JP4530751B2 - Positive photosensitive composition and pattern forming method using the same - Google Patents

Description

  The present invention relates to a positive photosensitive 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 photosensitive composition capable of forming a highly refined pattern using vacuum ultraviolet light of 193 nm or less and a pattern forming method using the same.

  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 (to form a pattern of 0.1 μm or less) 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. That is, in the conventional resist containing novolak resin and naphthoquinonediazide compound, since absorption in the far ultraviolet region of 248 nm is large, it becomes difficult for light to reach the bottom of the resist sufficiently, and only a taper-shaped pattern with low sensitivity can be obtained.

  In order to solve such a problem, a compound that generates an acid by irradiation with far ultraviolet light using, as a main component, a resin having a poly (hydroxystyrene) having a low absorption in the 248 nm region as a basic skeleton and protected by an acid-decomposable group ( A composition combining a photoacid generator), a so-called chemically amplified resist, has been developed. Since the chemically amplified resist changes the solubility in the developer by the catalytic decomposition reaction of the acid generated in the exposed area, a highly sensitive and high resolution pattern can be formed.

  However, when ArF excimer laser light (193 nm) is used, since the compound having an aromatic group essentially has a large absorption in the 193 nm wavelength region, sufficient performance was not obtained even with the above chemically amplified resist.

  To solve this problem, an acid-decomposable resin having poly (hydroxystyrene) as a basic skeleton is replaced with 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 the polymer. Improvement of the amplification type resist is attempted.

However, for the F2 excimer laser light (157 nm), it was found that the alicyclic resin also has a large absorption in the 157 nm region, which is insufficient to obtain a target pattern of 0.1 μm or less. In contrast, Non-Patent Document 1 (Proc. SPIE. Vol. 3678. p. 13 (1999)) reports that a resin into which a fluorine atom (perfluoro structure) is introduced has sufficient transparency at 157 nm. Non-Patent Document 2 (Proc. SPIE. Vol. 3999. 330 (2000)), Non-Patent Document 3 (357 (2000)), Non-Patent Document 4 (365 (2000)) )), Patent Document 1 (WO-00 / 17712), Patent Document 2 (German Patent No. 1005466), Patent Document 3 (US Patent Application Publication No. 2001 / 0018162A2), etc. Has reached.

  However, further improvements in sensitivity, line edge roughness, and profile have been desired for resists containing conventional fluororesins.

Proc. SPIE. Vol.3678. P.13. (1999) Proc. SPIE. Vol.3999. 330 p. (2000) Proc. SPIE. Vol.3999. 357. (2000) Proc. SPIE. Vol.3999. 365. (2000) WO-00 / 17712 pamphlet German Patent No. 1005466 US Patent Application Publication No. 2001 / 0018162A2 Specification

  Accordingly, an object of the present invention is to provide positive photosensitivity that is highly sensitive when using far ultraviolet light of 250 nm or less, particularly ArF excimer laser light and F2 excimer laser light as a light source, and has excellent line edge roughness and profile. It is providing the composition and the pattern formation method using the same.

  The present invention has the following configuration, whereby the above object of the present invention is achieved.

一般式（Ｉ−ａ）及び（ＩＩ−ａ）中、Ｒ^ａ１〜Ｒ^ａ３は、同じでも異なっていてもよく、水素原子又は置換基を有していてもよい、アルキル基、アルケニル基、アリール基若しくはアルコキシ基を表す。Ｒ^ａ４及びＲ^ａ５は、同じでも異なっていてもよく、水素原子、シアノ基又は置換基を有していてもよい、アルキル基、アリール基若しくはアルコキシ基を表す。Ｙ_１及びＹ_２は、同じでも異なっていてもよく、置換基を有していてもよい、アルキル基、アリール基、アラルキル基又はヘテロ原子を含む芳香族基を表す。ｎは、１〜４の整数を表す。ｎが２以上の場合に複数個存在するＲ^ａ１及びＲ^ａ２は、同じでも異なっていてもよい。Ｒ^ａ１〜Ｒ^ａ３、Ｒ^ａ４、Ｒ^ａ５、Ｙ_１及びＹ_２の内のいずれか２つ以上が結合して環構造を形成してもよい。また、Ｒ^ａ１〜Ｒ^ａ３、Ｒ^ａ４、Ｒ^ａ５、Ｙ_１及びＹ_２のいずれかの位置で、連結基を介して結合し、一般式（Ｉ−ａ）又は（ＩＩ−ａ）の構造を２つ以上有していてもよい。Ｘ_ａ ⁻は、非求核性アニオンを表す。 (1) (A) 5 to 20 parts by mass of a compound that generates an acid upon irradiation with actinic rays or radiation, and (B) a repeating unit having a fluorine atom and a repeating unit not having a fluorine atom, 100 parts by mass of a resin having (b) a repeating unit having a lactone structure, a fluorine atom, and a group that decomposes by the action of an acid to increase the solubility in an alkaline developer A positive photosensitive composition for ArF excimer laser exposure (excluding the following (a) and (b)):
(A) (a1) a fluorine-containing copolymer comprising repeating units derived from at least one ethylenically unsaturated compound, wherein at least one ethylenically unsaturated compound is polycyclic and at least one The ethylenically unsaturated compound comprises a fluorine-containing copolymer characterized by containing at least one fluorine atom covalently bonded to an ethylenically unsaturated carbon atom and (b1) at least one photoactive component. A photoresist, wherein the fluorine-containing copolymer does not contain an aromatic functional group, and the functional group is sufficient to make the photoresist developable to produce a relief image upon exposure to ultraviolet light having a wavelength of less than 365 nm. A photoresist, comprising:
(B) A stimulating composition comprising a compound represented by the following general formula (Ia) or (II-a) that generates an acid or a radical by external stimulation.

In the general formulas (Ia) and (II-a), R ^{a1 to} R ^a3 may be the same or different and may have a hydrogen atom or a substituent, an alkyl group, an alkenyl group, an aryl Represents a group or an alkoxy group. R ^a4 and R ^a5 may be the same or different and each represents an alkyl group, an aryl group, or an alkoxy group, which may have a hydrogen atom, a cyano group, or a substituent. Y ₁ and Y ₂ may be the same or different and may have a substituent, an alkyl group, an aryl group, an aromatic group containing aralkyl group or a hetero atom. n represents an integer of 1 to 4. When n is 2 or more, a plurality of R ^a1 and R ^a2 may be the same or different. Any two or more of R ^{a1 to} R ^a3 , R ^a4 , R ^a5 , Y ₁ and Y ₂ may be bonded to form a ring structure. In addition, at any position of R ^{a1 to} R ^a3 , R ^a4 , R ^a5 , Y ₁ and Y ₂ , they are bonded via a linking group to form a structure of the general formula (Ia) or (II-a) You may have two or more. X _a ⁻ represents a non-nucleophilic anion.

(2) (B) as component, ArF excimer laser exposure Po di photosensitive composition as described in the main chain, characterized in that it contains a resin having a fluorine atom in (1).

(3) The ArF excimer according to (1), wherein the resin of the component (B) is a resin having a repeating unit having 1 to 3 groups represented by the following general formula (A-1) laser exposure Po di-type photosensitive composition.

In general formula (A-1),
R _1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or a group capable of decomposing by the action of an acid.

一般式（ｐＡ）中、Ｒは、水素原子、ハロゲン原子又は１〜４個の炭素原子を有する直鎖もしくは分岐のアルキル基を表す。複数のＲは、各々同じでも異なっていてもよい。
Ａは、単結合、アルキレン基、エーテル基、チオエーテル基、カルボニル基、エステル基、アミド基、スルホンアミド基、ウレタン基、又はウレア基よりなる群から選択される単独あるいは２つ以上の基の組み合わせを表す。
Ｒａは、一般式（ｐＩ）〜（ｐＶＩ）のいずれかで表される基を表す。

一般式（ｐＩ）〜（ｐＶＩ）中、
Ｒ₁₁は、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基又はｓｅｃ−ブチル基を表し、Ｚは、炭素原子とともにシクロアルキル基を形成するのに必要な原子団を表す。
Ｒ₁₂〜Ｒ₁₆は、各々独立に、炭素数１〜４個の、直鎖もしくは分岐のアルキル基又はシクロアルキル基を表し、但し、Ｒ₁₂〜Ｒ₁₄のうち少なくとも１つ、もしくはＲ₁₅、Ｒ₁₆のいずれかはシクロアルキル基を表す。
Ｒ₁₇〜Ｒ₂₁は、各々独立に、水素原子、炭素数１〜４個の、直鎖もしくは分岐のアルキル基又はシクロアルキル基を表し、但し、Ｒ₁₇〜Ｒ₂₁のうち少なくとも１つはシクロアルキル基を表す。また、Ｒ₁₉、Ｒ₂₁のいずれかは炭素数１〜４個の、直鎖もしくは分岐のアルキル基又はシクロアルキル基を表す。
Ｒ₂₂〜Ｒ₂₅は、各々独立に、水素原子、炭素数１〜４個の、直鎖もしくは分岐のアルキル基又はシクロアルキル基を表し、但し、Ｒ₂₂〜Ｒ₂₅のうち少なくとも１つはシクロアルキル基を表す。また、Ｒ₂₃とＲ₂₄は、互いに結合して環を形成していてもよい。
（６）前記（ｂ）ラクトン構造を有する繰り返し単位が、下記一般式（ＡＩ）で表される繰り返し単位であることを特徴とする（１）〜（５）のいずれかに記載のＡｒＦエキシマレーザー露光用ポジ型感光性組成物。

一般式（ＡＩ）中、Ｒ_b0は、水素原子、ハロゲン原子、又は炭素数１〜４のアルキル基を表す。Ａ_bは、単結合、エーテル基、エステル基、カルボニル基、アルキレン基、又はこれらを組み合わせた２価の基を表す。Ｖは、下記一般式（Ｌｃ）又は下記一般式（Ｖ−１）〜（Ｖ−５）のうちのいずれかで表される基を表す。

一般式（Ｌｃ）中、Ｒａ₁、Ｒｂ₁、Ｒｃ₁、Ｒｄ₁及びＲｅ₁は、各々独立に、水素原子又はアルキル基を表す。ｍ、ｎは各々独立に０〜３の整数を表し、ｍ＋ｎは、２以上６以下である。
一般式（Ｖ−１）〜（Ｖ−５）中、Ｒ_1b〜Ｒ_5bは、各々独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、アルコキシカルボニル基、アルキルスルホニルイミノ基又はアルケニル基を表す。Ｒ_1b〜Ｒ_5bの内の２つは、結合して環を形成してもよい。
（７）前記（ｃ）単環又は多環の脂環炭化水素構造及び水酸基を有する繰り返し単位が、下記一般式（ＡII）で表される繰り返し単位であることを特徴とする（４）に記載のＡｒＦエキシマレーザー露光用ポジ型感光性組成物。

一般式（ＡII）中、Ｒ_1cは、水素原子又はメチル基を表す。Ｒ_2c〜Ｒ_4cは、各々独立に水素原子又は水酸基を表す。ただし、Ｒ_2c〜Ｒ_4cのうち少なくとも１つは水酸基を表す。 (4) Any one of (1) to (3), wherein the repeating unit having no fluorine atom further contains at least one repeating unit selected from the following (a) or (c): A positive photosensitive composition for ArF excimer laser exposure described in 1.
(A) Acid-decomposable repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure (c) Repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure and a hydroxyl group
(5) wherein (a) monocyclic or polycyclic acid-decomposable repeating unit having an alicyclic hydrocarbon structure is, to being a repeating unit represented by the following general formula (pA) (4) The positive photosensitive composition for ArF excimer laser exposure described.

In general formula (pA), R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different.
A represents a single bond, an alkylene 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, or a combination of two or more groups. Represents.
Ra represents a group represented by any one of the general formulas (pI) to (pVI).

In general formulas (pI) to (pVI),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or R ₁₅ , Any of R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group, provided that at least one of R _{17 to} R ₂₁ is cyclo Represents an alkyl group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group, provided that at least one of R _{22 to} R ₂₅ is cyclo Represents an alkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.
(6) The ArF excimer laser according to any one of (1) to (5), wherein the repeating unit (b) having a lactone structure is a repeating unit represented by the following general formula (AI): A positive photosensitive composition for exposure.

In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. A _b represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these. V represents a group represented by any one of the following general formula (Lc) or the following general formulas (V-1) to (V-5).

In general formula (Lc), Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ and Re ₁ each independently represents a hydrogen atom or an alkyl group. m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.
In general formulas (V-1) to (V-5), R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonylimino group, or an alkenyl group. Represents. Two of R _{1b to} R _5b may combine to form a ring.
(7) the (c) monocyclic or polycyclic alicyclic hydrocarbon structure and the repeating unit having a hydroxyl group is described characterized in that it is a repeating unit represented by the following general formula (AII) (4) A positive photosensitive composition for ArF excimer laser exposure.

In general formula (AII), R _1c represents a hydrogen atom or a methyl group. R _{2c to} R _4c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R _{2c to} R _4c represents a hydroxyl group.

(8) A step of forming a resist film from the positive resist composition for ArF excimer laser exposure according to any one of (1) to (7) , and exposing and developing the resist film with an ArF excimer laser. A pattern forming method comprising:
(9) The pattern forming method according to (8) , wherein the exposure is immersion exposure.

  The preferred embodiments of the present invention will be further described below.

(10) (A) The positive photosensitivity for ArF excimer laser exposure according to any one of (1) to (7) , wherein the compound that generates an acid upon irradiation with actinic rays or radiation is a sulfonium salt. Sex composition.

(11) a compound generating an acid by irradiation of (A) an actinic ray or radiation, characterized in that a number 4-8 fluorine-substituted aliphatic sulfonate sulfonium salt carbon (1) to (7) The positive photosensitive composition for ArF excimer laser exposure according to any one of the above.
Although this invention is invention which concerns on said (1)- (11) , below, other matters are also described.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a positive photosensitive composition having high sensitivity, good line edge roughness, and good profile, and a pattern forming method using the same.

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 does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The positive photosensitive composition of the present invention comprises (A) 5 to 20 parts by mass of a compound that generates an acid upon irradiation with actinic rays or radiation, and (B) a fluorine atom, which decomposes by the action of an acid and undergoes alkali development. Contains 100 parts by weight of a resin having a group that increases the solubility in the liquid.

[1] (A) Compound that generates acid upon irradiation with actinic ray or radiation As a compound (photoacid generator) that generates acid upon irradiation with actinic ray or radiation that can be used in the present invention, photocationic polymerization light is used. Preferably used for initiators, photoinitiators of radical photopolymerization, photodecolorants of dyes, photochromic agents, or micro resists, preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, Specifically, known compounds that generate acids upon irradiation with actinic rays or radiation such as KrF, ArF, F ₂ excimer laser, X-rays, and electron beams, and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

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

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

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be exemplified.

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (Z1-1), (Z1-2) and (Z1-3) described later.

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

  More preferable examples of the (ZI) component include compounds (Z1-1), (Z1-2), and (Z1-3) described below.

Compound (Z1-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.

Arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group or a part of R ₂₀₁ to R ₂₀₃ is an aryl group and the remainder may be an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkyl or cycloalkylsulfonium compound, and an aryldialkyl or dicycloalkylsulfonium compound.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec. -A butyl group, a t-butyl group, etc. can be mentioned.

  The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms, and most preferably an alkyl group having 1 to 4 carbon atoms and 1 carbon atom. It is an alkoxy group of ~ 4. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

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

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

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

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

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

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

  The alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent.

  Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an alkylthio group.

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

  As the alkyl group, for example, preferably an alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. it can.

  As an alkoxy group, Preferably a C1-C5 alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. can be mentioned, for example.

  As the alkylthio group, for example, preferably an alkylthio group having 1 to 15 carbon atoms, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, pentylthio group, Neopentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, tridecylthio group, tetradecylthio group, pentadecylthio group, hexadecylthio group, heptadecylthio group, octadecylthio group, nonadecylthio group Group, eicosylthio group and the like. The alkyl group, alkoxy group, and alkylthio group may be further substituted with a halogen atom (preferably a fluorine atom).

  Examples of the aliphatic hydrocarbon group in the aliphatic carboxylate anion include those similar to the aliphatic hydrocarbon group in the aliphatic sulfonate anion.

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

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

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

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. These alkyl groups may have a substituent, and examples of the substituent include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, and the like, which are substituted with a fluorine atom. Alkyl groups are preferred.

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

As the non-nucleophilic anion of X ⁻ , an aliphatic sulfonate anion substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group substituted with a fluorine atom A bis (alkylsulfonyl) imide anion and a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion of X ⁻ is more preferably a fluorine-substituted aliphatic sulfonate anion having 4 to 8 carbon atoms, particularly preferably a nonafluorobutane sulfonate anion or a perfluorooctane sulfonate anion.

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

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an aliphatic hydrocarbon group, more preferably a linear, branched, cyclic 2-oxoalkyl group or alkoxycarbonylmethyl group, most preferably a linear, branched 2- An oxoalkyl group;

The aliphatic hydrocarbon group as R _{201 to} R ₂₀₃ may be a linear or branched alkyl group or a cycloalkyl group, and preferably a linear or branched alkyl group having 1 to 10 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group, and a norbornyl group). As the aliphatic hydrocarbon group, a 2-oxoalkyl group and an alkoxycarbonylmethyl group are more preferable.

  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 or cycloalkyl group.

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

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

Two members out of R _{201 to} R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

  The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _1c to R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
R _6c and R _7c represent a hydrogen atom, an alkyl group, or a cycloalkyl group.
Rx and Ry each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
Any two or more of R _{1c to} R _5c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom, an ester bond, and an amide bond. May be included.
Zc ⁻ represents a non-nucleophilic anion and is the same as the non-nucleophilic anion of X ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a straight chain having 1 to 12 carbon atoms. Examples thereof include a chain or branched alkyl group (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).

Examples of the cycloalkyl group as R _{1c to} R _7c include a cycloalkyl group having 3 to 20 carbon atoms, preferably a cycloalkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group). .

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

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

Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same as the alkyl group and cycloalkyl group as R _{1c to} R _5c , and a 2-oxoalkyl group and an alkoxycarbonylmethyl group are more preferable. preferable.

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

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

Examples of the group formed by combining R _x and R _y include a butylene group and a pentylene group.

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

In formula (ZII), (ZIII), R 204 ~R 207 each independently represents an aryl group, an alkyl group or a cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group.

The alkyl group represented by R _{204 to} R ₂₀₇ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group). Butyl group, pentyl group).

Cycloalkyl groups R ₂₀₄ to R ₂₀₇ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).

Aryl group R ₂₀₄ to R _207, an alkyl group, a cycloalkyl group may have a substituent, an aryl group of R ₂₀₄ to R _207, an alkyl group, substituent that the cycloalkyl group have As, for example, an alkyl group (for example, carbon number 1-15), a cycloalkyl group (for example, carbon number 3-15), an aryl group (for example, carbon number 6-15), an alkoxy group (for example, carbon number 1-15), A halogen atom, a hydroxyl group, a phenylthio group, etc. can be mentioned.

X ⁻ represents a non-nucleophilic anion and is the same as the non-nucleophilic anion of X ^{− in} formula (ZI).

Among the other compounds that generate acid upon decomposition by irradiation with actinic rays or radiation used in the present invention, those represented by the following formulas (ZIV) to (ZVII) are particularly effective. Is mentioned.

In general formulas (ZIV) to (ZVII),
Ar ³ and Ar ⁴ each independently represents an aryl group.
R ₂₀₆ represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
R represents an alkyl group, a cycloalkyl group, or an aryl group.
_R207 represents an electron-withdrawing group, and preferably represents a cyano group or a fluoroalkyl group.
R ₂₀₈ represents an alkyl group, a cycloalkyl group, or an aryl group.

  Of the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by general formulas (ZI) to (ZIII) are more preferable.

Of the compounds that generate an acid upon irradiation with actinic rays or radiation, a sulfonium salt represented by the general formula (ZI) is more preferable, a sulfonium salt having a carbonyl group is particularly preferable, and a compound (ZI) is most preferable. -2), a compound having a 2-oxoalkyl group in any one of R _{201 to} R ₂₀₃ or a compound represented by the general formula (ZI-3). The sensitivity is particularly improved by using a compound having a carbonyl group.

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

[2] (B) Resin having a fluorine atom and a group that decomposes by the action of an acid to increase the solubility in an alkaline developer The positive photosensitive composition of the present invention has a fluorine atom, It contains a resin having a group that decomposes under the action of an acid to increase the solubility in an alkaline developer (hereinafter also referred to as “fluorine atom-containing resin”).

  The fluorine atom-containing resin is a resin having a fluorine atom in the main chain and / or side chain, and examples thereof include resins having a repeating unit represented by the following general formulas (I) to (X).

  The fluorine atom-containing resin is preferably a resin having a fluorine atom in the main chain, and is represented by, for example, repeating units represented by the following general formulas (I) to (III) and the following general formulas (IV) to (X) A resin having a repeating unit is preferable.

  The fluorine atom-containing resin is preferably a resin having a repeating unit having 1 to 3 groups represented by the following general formula (A-1).

In general formula (A-1),
R _1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or a group capable of decomposing by the action of an acid.
R _1a is preferably a hydrogen atom.

  Examples of the repeating unit having 1 to 3 groups represented by the general formula (A-1) include the repeating units represented by the following general formulas (IV) to (VII).

In general formulas (I) to (X),
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.
R _1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or a group capable of decomposing by the action of an acid.
R ₆ , R ₇ and R ₈ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
R ₉ and R ₁₀ represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
R ₁₁ and R ₁₂ may be the same or different and each represents a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. .
R ₁₃ and R ₁₄ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
R ₁₅ represents a hydrogen atom, a hydroxyalkyl group, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, an alkenyl group having a fluorine atom, an aralkyl group having a fluorine atom, an aryl group having a fluorine atom, -C ( _{R 36) (R 37) (} R 38), - represents a group of _{C (R 36) (R 37} ) (oR 39) or the following general formula (XI).

R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ may be the same or different and each represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. Two of _{R 36, R 37, R 38} , or R _36, R _37, two of R ₃₉ may be combined with each other to form a ring.
R ₄₀ represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl 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.
A ₁ and A ₂ are a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, an arylene group, a divalent alicyclic group, or a divalent linking group formed by combining two or more thereof, or —O—CO—R. _22- , -CO-O-R _23- , -CO-N (R ₂₄ ) -R ₂₅ -are represented.
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.
n represents 0 or 1, x, y, z represents an integer of 0 to 4, and m represents 1 or 2.

In general formulas (I) to (XI),
Examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, and specifically include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and a hexyl group. ,
Preferred examples include 2-ethylhexyl group and octyl 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, and includes, for example, an adamantyl group, norbornyl group, isobornyl group, camphanyl 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.

  The divalent alicyclic group may be any polycyclic structure such as bicyclo, tricyclo, and tetracyclo. The carbon number is preferably 6-30, and more preferably 7-25. Preferred examples of the divalent alicyclic group include, for example, an adamantane residue (residue obtained by removing two hydrogen atoms from adamantane, the same shall apply hereinafter), a noradamantane residue, a decalin residue, a tricyclodecane residue, tetra A cyclododecane residue, a norbornane residue, etc. can be mentioned. More preferable examples of the divalent alicyclic group include an adamantane residue and a norbornane residue.

The ring formed by combining R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ is, for example, a 5- to 7-membered ring, specifically, a pentane ring substituted with fluorine, a hexane ring, Examples include a furan ring, a dioxole ring, and a 1,3-dioxolane ring.

The ring formed by combining two of R _{36 to} R ₃₈ or two of R _{36 to} R ₃₇ and R ₃₉ is, for example, a 3- to 8-membered ring, specifically a cyclopropane ring. , Cyclopentane ring, cyclohexane ring, furan ring, pyran ring and the like.

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

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

  Here, examples of the alkyl group, cycloalkyl group, and aryl group include those described above. The alkyl group may be further substituted with a fluorine atom or a cycloalkyl group.

Examples of the group that decomposes by the action of an acid of R _1a include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), —C (R ₃₆ ). ) (R ₃₇ ) (OR ₃₉ ), —COO—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₀₁ ) (R ₀₂ ) COO—C (R ₃₆ ) (R ₃₇ ) (R _38), and the like.

Examples of the group contained in the fluorine atom-containing resin that decomposes by the action of an acid to increase the solubility in an alkali developer (hereinafter also referred to as “acid-decomposable group”) include —O—C (R ₃₆ ). (R ₃₇ ) (R ₃₈ ), —O—C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), —O—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), - COO-C (R 36) (R _{37) (R 38), -} COO-C (R 36) (R 37) (OR 39) , and the like.

R ₃₆ to R ₃₉ in general formula (VIII), have the same meaning as in R ₃₆ to R ₃₉ in R ₁₅ in _{(IX), R 01, R} 02 are have a substituent shown hydrogen atom, the above Represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group, which may be substituted.

  Preferable specific examples include t-butyl group, t-amyl group, 1-alkyl-1-cyclohexyl group, 2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- (4-methylcyclohexyl). ) Ether group or ester group of tertiary alkyl group such as 2-propyl group, acetal group or acetal ester group such as 1-alkoxy-1-ethoxy group, tetrahydropyranyl group, t-alkyl carbonate group, t-alkyl A carbonylmethoxy group etc. are mentioned preferably.

Examples of the group that is decomposed by the action of an acid to increase the solubility in an alkali developer include the —OR _1a group in the repeating units represented by the general formulas (IV) to (VII), the general formula (VIII) to It can be formed as a —COOR ₁₅ group in the repeating unit represented by (IX).

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

  The fluorine atom-containing resin preferably further has a repeating unit represented by the following general formula (XII).

In general formula (XII), R _{a1 to} R _a3 each independently represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group. R _a4 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. n represents an integer of 1 to 5. When n is 2 or more, two or more R _a4 may be the same or different. (Z) represents an alicyclic hydrocarbon group. Q represents a hydroxyl group or an acid-decomposable group. L ₁ and L ₂ each independently represent a single bond or a divalent linking group.

In the general formula (XII), _examples of the halogen atom represented by R _{a1 to} R _a3 and R _a4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group in the alkyl group of R _{a1 to} R _a3 and R _{a4 and} the alkoxy group of R _a4 is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. Can do.

Aryl group R _a4 is preferably a number 6-10 aryl group having a carbon, for example, a phenyl group, a tolyl group, a naphthyl group.

The aralkyl group for R _a4 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

The alkyl group, alkoxy group, aryl group, aralkyl group, and the like of R _{a1 to} R _a3 and R _a4 may not have a substituent or may have a substituent.

Examples of the substituent that the alkyl group, alkoxy group, aryl group, and aralkyl group of R _{a1 to} R _a3 and R _a4 may have include, for example, a halogen atom such as a fluorine atom, a hydroxyl group, and an alkoxy group (preferably And a cyano group.

R _a4 is preferably a hydrogen atom, a fluorine atom, a trifluoromethyl group, a hydroxyl group, a cyano group, a methyl group, or an ethyl group.

  (Z) The alicyclic hydrocarbon group generally has 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, and more preferably 7 to 15 carbon atoms. The alicyclic hydrocarbon group may be monocyclic or polycyclic, for example, cycloheptane residue, cyclooctane residue, norbornane residue, adamantane residue, tricyclodecane residue, tetracyclododecane residue, etc. Preferably, a norbornane residue, an adamantane residue, a tricyclodecane residue, and a tetracyclododecane residue can be mentioned.

  Examples of the acid-decomposable group for Q include the acid-decomposable groups described above.

Examples of the divalent linking group of L ₁ and L ₂ include an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, —O—R _22a —, —O—CO, which may have a substituent. -R22b-, _-CO -O- _R22c- , -CO-N ( _R22d ) _-R22e-, etc. can be mentioned. R _22a , R _22b , R _22c and R _{22e each} may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, a cycloalkylene group, an alkenylene. Represents a group or an arylene group. R _22d represents a hydrogen atom or an _optionally substituted alkyl group, cycloalkyl group, aralkyl group or aryl group.

  Examples of the alkylene group include linear and branched alkylene groups, and examples thereof include those having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. It is done.

Examples of the cycloalkylene group include monocyclic residues such as a cyclopentylene group and a cyclohexylene group, and polycyclic residues such as a normornan skeleton and an adamantane skeleton (having 5 to 12 carbon atoms).

  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.

  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.

Examples of the substituent that the divalent linking group of L ₁ and L ₂ may have include a halogen atom such as a fluorine atom and a chlorine atom, a cyano group, and the like, and a fluorine atom is preferable.

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

  The fluorine atom-containing resin may further have repeating units represented by the following general formulas (XIII) to (XV).

In the formula, R ₄₁ represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.
R ₄₂ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
A ₅ 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 -is represented.
R ₂₂ , R ₂₃ and R ₂₅ may be the same or different and each may have a single bond, an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, an alkenylene group Represents a cycloalkylene group or an arylene group.
R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent.

  Although the specific example of the repeating structural unit represented by general formula (XIII)-(XV) is shown, this invention is not limited to this.

  In addition to the above repeating structural unit, the fluorine atom-containing resin may further be copolymerized with other polymerizable monomers.

  When the fluorine atom-containing resin is used for ArF excimer laser exposure, the fluorine atom-containing resin is preferably a resin having a repeating unit having a fluorine atom and a repeating unit having no fluorine atom.

  Examples of the repeating unit having a fluorine atom include the repeating units represented by the general formulas (I) to (VII), and the repeating units represented by the general formulas (IV) to (VII) are as follows. preferable.

Examples of the repeating unit having no fluorine atom include the following repeating units (a) to (c).
(A) Acid-decomposable repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure (b) A repeating unit having a lactone structure and (c) A repeating having a monocyclic or polycyclic alicyclic hydrocarbon structure and a hydroxyl group unit

(A) Acid-decomposable repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure As the acid-decomposable repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure, the following general formula (pI) to general An acid-decomposable repeating unit having an alicyclic hydrocarbon structure represented by the formula (pVI) is preferred.

In general formulas (pI) to (pVI),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or R ₁₅ , Any of R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group, provided that at least one of R _{17 to} R ₂₁ is cyclo Represents an alkyl group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group, provided that at least one of R _{22 to} R ₂₅ is cyclo Represents an alkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

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

In addition, examples of the substituent that each alkyl group may have include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano. Group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The cycloalkyl group in R _{11 to} R ₂₅ or the cycloalkyl group formed by Z and the carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These cycloalkyl groups may have a substituent.

  Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, A cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

  Examples of the substituent for these cycloalkyl groups include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from the group consisting of a methyl group, an ethyl group, a propyl group, and an isopropyl group. As said alkoxy group, a C1-C4 methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. can be mentioned. Examples of the substituent that the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom, and an alkoxy group.

  As the acid-decomposable repeating unit having an alicyclic hydrocarbon structure represented by general formula (pI) to general formula (pVI), a repeating unit represented by the following general formula (pA) is preferable.

Here, R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different.
A represents a single bond, an alkylene 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, or a combination of two or more groups. Represents.
Ra represents any group of the above formulas (pI) to (pVI).

  The acid-decomposable repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure is most preferably a repeating unit of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate. It is.

  Specific examples of the acid-decomposable repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure are shown below.

(B) Repeating unit having a lactone structure The repeating unit having a repeating unit having a lactone structure is represented by, for example, the following general formula (Lc) or any one of the following general formulas (V-1) to (V-5). And a repeating unit having a group having a lactone structure.

In general formula (Lc), Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ and Re ₁ each independently represents a hydrogen atom or an alkyl group. m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.

In the general formulas (V-1) to (V-5), R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonylimino group, or an alkenyl group. Represents. Two of R _{1b to} R _5b may combine to form a ring.

R _{1 to} Re ₁ alkyl groups in general formula (Lc) and R _{1b to} R _5b alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkyl groups in general formulas (V-1) to (V-5) Examples of the alkyl group in the sulfonylimino group include linear and branched alkyl groups, which may have a substituent. Preferable substituents that may be included include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, and a cycloalkyl group.

  As the repeating unit having a group having a lactone structure represented by any one of the general formula (Lc) and general formulas (V-1) to (V-5), a repeating unit represented by the following general formula (AI) Can be mentioned.

In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. As a preferable substituent that the alkyl group of R _b0 may have, as a preferable substituent that the alkyl group as R _1b in the general formulas (V-1) to (V-5) may have. What was illustrated previously is mentioned.
Examples of the halogen atom for R _b0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R _b0 is preferably a hydrogen atom.
A _b represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these.
V represents a group represented by any one of the general formula (Lc) and the general formulas (V-1) to (V-5).

  Specific examples of the repeating unit having a lactone structure are given below, but the present invention is not limited thereto.

(C) Repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure and a hydroxyl group Examples of the group having a monocyclic or polycyclic alicyclic hydrocarbon structure and a hydroxyl group include, for example, the following general formula (VII having an adamantane skeleton) ) Can be mentioned.

In general formula (VII), R _{2c to} R _4c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R _{2c to} R _4c represents a hydroxyl group.

  The group represented by the general formula (VII) is preferably a dihydroxy body or a monohydroxy body, and more preferably a dihydroxy body.

Examples of the repeating unit having a group represented by the general formula (VII) include a repeating unit represented by the following general formula (AII).

In general formula (AII), R _1c represents a hydrogen atom or a methyl group.
R _{2c to} R _4c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R _{2c to} R _4c represents a hydroxyl group. Those in which two of R _{2c to} R _4c are hydroxyl groups are preferred.

  Although the specific example of the repeating unit which has a monocyclic or polycyclic alicyclic hydrocarbon structure and a hydroxyl group is given below, this invention is not limited to these.

  In addition to the above repeating units, the fluorine atom-containing resin having a repeating unit having a fluorine atom and a repeating unit having no fluorine atom may be copolymerized with another polymerizable monomer.

  In the fluorine atom-containing resin, the total content of the repeating units represented by the general formulas (I) to (X) is generally 2 to 80 mol%, preferably 5 to 5 in the total polymer composition. It is 70 mol%, More preferably, it is 10-60 mol%.

When the fluorine atom-containing resin has repeating units represented by the general formulas (I) to (III) and repeating units represented by the general formulas (IV) to (X), the general formulas (1) to (III)
The content of the repeating unit represented by is generally 10 to 70 mol%, preferably 20 to 60 mol%, more preferably 30 to 50 mol% in the total polymer composition.

  When the fluorine atom-containing resin has a repeating unit represented by the general formulas (I) to (III) and a repeating unit represented by the general formulas (IV) to (X), the general formula (1V) to The content of the repeating unit represented by (X) is generally 10 to 65 mol%, preferably 15 to 60 mol%, more preferably 20 to 40 mol% in the total polymer composition.

  In the fluorine atom-containing resin, the content of the repeating unit represented by the general formula (XII) is generally 20 to 80 mol%, preferably 30 to 70 mol%.

  In the fluorine atom-containing resin, the content of the repeating units represented by the general formulas (XIII) to (XV) is generally 0 to 70 mol%, preferably 10 to 60 mol%, more preferably 20 to 50 mol%. Used in the mol% range.

  When the fluorine atom-containing resin has a repeating unit having a group represented by the general formula (A-1), the content of the repeating unit having a group represented by the general formula (A-1) is generally 5 It is -70 mol%, Preferably it is 10-50 mol%.

When the fluorine atom-containing resin has a repeating unit having a fluorine atom and a repeating unit not having a fluorine atom, the content of the repeating unit having a fluorine atom is generally 5 in the total polymer composition. It is -70 mol%, Preferably it is 10-50 mol%, More preferably, it is 10-30 mol%.
When the fluorine atom-containing resin has a repeating unit having a fluorine atom and a repeating unit not having a fluorine atom, the content of the repeating unit having no fluorine atom is generally in the whole polymer composition. 5 to 70 mol%, preferably 10 to 50 mol%, more preferably 10 to 30 mol%.

  In the fluorine atom-containing resin, the content of the repeating unit having a group that is decomposed by the action of an acid to increase the solubility in an alkali developer is generally 5 to 70 mol% in the total polymer composition, Preferably it is 10-65 mol%, More preferably, it is 15-50 mol%.

  Each of the repeating structural units represented by the above specific examples may be used alone or in combination.

  A preferred molecular weight of the fluorine atom-containing resin is 1,000 to 200,000 on a weight average, and more preferably 3,000 to 20,000. The molecular weight distribution is 1 to 10, preferably 1 to 3, and more preferably 1 to 2. The smaller the molecular weight distribution, the smoother the resolution, the resist shape, and the side wall of the resist pattern, and the better the roughness.

  Since the fluorine atom-containing resin further improves development defects, the content of components having a molecular weight of 1000 or less may be reduced to 15% by mass, preferably 10% by mass or less, and more preferably 8% by mass or less. preferable.

  Reduction of the low molecular weight component can be performed by a fractionation treatment in which the resin obtained by the polymerization reaction is dissolved in a good solvent, and then the poor solvent is added to precipitate the high molecular weight component of the resin.

The addition amount of the fluorine atom-containing resin is generally 50 to 100% by mass, preferably 60 to 98% by mass, more preferably 65 to 95% by mass, based on the total solid content of the composition. .

  In this invention, 5-20 mass parts of compounds which generate | occur | produce an acid by irradiation of actinic light or a radiation are mix | blended with respect to 100 mass parts of fluorine atom containing resin. More preferably, it is 5-16 mass parts with respect to 100 mass parts of fluorine atom containing resin, More preferably, it is 6-15 mass parts, Most preferably, it is 7-12 mass parts. By blending 5 to 20 parts by mass of a compound that generates an acid upon irradiation with actinic rays or radiation with respect to 100 parts by mass of the fluorine atom-containing resin, the line edge roughness can be improved with high sensitivity and is rectangular. A pattern profile can be obtained.

[3] (C) Fluorine-based and / or silicon-based surfactant The positive photosensitive composition of the present invention further comprises (C) a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant). It is preferable to contain any one of surfactants, surfactants containing both fluorine atoms and silicon atoms, or two or more thereof.

  When the positive photosensitive composition of the present invention contains the surfactant (C), 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 (C) surfactants, for example, JP-A 62-36663, JP-A 61-226746, JP-A 61-226745, JP-A 62-170950, JP 63-3345, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2002-277862, US Pat. No. 5,405,720. , No. 5,360,692, No. 5,529,881, No. 5,296,330, No. 5,543,098, No. 5,576,143, No. 5,294,511, No. 5,824,451 The following commercially available surfactants can also be used as they are.

  Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) 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.

  (C) The usage-amount of surfactant becomes like this. Preferably it is 0.0001-2 mass% with respect to positive photosensitive composition whole quantity (except a solvent), More preferably, it is 0.001-1 mass%.

[4] (D) Basic Compound The positive photosensitive composition of the present invention preferably contains (D) a basic compound in order to reduce a change in performance over time from exposure to heating.

  Preferable structures include structures represented by the following formulas (A) to (E).

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, And R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring. The alkyl group, cycloalkyl group and aryl group may be unsubstituted or have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, and a 3 to 20 carbon atom. A hydroxycycloalkyl group is preferred.

  These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represents an alkyl group having 1 to 6 carbon atoms).

  Preferred compounds include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or An unsubstituted aminoalkylmorpholine, a substituted or unsubstituted piperidine can be mentioned, and more preferable compounds are imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine. Examples thereof include a compound having a structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. The compound having a diazabicyclo structure is 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] noner-5-ene, 1,8-diazabicyclo [5,4,0]. Undecar 7-ene. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of aniline compounds include 2,6-diisopropylaniline and N, N-dimethylaniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  These basic compounds are used alone or in combination of two or more. The usage-amount of a basic compound is 0.001-10 mass% normally based on solid content of a positive photosensitive composition, Preferably it is 0.01-5 mass%. In order to obtain a sufficient addition effect, 0.001% by mass or more is preferable, and 10% by mass or less is preferable in terms of sensitivity and developability of the non-exposed area.

[5] Organic solvent The positive photosensitive composition of the present invention is used by dissolving the above components in a predetermined organic solvent.

  Examples of the organic solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl. Ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc.

  In the present invention, the organic solvent may be used alone or in combination, but it is preferable to use a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group are mixed. . Thereby, the generation of particles during storage of the resist solution can be reduced.

  Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.

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

  The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

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

  The film thickness of the resist film formed by applying and drying the positive photosensitive composition of the present invention on a substrate is preferably 50 to 200 nm. By setting the thickness of the resist film to 50 to 200 nm, it is possible to improve the dry etching resistance and the pattern profile and increase the transmittance of the resist film.

  The film thickness of the resist film can be adjusted by the solid content concentration excluding the solvent of the composition, the preferable solid content concentration is 5 to 18% by mass, the more preferable solid content concentration is 7 to 15% by mass, and the particularly preferable solid content is The partial concentration is 9-14% by mass.

  Examples of the alkaline developer of the positive photosensitive composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, etc. 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 Further, aqueous solutions 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.

<Fluorine group-containing resin>
Hereinafter, the structures of the fluorine group-containing resins (FII-1) to (FII-40) used in the examples are shown.

  Tables 1 and 2 below show the weight average molecular weights and the like of the fluorine group-containing resins (FII-1) to (FII-40).

Examples 1 to 20 and Comparative Examples 1 and 2 (Examples 1 to 20 are reference examples)
<Resist preparation>
The components shown in Table 3 below were dissolved in a solvent to prepare a solution having a solid content concentration of 12% by mass, and this was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a positive resist solution.

Hereinafter, the abbreviations in Table 3 are as follows.
DBN; 1,5-diazabicyclo [4.3.0] non-5-ene TPI; 2,4,5-triphenylimidazole TPSA; triphenylsulfonium acetate HEP; N-hydroxyethylpiperidine DIA; 2,6-diisopropyl Aniline DCMA; dicyclohexylmethylamine TPA; tripentylamine TOA; tri-n-octylamine HAP; hydroxyantipyrine TBAH; tetrabutylammonium hydroxide TMEA; tris (methoxyethoxyethyl) amine PEA; N-phenyldiethanolamine W-1; Fuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine) W-2; MegaFuck R08 (Dainippon Ink Chemical Co., Ltd.)
(Fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Silicon)
W-4; Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
A1; propylene glycol monomethyl ether acetate A2; ethyl ethoxypropionate A3; γ-butyrolactone B1; propylene glycol monomethyl ether B2; cyclohexanone B3; 2-heptanone B4;

<Resist evaluation>
Each positive resist solution was applied to a silicon wafer subjected to hexamethyldisilazane treatment by a spin coater and dried by heating on a vacuum contact hot plate at 120 ° C. for 90 seconds to obtain a resist film having a thickness of 100 nm.

  The obtained resist film was subjected to pattern exposure with an exposure apparatus of 157 nm, and immediately after the exposure, it was heated on a hot plate at 120 ° C. for 90 seconds. Development was carried out with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds and rinsed with pure water. The obtained pattern was evaluated by the following method.

[Profile / Sensitivity]
The cross-sectional shape of the obtained pattern was observed with a scanning electron microscope. The minimum energy when resolving a 0.1 μm line (line: space = 1: 1) was defined as sensitivity.

[Line edge roughness]
For the range of 5 μm edge in the longitudinal direction of the line pattern (line width 100 nm, line / space = 1: 1), the distance from the reference line where the edge should be is 50 points by measuring SEM (S-8840 manufactured by Hitachi, Ltd.) Measurement was performed to obtain a standard deviation, and 3σ was calculated. A smaller value indicates better performance.

  The evaluation results are shown in Table 3.

  From Table 3, it is clear that the positive photosensitive composition of the present invention has high sensitivity and good line edge roughness and profile.

Examples 21 to 30 and Comparative Example 3 (Note that Examples 26 to 28 are reference examples.)
<Resist preparation>
The components shown in Table 4 below were dissolved in a solvent to prepare a solution having a solid content concentration of 6% by mass, and this was filtered through a 0.1 μm polyethylene filter to prepare a positive resist solution. The prepared positive resist solution was evaluated by the following method, and the results are shown in Table 4.

  The structures, weight average molecular weights, and dispersities of the fluorine atom-containing resins (FII-41) to (FII-50) and the comparative resin (C1) in Table 4 are shown below.

The abbreviations in Table 4 are shown below.
N-1, N, N-dibutylaniline N-2; N, N-dipropylaniline N-3; N, N-dihydroxyethylaniline N-4: 2,4,5-triphenylimidazole N-5; 2 , 6-Diisopropylaniline N-6; Hydroxyantipyrine
N-7; Tributylamine

W-1; Megafuck F176 (Dainippon Ink Chemical Co., Ltd.) (fluorine)
W-2; Mega W-2; Fuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3; Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based) W-4; Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)

SL-1: cyclopentanone SL-2: cyclohexanone SL-3: 2-methylcyclohexanone SL-4; propylene glycol monomethyl ether acetate SL-5: ethyl lactate SL-6: propylene glycol monomethyl ether SL-7: 2-heptanone SL-8: γ-butyrolactone SL-9: propylene carbonate In Table 4, the ratio when a plurality of solvents are used is a mass ratio.

<Resist evaluation>
ARC29A manufactured by Brewer Science Co., Ltd. was uniformly applied to a silicon wafer with a spin coater at 78 nm, and heat-dried at 205 ° C. for 60 seconds to form an antireflection film. Thereafter, each positive resist composition immediately after preparation was applied by a spin coater and dried (PB) at 115 ° C. for 90 seconds to form a 170 nm resist film.
This resist film is exposed with an ArF excimer laser stepper (PAS5500 / 1100 NA = 0.75 (2/3 annular illumination) manufactured by ASML) through a mask, and immediately after exposure, heated on a hot plate at 120 ° C. for 90 seconds. (PEB). Further, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a resist pattern.

(sensitivity)
The exposure amount for reproducing the 80 nm line and space 1/1 mask pattern was defined as sensitivity.

(Line edge roughness)
The line edge roughness is measured by observing an 80 nm line-and-space 1/1 pattern using a length-measuring scanning electron microscope (SEM), and the edge of the line pattern in the longitudinal direction should have an edge of 5 μm. The distance from the reference line was measured at 50 points using a length measurement SEM (S-8840 manufactured by Hitachi, Ltd.), the standard deviation was obtained, and 3σ was calculated. A smaller value indicates better performance.

(Profile)
A cross-sectional shape at an exposure amount for reproducing a mask pattern of 80 nm line and space 1/1 was observed with a scanning electron microscope.

  From the results in Table 4, it is clear that the positive photosensitive composition of the present invention is excellent in sensitivity and profile, and has good line edge roughness.

Immersion exposure <Resist preparation>
The components of Examples 21 to 30 were dissolved in a solvent to prepare a solution having a solid content concentration of 6% by mass, and this was filtered through a 0.1 μm polyethylene filter to prepare a positive resist composition. The prepared positive resist composition was evaluated by the following method.

<Resolution evaluation>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The positive resist composition prepared thereon was applied and baked at 115 ° C. for 60 seconds to form a 150 nm resist film. The wafer thus obtained was subjected to two-beam interference exposure (wet exposure) as shown in FIG. 1 using pure water as the immersion liquid. In the two-beam interference exposure (wet), a laser 1, an aperture 2, a shutter 3, three reflecting mirrors 4, 5, 6 and a condenser lens 7 are used, a prism 8, an immersion liquid (pure water) 9 is used. Then, the wafer 10 having the antireflection film and the resist film was exposed. The wavelength of the laser 1 was 193 nm, and the prism 8 forming a 65 nm line and space pattern was used. Immediately after the exposure, the resist pattern obtained by heating at 115 ° C. for 90 seconds, developing with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 60 seconds, rinsing with pure water, and spin drying is applied to the scanning pattern. When observed with a microscope (S-9260, manufactured by Hitachi), a 65 nm line and space pattern was resolved.
It is clear that the positive photosensitive composition of the present invention has a good image forming ability even in an exposure method using an immersion liquid.

It is the schematic of a two-beam interference exposure experiment apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Laser 2 Aperture 3 Shutter 4, 5, 6 Reflection mirror 7 Condensing lens 8 Prism 9 Immersion liquid 10 Wafer having antireflection film and resist film 11 Wafer stage

Claims (9)

(A) 5 to 20 parts by mass of a compound that generates an acid upon irradiation with actinic rays or radiation, and
(B) a repeating unit having a fluorine atom and a repeating unit not having a fluorine atom, and a repeating unit having no fluorine atom, (b) having a repeating unit having a lactone structure, by the action of an acid A positive photosensitive composition for ArF excimer laser exposure characterized by containing 100 parts by mass of a resin having a group that decomposes and increases the solubility in an alkali developer (however, the following (A) and (B)) Is excluded.)
(A) (a1) a fluorine-containing copolymer comprising repeating units derived from at least one ethylenically unsaturated compound, wherein at least one ethylenically unsaturated compound is polycyclic and at least one The ethylenically unsaturated compound comprises a fluorine-containing copolymer characterized by containing at least one fluorine atom covalently bonded to an ethylenically unsaturated carbon atom and (b1) at least one photoactive component. A photoresist, wherein the fluorine-containing copolymer does not contain an aromatic functional group, and the functional group is sufficient to make the photoresist developable to produce a relief image upon exposure to ultraviolet light having a wavelength of less than 365 nm. A photoresist, comprising:
(B) A stimulating composition comprising a compound represented by the following general formula (Ia) or (II-a) that generates an acid or a radical by external stimulation.

In the general formulas (Ia) and (II-a), R ^{a1 to} R ^a3 may be the same or different and may have a hydrogen atom or a substituent, an alkyl group, an alkenyl group, an aryl Represents a group or an alkoxy group. R ^a4 and R ^a5 may be the same or different and each represents an alkyl group, an aryl group, or an alkoxy group, which may have a hydrogen atom, a cyano group, or a substituent. Y ₁ and Y ₂ may be the same or different and may have a substituent, an alkyl group, an aryl group, an aromatic group containing aralkyl group or a hetero atom. n represents an integer of 1 to 4. When n is 2 or more, a plurality of R ^a1 and R ^a2 may be the same or different. Any two or more of R ^{a1 to} R ^a3 , R ^a4 , R ^a5 , Y ₁ and Y ₂ may be bonded to form a ring structure. In addition, at any position of R ^{a1 to} R ^a3 , R ^a4 , R ^a5 , Y ₁ and Y ₂ , they are bonded via a linking group to form a structure of the general formula (Ia) or (II-a) You may have two or more. X _a ⁻ represents a non-nucleophilic anion.   The positive photosensitive composition for ArF excimer laser exposure according to claim 1, wherein the component (B) contains a resin having a fluorine atom in the main chain. The resin for component (B) is a resin having a repeating unit having 1 to 3 groups represented by the following general formula (A-1), for ArF excimer laser exposure according to claim 1 Positive photosensitive composition.

In general formula (A-1),
R _1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or a group capable of decomposing by the action of an acid. As the repeating unit having no a fluorine atom, further the following (a) or according to any one of claims 1 to 3, characterized in that it contains at least one repeating unit selected from (c) A positive photosensitive composition for ArF excimer laser exposure.
(A) Acid-decomposable repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure (c) Repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure and a hydroxyl group The ArF according to claim 4 , wherein the (a) acid-decomposable repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure is a repeating unit represented by the following general formula (pA). A positive photosensitive composition for excimer laser exposure.

In general formula (pA), R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different.
A represents a single bond, an alkylene 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, or a combination of two or more groups. Represents.
Ra represents a group represented by any one of the general formulas (pI) to (pVI).

In general formulas (pI) to (pVI),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or R ₁₅ , Any of R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group, provided that at least one of R _{17 to} R ₂₁ is cyclo Represents an alkyl group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group, provided that at least one of R _{22 to} R ₂₅ is cyclo Represents an alkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring. Wherein (b) repeating unit having a lactone structure, ArF excimer laser exposure positive according to any one of claims 1-5, characterized in that the repeating unit represented by the following general formula (AI) Type photosensitive composition.

In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. A _b represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these. V represents a group represented by any one of the following general formula (Lc) or the following general formulas (V-1) to (V-5).

In general formula (Lc), Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ and Re ₁ each independently represents a hydrogen atom or an alkyl group. m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.
In general formulas (V-1) to (V-5), R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonylimino group, or an alkenyl group. Represents. Two of R _{1b to} R _5b may combine to form a ring. The ArF excimer according to claim 4 , wherein the repeating unit (c) having a monocyclic or polycyclic alicyclic hydrocarbon structure and a hydroxyl group is a repeating unit represented by the following general formula (AII). A positive photosensitive composition for laser exposure.

In general formula (AII), R _1c represents a hydrogen atom or a methyl group. R _{2c to} R _4c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R _{2c to} R _4c represents a hydroxyl group. Characterized by ArF excimer laser exposure for a positive resist composition according to any one of claims 1 to 7, a resist film is formed, the resist film, exposure by ArF excimer laser, further comprising the step of developing A pattern forming method. The pattern forming method according to claim 8 , wherein the exposure is immersion exposure.

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