group.
R _{81 to} R ₈₆ each independently represents a hydrogen atom, a 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 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 or an organic 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 of 0 or more and 5 or less.
d and e each independently represents an integer of 0 or more and 5 or less. However, 1 ≦ d + e ≦ 10 is satisfied.
f represents an integer of 0 to 5 independently of each other.
g represents an integer of 2 to 6.
h represents an integer of 0 to 5.
The compound represented by the general formula (IA) or (IB) contains at least two acid-decomposable groups.

(8) The AR in the general formula (IA) or (IB) is a benzene residue, a cyclohexane residue, a norbornane residue, an adamantane residue, or a tetracyclododecane residue, The positive resist composition as described in (7).
(9) The positive resist composition as described in any one of (1) to (8) above, further comprising (E) an organic basic compound.
(10) The positive resist composition as described in any one of (1) to (9) above, further comprising (D) a surfactant.

(11) Xa ⁻ and Xb ^{− in the} general formula (PA) or (PB) are anions of an organic sulfonic acid, and the general formula (PA) or (PB) is organic by the action of actinic rays or radiation. The positive resist composition as described in any one of (1) to (10) above, which is a compound that generates sulfonic acid.
(12) wherein Xa in the general formula (PA) or (PB) ^- and Xb ^- is the anion of an organic sulfonic acid containing at least one fluorine atom, the formula (PA) or (PB) is, The positive resist composition as described in (11) above, which is a compound that generates an organic sulfonic acid containing at least one fluorine atom by the action of actinic rays or radiation.

(13) The positive resist composition as described in (12) above, further comprising, as component (B1), a compound that generates an organic sulfonic acid that does not contain a fluorine atom by the action of actinic rays or radiation. Stuff.
(14) The positive resist composition as described in (11) or (12) above, further comprising (B2) a compound capable of generating a carboxylic acid by the action of actinic rays or radiation.
(15) A pattern forming method comprising: forming a resist film from the resist composition according to any one of (1) to (14); and exposing and developing the resist film.

Accordingly, an object of the present invention is to provide a positive resist composition suitable for use as an exposure light source of 160 nm or less, particularly F ₂ excimer laser light (157 nm), and is specifically sufficient when a light source of 157 nm is used. The present invention provides a positive resist composition that exhibits excellent transparency, suppresses line edge roughness, and has a wide defocus latitude.

  According to the present invention, a positive resist exhibiting sufficient transmission even at a wavelength shorter than 160 nm, particularly at a short wavelength of F2 excimer laser light (157 nm), excellent in sensitivity and pattern profile at the time of pattern formation, and generating less development residue (scum). A composition can be provided.

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] (A) Fluorine Atom-Containing Resin The fluorine atom-containing resin in the present invention (A) is a resin (hereinafter referred to as resin (A), ( A) also referred to as component). The resin (A) may be a resin soluble in an alkali developer (alkali-soluble resin), and has a group (acid-decomposable resin) that decomposes by the action of an acid and increases the solubility in an alkali developer. ).
More preferably, the fluorine atom-containing resin has at least one site selected from a perfluoroalkylene group and a perfluoroarylene group in the main chain of the polymer skeleton, or a perfluoroalkyl group, a perfluoroaryl group, a hexafluoro-2. -A fluorine atom-containing resin having at least one site selected from a group in which a propanol group and an OH group of a hexafluoro-2-propanol group are protected in the side chain of the polymer skeleton.

  The alkali-soluble resin is a resin that has a group such as —OH or —COOH in the side chain and is soluble in an alkali developer. When the alkali-soluble resin is used as a film, the dissolution rate (23 ° C.) with respect to 0.261N tetramethylammonium hydroxide (TMAH) is preferably 170 A / second or more, and k is 330 A / second or more. More preferred (A is angstrom).

The acid-decomposable resin is a resin that is decomposed by the action of an acid and becomes alkali-soluble, and is a resin containing an acid-decomposable group described later. When decomposed by the action of an acid, it is preferable to have the above-mentioned dissolution rate in an alkali developer.
The fluorine atom-containing resin in the present invention is preferably a resin having a repeating unit having a group represented by the general formula (a).

In general formula (a),
R _{31 to} R ₃₆ each independently represents 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 a single bond or a carbon chain and may be connected to the main chain of the resin as the component (A).
Y ₀ represents a hydrogen atom or an organic 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 carboxyl group or a group obtained by protecting the 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 resin in the present invention is more preferably a resin having at least one selected from the group of repeating units represented by the general formulas (I) to (XII).

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 0 to 5, and more preferably 0 to 3.
A ₁ is a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₂₂ —, —CO—O—R ₂₃ —, —CO—N (R ₂₄ ). -R ₂₅ - represents a.
R ₂₂ , R ₂₃ and R _{25 each} have a single bond or an ether group, ester group, amide group, urethane group or ureido group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group. Represents.
R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.
In the formula (V), the group represented by R ₇ 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.
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. Ra _{1 to} Ra ₃ are preferably a hydrogen atom, a halogen atom or an alkyl group substituted with at least one halogen atom. The halogen atom is preferably a fluorine atom. Ra _{1 to} Ra ₃ are more preferably a hydrogen atom, a fluorine atom or a trifluoromethyl group, and Ra ₁ is particularly preferably a fluorine atom or a trifluoromethyl group.
Y ₄ represents a hydrogen atom or an organic group.
m represents 1 or 2.
In general formula (XII),
Ra _{4 to} Ra ₆ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an aryl group, an alkoxy group or an aralkyl group. Ra _{4 to} Ra ₆ are preferably a hydrogen atom or a halogen atom. When any one of the plurality of Ra ₄ to Ra ₆ is a halogen atom, the halogen atom is preferably a fluorine atom. It is particularly preferred that Ra ₄ is a fluorine atom.
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.

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, or 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. More preferably, it is a perfluoroalkyl group, for example, one having 4 to 12 carbon atoms, specifically, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorooctylethyl group, a perfluoro group. A more preferred example is a dodecyl group.

  The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferred examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The polycyclic type has 6 to 20 carbon atoms, such as an adamantyl group, norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, 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.

As the divalent linking group, one or two selected from the group consisting of an alkylene 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, or a urea group It represents a combination of the above groups. Examples of the alkylene group in A include groups represented by the following formulas.
− [C (Rb) (Rc)] r −
In the formula, Rb and Rc each represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and they may be the same or different. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the substituent that the alkyl group has include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms). Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.
As the divalent linking group, a single bond or a methylene group is particularly preferable.
The organic group may be an acid-decomposable organic group (acid-decomposable group) or a non-acid-decomposable organic group, and the same as Zb in the general formula (a) Can be mentioned.

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

The 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, the resin (A) may further contain other repeating units. Other repeating units that can be contained are not particularly limited, but are preferably repeating units represented by the following formula (D).

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 (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 addition to the above repeating structural unit, the resin of the present invention (A) may be copolymerized with other polymerizable monomers for the purpose of further improving the performance of the positive resist of the present invention.

  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 addition amount of the resin (A) is generally 50 to 99.5% by mass, preferably 60 to 98% by mass, more preferably 65 to 95% by mass, based on the total solid content of the composition. The
In the resin (A), the content of the repeating unit having an acid-decomposable group is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol%.

In the resin (A), the content of the repeating unit including the partial structure represented by the general formula (a) is usually 3 to 95 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol%. is there.
In the resin (A), the content of the repeating units represented by the general formulas (I) to (III) is usually 3 to 90 mol%, preferably 5 to 80 mol%, more preferably 7 to 70 mol%. is there.
In the resin (A), the content of the repeating units represented by the general formulas (IV) to (XII) is usually 1 to 80 mol%, preferably 3 to 65 mol%, more preferably 5 to 50 mol%. is there.

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

  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.

  It is preferable that the amount of metal components such as Na, K, Ca, Fe, and Mg contained in the resin (A) is small. 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.

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

[2] (B) A compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter sometimes referred to as an acid generator or a component (B)).
In the composition of the present invention, an acid is generated by the action of at least one actinic ray or radiation selected from the compound represented by the general formula (PA) and the compound represented by the general formula (PB) as the acid generator. Contains at least one compound to be generated.

  The compound represented by the general formula (PA) is a sulfonium salt having no aromatic ring, that is, a salt having sulfonium as a cation.

In general formula (PA), R ^<1b > -R < ^3b > represents the organic group which does not contain an aromatic ring each independently. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group that does not contain an aromatic ring as R ^{1b to} R ^3b generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R ^{1b to} R ^3b are each independently preferably an alkyl group, an allyl group, or a vinyl group, more preferably a linear, branched, cyclic 2-oxoalkyl group, an alkoxycarbonylmethyl group, most preferably a linear group, A branched 2-oxoalkyl group. The 2-oxoalkyl group may be linear, branched or cyclic, and preferably includes a group having> C═O at the 2-position of the above alkyl group. The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
The alkyl group as R ^{1b to} R ^3b may be linear, branched or cyclic, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group). Group, butyl group, pentyl group) and cyclic alkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
R ^{1b to} R ^3b may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
Two of R ^{1b to} R ^3b may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R ^{1b to} R ^3b include an alkylene group (eg, butylene group, pentylene group).
From the viewpoint of photoreactivity, any one of R ^{1b to} R ^3b is preferably a group having a carbon-carbon double bond or a carbon-oxygen double bond.

Xa ^- represents a sulfonic acid, carboxylic acid, or sulfonyl imide anions. Preferred is a sulfonate anion, and more preferred is an alkane sulfonate anion substituted at the 1-position by a fluorine atom, or a benzene sulfonate substituted with an electron-withdrawing group. The alkane portion of the alkanesulfonate anion may be substituted with a substituent such as an alkoxy group (for example, having 1 to 8 carbon atoms) or a perfluoroalkoxy group (for example, having 1 to 8 carbon atoms).
Examples of the electron withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkoxycarbonyl group, an acyloxy group, and an acyl group.
Xa ^- it is more preferably a perfluoro alkanesulfonic acid anion having 1 to 8 carbon atoms, particularly preferably perfluorooctane sulfonate anion, a perfluoro butane sulfonic acid anion, trifluoromethanesulfonic acid anion, and most preferably Par Fluorobutane sulfonate anion and trifluoromethane sulfonate anion. By using these, the decomposition rate of the acid-decomposable group is improved, the sensitivity is excellent, the diffusibility of the generated acid is controlled, and the resolution is improved.
Formula at least one of R ^1b to R ^3b of the compounds represented by (PA) is, may take at least one and coupled to the structure of R ^1b to R ^3b of the general formula (PA) Other compounds of the general.

  Although the specific example of the sulfonium salt which does not have an aromatic ring which can be used by this invention is shown below, this invention is not limited to these.

  The compounds represented by the formula (PA) can be used singly or in combination of two or more.

The compound represented by the formula (PA) can be synthesized by a usual method. An example is given below. (Synthesis of Specific Example (II-11))
11.8 g of tetrahydrothiophene was dissolved in 100 ml of acetonitrile, and 20 g of 1-bromo-3,3-dimethyl-2-butanone was slowly added to this solution. When stirred at room temperature for 2 days, a powder precipitated. After adding 100 ml of ethyl acetate to the reaction solution, the powder was collected by filtration, washed with ethyl acetate and dried to obtain 24 g of 2-oxo-3,3-dimethylbutyltetrahydrothiophenium bromide.
10 g of potassium perfluorobutanesulfonate was dissolved in a mixed solvent of 500 ml of water and 100 ml of methanol, and a solution obtained by dissolving 7.75 g of 2-oxo-3,3-dimethylbutyltetrahydrothiophenium bromide in 50 ml of methanol was added thereto. It was. This aqueous solution was extracted twice with 100 ml of chloroform, and the organic phase was washed with water and concentrated to obtain an oily substance. When ethyl acetate was added thereto and re-concentrated, a solid substance was obtained, which was collected by filtration and reslurried with diisopropyl ether to obtain 9 g of 2-oxo-3,3-dimethylbutyltetrahydrothiophenium perfluorobutane sulfonate. It was.

  2-oxocyclohexylmethyl (2-norbornyl) sulfonium trifluoromethanesulfonate (II-1) can be synthesized using the method described in JP-A-8-27102 and Synthesis Example 1.

  The compound represented by the general formula (PB) is a compound having the following phenacylsulfonium salt structure.

R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, or an aryl group.
Rx and Ry each independently represents an alkyl group, an allyl group, or a vinyl group. The 2-oxoalkyl group may be linear, branched or cyclic, and preferably includes a group having> C═O at the 2-position of the above alkyl group. The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
Any two or more of R _1c to R _7c, and Rx and Ry may combine with each other to form a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond You may go out.
Xb ^- represents a sulfonic acid, carboxylic acid, or sulfonyl imide anions.

The alkyl group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkyl group having 1 to 10 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms. (For example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group), a C3-C8 cyclic alkyl group (for example, a cyclopentyl group, a cyclohexyl group). Can be mentioned.
The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).
Preferably either a straight chain of R _1c to R _5c, branched, cyclic alkyl group, or a linear, branched or cyclic alkoxy group, more preferably the sum of the carbon atoms of R _5c from R _1c 2 to 15 It is. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of the preservation | save of a resist composition.

_Examples of the alkyl group as R _6c and R _7c include the same alkyl groups as R _{1c to} R _5c . As an aryl group, a C6-C14 aryl group (for example, phenyl group) can be mentioned, for example.
The alkyl group as Rx and Ry may be the same as those of the alkyl group as R _1c to R _5c.
Examples of the group formed by combining Rx and Ry include a butylene group and a pentylene group.

In the compound of the formula (PB), the three-dimensional structure is fixed by forming a ring, and the optical resolution is improved. When any two of R _{1c to} R _7c are combined to form a ring structure, any one of R _{1c to} R _5c and one of R _6c and R _7c are combined to form a single bond or a linkage A case where a ring is formed is preferable, and a case where R _5c and R _6c or R _7c are bonded to each other to form a single bond or a linking group is preferable.
As the linking group, an alkylene group which may have a substituent, an alkenylene group which may have a substituent, -O-, -S-, -CO-, -CONR- (R is a hydrogen atom, An alkyl group, an acyl group), and a group formed by combining two or more of these, and an alkylene group, an alkylene group containing an oxygen atom, or a sulfur atom which may have a substituent. An alkylene group is preferred.
Examples of the substituent include an alkyl group (preferably having 1 to 5 carbon atoms), an aryl group (preferably having 6 to 10 carbon atoms, for example, a phenyl group), an acyl group (for example, having 2 to 11 carbon atoms), and the like. .
Further, a methylene group, an ethylene group, a propylene group, -CH ₂ -O -, - preferably a linking group to form a 5- to 7-membered ring as CH ₂ -S-, ethylene group, -CH ₂ -O-, A linking group that forms a 6-membered ring such as —CH ₂ —S— is particularly preferred. By forming a 6-membered ring, the carbonyl plane and the C—S + sigma bond become more perpendicular, and the optical resolution is improved by orbital interaction.
Further, it may be a compound that is bonded via a single bond or a linking group at any position of R _{1c to} R _7c and Rx and Ry and has two or more structures of the formula (PB).

Xb ^- is preferably a sulfonate anion, more preferably 1-position benzenesulfonic acid substituted with substituted alkanesulfonic acid anion, or an electron-withdrawing group by a fluorine atom. The alkane portion of the alkanesulfonate anion may be substituted with a substituent such as an alkoxy group (for example, having 1 to 8 carbon atoms) or a perfluoroalkoxy group (for example, having 1 to 8 carbon atoms). Examples of the electron withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkoxycarbonyl group, an acyloxy group, and an acyl group.
Xb ^- it is more preferably a perfluoro alkanesulfonic acid anion having 1 to 8 carbon atoms, particularly preferably perfluorooctane sulfonate anion, a perfluoro butane sulfonic acid anion, trifluoromethanesulfonic acid anion, and most preferably Par Fluorobutane sulfonate anion and trifluoromethane sulfonate anion. By using these, the decomposition rate of the acid-decomposable group is improved, the sensitivity is excellent, and the diffusibility of the generated acid is controlled to improve the resolution.
Specific examples of the compound having a phenacylsulfonium salt structure that can be used in the present invention are shown below, but the present invention is not limited thereto.

  The compound represented by the formula (PB) can be used alone or in combination of two or more.

  The compound represented by the formula (PB) is synthesized, for example, by reacting a corresponding acylbenzene derivative with a trialkylsilyl halide under basic conditions to form a silyl enol ether, and reacting this with a sulfoxide to synthesize a sulfonium skeleton. It can be obtained by salt exchange with the corresponding anion. As another synthesis method, a method in which a corresponding phenacyl halide and a sulfide compound are reacted in the presence of a non-catalyst or a silver catalyst to synthesize a sulfonium skeleton and salt-exchange it with the corresponding anion can be mentioned.

In the present invention, Xa ⁻ and Xb ^{− in the} general formulas (PA) and (PB) are preferably anions of organic sulfonic acid. The compounds represented by the general formulas (PA) and (PB) are preferably compounds that generate an organic sulfonic acid by the action of actinic rays or radiation, and more preferably, the general formula (PA) or Xa ⁻ and Xb ^{− in} (PB) are anions of an organic sulfonic acid containing at least one fluorine atom, and the general formula (PA) or (PB) is at least one by the action of actinic rays or radiation. It is a compound that generates an organic sulfonic acid containing a fluorine atom.

In the present invention, the amount of the compound represented by the general formula (PA) or (PB) is generally 1% by mass or more, preferably 1.5 to 12 based on the total solid content of the positive resist composition. It is 2 mass%, More preferably, it is 2-8 mass%.
In addition, a sulfonium salt having no aromatic ring represented by the general formula (PA) or a compound having a phenacylsulfonium salt structure represented by the general formula (PB) may be used alone, or a plurality of them may be mixed. May be used.
When the compound represented by the formula (PA) and the compound represented by the formula (PB) are used in combination, it is preferably used in a molar ratio of (PA) :( PB) = 1: 99 to 99: 1. More preferably, (PA) :( PB) = 5: 95 to 95: 5.

  Further, the following other acid-generating compounds that can be used in combination may be used alone or in combination.

The positive resist composition of the present invention is a compound that generates an acid upon irradiation with other actinic rays or radiation, particularly F ₂ excimer laser light, in addition to the compounds represented by the general formulas (PA) and (PB). May be contained.

The acid generator that can be used in combination is preferably a compound (B1 component) that generates an organic sulfonic acid that does not contain a fluorine atom when irradiated with actinic rays or radiation, particularly F ₂ excimer laser light.

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

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

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

  Examples of such compounds include diazonium salts described in, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), TSBaletal, Polymer, 21, 423 (1980), U.S. Pat.No. 4,069,055, 4,069,056, Re27,992, ammonium salts described in JP-A-3-140140, DCNecker et al, Macromolecules, 17, 2468 (1984), CS Wen et al, Teh, Proc. Conf. Rad. CuringASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056, etc., phosphonium salts, JVCrivelloetal, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent Nos. 104,143, 339,049, 410,201, JP-A-2-150848, JP-A-2-96514 and the like, JVCrivelloetal, Polymer J. 17, 73 (1985) ), JV Crivello etal., J. Org. Chem., 43, 3055 (1978), WR Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JVCrivello etal, Polymer Bull ., 14, 279 (1985), JV Crivelloetal, Macromorecules, 14 (5), 1141 (1981), JV Crivello et al, J. PolymerSci., Polymer Chem. Ed., 17, 2877 (1979), European Patent Nos. 370,693, 161,811, 410,201, 339,049, 233,567, 297,443 No. 297,442, U.S. Pat.Nos. Selenonium salts described in Crivelloetal, Macromorecules, 10 (6), 1307 (1977), JV Crivello et al, J. PolymerSci., Polymer Chem. Ed., 17, 1047 (1979), CS Wen etal, Teh, Proc. Onium salts such as arsonium salts described in Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B 46-4605, JP-A 48-36281, JP-A 55- 32070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63-70243 Organic halogen compounds described in JP-A-63-298339 K. Meieretal, J. Rad. Curing, 13 (4), 26 (1986), TP Gill et al, Inorg. Chem., 19, 3007 (1980), D. Astruc, Acc. Chem. Res., 19 ( 12), 377 (1896), and organometallic / organic halides described in JP-A-2-16145, S. Hayasetal, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al, J. holymerSci., PolymerChem. Ed., 23, 1 (1985), QQ Zhuetal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahedron Lett., (24) 2205 (1973), DHR Bartonetal, J. ChemSoc., 3571 (1965), PM Collins et al, J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinsteinet al, Tetrahedron Lett., (17), 1445 (1975), JW Walkeret al, J. Am. Chem. Soc., 110, 7170 (1988), SC Busman et al, J. ImagingTechnol., 11 (4), 191 (1985), HMHoulihan et al, Macromolecules, 21, 2001 ( 1988), PMCollinset al, J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayaseet al, Macromolecules, 18, 1799 (1985), E. Reichmanis et al, J. Electrochem. Soc. , SolidState Sci. Technol., 130 (6), FM Houlihan et al, Macromolcules, 21, 2001 (1988), European Patent 0290,750 No. 046,083, No. 156,535, No. 271,851, No. 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, JP-A-53-133022, etc. Photoacid generator having a protecting group, M.TUNOOKAetal, PolymerPreprints Japan, 35 (8), G. Berneret al, J. Rad. Curing, 13 (4), WJMijs etal, CoatingTechnol., 55 (697), 45 ( 1983), Akzo, H. Adachi et al, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 044,115, 618,564, 0101,122, U.S. Patent No. 4,371,605 No. 4,431,774, JP-A No. 64-18143, JP-A No. 2-245756, JP-A No. 3-140109, etc. Examples thereof include disulfone compounds described in JP-A-61-166544.

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

B1 component is a compound that generates an aliphatic or aromatic sulfonic acid containing no fluorine atom as an anion,
A combination in which the component B2 is an ionic compound having an aliphatic or aromatic carboxylic acid which may have a fluorine atom.

[A] Compound that generates fluorine-free sulfonic acid upon irradiation with actinic light or radiation and ionic compound having fluorine-free sulfonic acid as an anion Compound and anion that generates fluorine-free sulfonic acid upon irradiation with actinic light or radiation Examples of the ionic compound having a fluorine-free sulfonic acid include an iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the general formula (PAG4).

In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group.
Z ⁻ represents a sulfonate anion containing no fluorine atom.
Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

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

Preferred examples of the sulfonate anion containing no fluorine atom as Z ⁻ include aliphatic hydrocarbons having 1 to 20 carbon atoms and aromatic hydrocarbons having 5 to 20 carbon atoms. These may have a substituent. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms, a phenylamino group, a phenylcarbonyl group, a halogen atom, and a hydroxyl group. Can be mentioned. For aromatic hydrocarbons, there can be further mentioned alkyl groups having 1 to 15 carbon atoms.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The photoacid generator, that is, the compound represented by the general formula (AI), the general formula (AII), or the general formula (AIII) is prepared by the method described in US Pat. No. 3,734,928, Macromolecules, vol. 10.1307 (1977), Journalof Organic Chemistry, vol. 55, 4222 (1990), J. Radiat.Curing, vol. 5 (1), 2 (1978) It can be synthesized by exchanging. The compounds represented by formulas (AIV) and (AV) are prepared by reacting an N-hydroxyimide compound and carboxylic acid chloride under basic conditions, or reacting nitrobenzyl alcohol and carboxylic acid chloride under basic conditions. Can be obtained.

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

  In the resist composition of the present invention, in addition to the acid generators represented by the general formulas (PA) and (PB), fluorine is irradiated by actinic rays or radiation represented by the following formulas (PAG3a) and (PAG4a). A compound that generates an atom-containing sulfonic acid is also preferably used in combination.

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

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

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

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

[3] Non-polymer type dissolution inhibitor (X)
The positive resist composition of the present invention contains a non-polymer type dissolution inhibitor (X component). Non-polymer type dissolution inhibitors are compounds whose solubility in an alkaline developer is increased by the action of an acid.
Here, the non-polymer type dissolution inhibitor is a compound in which at least two or more acid-decomposable groups are present in a compound having a molecular weight of 3000 or less, and the solubility in an alkali developer is increased by the action of an acid. is there.
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),
Each AR independently represents an alicyclic hydrocarbon group.
R _{81 to} R ₈₆ each independently represents a hydrogen atom, a 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 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. However, the compounds represented by formula (XA) and formula (XB) each contain two or more acid-decomposable groups.
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 of 0 or more and 5 or less.
d and e each independently represents an integer of 0 or more and 5 or less. However, 1 ≦ d + e ≦ 10 is satisfied.
f represents an integer of 0 to 5 independently of each other.
g represents an integer of 2 to 6.
h represents an integer of 0 to 5.

  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 divalent linking groups include alkylene groups, cycloalkylene groups, arylene groups, and combinations thereof with ether groups, thioether groups, carbonyl groups, ester groups, amide groups, sulfonamide groups, urethane groups, urea groups, and the like. 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.

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 3 or more carbon atoms. The aromatic ring residue is preferably one having 5 to 30 carbon atoms, more preferably one having 6 to 25 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 hydrocarbon group of AR may be monocyclic or polycyclic, and specifically includes those having an alicyclic structure such as monocyclo, bicyclo, tricyclo, tetracyclo, etc. having 3 or more carbon atoms. The carbon number is preferably 5 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 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.

  Specific examples of the compound represented by (XA) are shown below, but the present invention is not limited to these specific examples.

  Specific examples of the compound represented by (XB) 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 addition amount of the non-polymer type dissolution inhibitor (X) is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 7 to 30% by mass with respect to the polymer in the composition.

  The non-polymeric dissolution inhibitor (X) can be synthesized by protecting a readily available compound containing a plurality of alkali-soluble groups in one molecule with a degradable 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.

[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. By setting the molar ratio to 2.5 or more, high sensitivity is obtained, and by setting the molar ratio to 300 or less, it is possible to reduce the thickness of the resist pattern over time until post-exposure heat treatment and improve resolution. . (Acid generator) / (organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

  The composition of the present invention is dissolved in a solvent that dissolves each of the above components and coated on a support. Solvents used here include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol 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, tetrahi Preferably such Rofuran, the use of these solvents alone or in combination.

  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.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

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

(1) Synthesis of intermediate (M-1) 147.9 g (0.564 mol) of 5-norbornene-2-trifluoromethyl-2-carboxylic acid tbutyl ester was stirred and dissolved in 150 g of tetrahydrofuran, and while cooling, borane- 750 ml of tetrahydrofuran complex (1.0 M solution) was added dropwise over 1 hour. After the addition, the mixture was further stirred for 2 hours, 282 g of a sodium hydroxide aqueous solution (40 wt%) was added, and 241.2 g of hydrogen peroxide (30 wt% aqueous solution) was added dropwise over 1 hour. After dropping, the mixture was further stirred for 3 hours. Thereafter, the mixture was neutralized with an HCl acid solution, and 600 g of ethyl acetate was added to carry out a liquid separation operation. The organic layer was dehydrated using 50 g of magnesium sulfate and the solvent was distilled off, and then the product was purified by silica gel chromatography to obtain 134.37 g of intermediate (M-1) (yield 85%).

(2) Synthesis of Non-polymer Type Dissolution Inhibitor (XB-5) To a dry, nitrogen-substituted reaction vessel, 500 ml of dehydrated tetrahydrofuran and 16 g (0.4 mol) of sodium hydroxide (60%) were added and stirred at 0 ° C. Cooled to. Thereto was added dropwise a dehydrated tetrahydrofuran solution (200 ml) of 112.11 g (0.4 mol) of the intermediate (M-1) over 1 hour, and the mixture was further stirred for 1 hour. Thereafter, 27.40 g (0.2 mol) of epibromohydrin in dehydrated tetrahydrofuran (200 ml) was titrated over 1 hour, and after the dropwise addition, the reaction solution was stirred for 3 hours while warming to room temperature. Thereafter, an HCl solution was added for neutralization, and ethyl acetate / water was added to carry out a liquid separation operation. The organic layer was dehydrated using magnesium sulfate, the solvent was distilled off, and the product was purified by silica gel chromatography to obtain 77.70 g of non-polymer type dissolution inhibitor (XB-5) (yield 63%). .
Similarly, each dissolution inhibitor of the present invention was prepared.

(3) Synthesis of Resin (A-1) In a 1 L autoclave, 15.42 g (0.10 mol) of 5-norbornene-2-exo-3-exo-dimethanol, norbornene-2-carboxylic acid t-butyl ester 19 A solution of .4 g (0.10 mol) of 1,1,2-trichloro-trifluoroethane in 150 ml was charged and pressurized to 200 psi under a nitrogen atmosphere. Further, 20 g (0.20 mol) of tetrafluoroethylene was injected and heated to 50 ° C. with stirring. To this reaction solution, a solution of 1.2 g of di (4-t-butylcyclohexyl) peroxydicarbonate in 15 ml of 1,1,2-trichloro-trifluoroethylene was poured over 20 minutes, and stirring was further continued for 20 hours. After completion of the reaction, the reaction solution was poured into 2 L of methanol with vigorous stirring to precipitate a white resin. The precipitated resin was separated by filtration and dried under vacuum to obtain 23.5 g of the resin (A-1) of the present invention.
According to GPC measurement, the molecular weight of the resin (A-1) was 6,200 in terms of weight average (Mw). Further, the composition of the resin (A-1) was examined by C ¹³ -NMR measurement. As a result, the structural example was tetrafluoroethylene / 5-norbornene-2-exo-3-exo-dimethanol / norbornene-2-carboxylic acid. Acid t-butyl ester = 50/25/25.

(4) Synthesis of Resin (A-17) 11.05 g (0.06 mol) of 2-trifluoromethylacrylic acid (2-hydroxyethyl) ester and 7.77 g (0 of 5-norbornene-2-carboxylic acid tbutyl ester) 0.04 mol) was charged into a reaction vessel, and the reaction system was purged with nitrogen. Then, 0.248 g (0.001 mol) of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and nitrogen was introduced into the reaction system. The mixture was heated and stirred at 65 ° C. while flowing. Two hours later, 4 hours, 6 hours, 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 reaction solution was cooled to room temperature, and the reaction solution was dropped into 2 L of hexane. The powder was taken out by filtration and dried under reduced pressure at 50 ° C. to obtain 10.54 g of powder (yield 56%). The obtained powder had a weight average molecular weight of 13,400 and a dispersity of 1.51 as determined by gel permeation chromatography (GPC). The composition ratio of 2-trifluoromethylacrylic acid (2-hydroxyethyl) ester / 5-norbornene-2-carboxylic acid tbutyl ester by 1H-NMR, 13C-NMR, and 19F-NMR analysis was 60/40. It was.

  Similarly, each resin of the present invention was obtained. The weight average molecular weight and dispersity of the obtained resin are shown below.

Examples 1 to 12 and Comparative Example 1
Resin shown in Table 2 below: 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, solvent 19 The polymer solution dissolved in .6 was filtered through a 0.1 μm Teflon filter to prepare a positive resist solution.
In Table 2, the reference number of the photoacid generator refers to the number given to the specific examples described above in the specification.

Exposure Evaluation The positive resist solution prepared as described above was applied on a silicon wafer coated with an antireflection film (DUV42-6, manufactured by Brewer Science. Inc.) using a spin coater, and heated at 120 ° C. for 60 seconds. The film was dried to obtain a positive resist film having a thickness of 0.1 μm. The obtained resist film was subjected to pattern exposure using an ArFμ stepper using a line and space mask (line / space = 1/1), and immediately after the exposure, it was heated on a hot plate at 130 ° C. for 90 seconds. Further, the resist film was developed with 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 resist performance of the resist pattern obtained as described above was evaluated by the following method.

(1) LER (Line Edge Roughness)
Using a CD-SEM (measurement scanning electron microscope), the 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 variation in detected positions was used as an index of edge roughness (unit: nm). The smaller the value, the better.

(2) DOF (defocus latitude) evaluation Exposure that reproduces a 0.15 micron line and space pattern (line / space = 1/1) on the wafer using a CD-SEM (length measuring scanning electron microscope). In terms of quantity, the focus width (μm) capable of reproducing a 0.15 micron line pattern was observed as defocus latitude (DOF). A larger value is preferable.

In the above table, the abbreviations for surfactant mean the following.
D-1: Megafuck F176 (Dainippon Ink Co., Ltd.) (Fluorine)
D-2: Megafuck R08 (Dainippon Ink Co., Ltd.) (fluorine and silicon)

In the above table, the abbreviations for basic compounds mean the following.
N-1: 1,5-diazabicyclo [4.3.0] -5-nonene N-2: 2,4,5-triphenylimidazole N-3: N-hydroxyethylpiperidine N-4,2,6- Diisopropylaniline N-5: Dicyclohexylmethylamine N-6: Hexamethylenetetramine N-7: 1,8-diazabicyclo [5.4.0] -7-undecene

Further, the abbreviations for solvents mean the following.
S-1: Ethyl lactate S-2: Propylene glycol monomethyl ether acetate S-3: Propylene glycol monomethyl ether

The acid generator A used for comparison has the following structure.

  From the results in Table 7, it can be seen that the composition of the present invention has excellent line edge roughness, a wide defocus latitude, and is excellent.

Claims (6)

(A) a 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 at least one actinic ray or radiation selected from a compound represented by the following general formula (PA) and a compound represented by the general formula (PB); and
(X) A positive resist composition containing a non-polymer type dissolution inhibitor.

In general formula (PA),
R ^{1b to} R ^3b each independently represents an organic group containing no aromatic ring.
Xa ^- represents a sulfonic acid, carboxylic acid, or sulfonyl imide anions.
In general formula (PB),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an aryl group or an alkenyl group, and any two or more of R _{1c to} R _5c are bonded to form an aromatic ring. It may be formed.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, or an aryl group.
Rx and Ry each independently represents an alkyl group, an allyl group, or a vinyl group.
Any two or more of R _1c to R _7c, and Rx and Ry may combine with each other to form a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond You may go out.
Xb ^- represents a sulfonic acid, carboxylic acid, or sulfonyl imide anions.   The positive resist composition according to claim 1, wherein the resin (A) is an alkali-soluble resin.   2. The positive resist composition according to claim 1, wherein the resin (A) is a resin that decomposes by the action of an acid and increases the solubility in an alkali developer. The positive resist composition according to claim 1, wherein the resin (A) 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 represents 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 a single bond or a carbon chain and may be connected to the main chain of the resin as the component (A).
Y ₀ represents a hydrogen atom or an organic group. The positive resist according to any one of claims 1 to 4, wherein the resin (A) contains a repeating unit containing a carboxyl group or a group obtained by protecting a carboxyl group with an acid-decomposable group. Composition. A pattern forming method comprising: forming a resist film from the resist composition according to claim 1, and exposing and developing the resist film.