JP2005126706A - Resin, its preparation method and chemically amplified positive resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemically amplified positive resist composition which shows good resist performance such as sensitivity. <P>SOLUTION: A resin comprises at least one polymerization unit chosen from the group consisting of a polymerization unit derived from 3-hydroxy-1-adamanthyl (meth)acrylate, a polymerization unit derived from 3,5-dihydroxy-1-adamanthyl (meth)acrylate or the like and further, comprises a polymerization unit of formula (II). The resin itself is insoluble or hardly soluble in an aqueous alkaline solution but becomes soluble in the aqueous alkaline solution when treated with an acid. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a chemically amplified resist composition used for microfabrication of semiconductors, a resin used in the composition, and a method for producing the same.

In microfabrication of semiconductors, a lithography process using a resist composition is usually employed. In lithography, in principle, the exposure wavelength is expressed as expressed by the Rayleigh diffraction limit equation. The shorter the resolution, the higher the resolution. The exposure light source for lithography used in the manufacture of semiconductors has become a shorter wavelength year by year: g-line with a wavelength of 436 nm, i-line with a wavelength of 365 nm, KrF excimer laser with a wavelength of 248 nm, and ArF excimer laser with a wavelength of 193 nm. As an exposure light source, an F ₂ excimer laser with a wavelength of 157 nm is considered promising, and thereafter soft X-rays (EUV) with a wavelength of 13 nm or less have been proposed as a light source.

  Since light sources with wavelengths shorter than g-line and i-line, such as excimer laser, have low illuminance, it is necessary to increase the sensitivity of the resist. A so-called chemically amplified resist containing a resin having a group that can be cleaved by the acid is used (see, for example, Patent Document 1).

JP 2000-137327 A (pages 13-14)

However, with further advancement of microfabrication technology, there is a demand for a resist composition having a sensitivity that exceeds that of conventional chemically amplified resist compositions.
An object of the present invention is to provide a chemically amplified positive resist composition suitable for excimer laser lithography such as ArF and KrF, which has various resist performances such as resolution, and gives particularly improved sensitivity, and the composition It is providing the resin used for a thing, and its manufacturing method.

  As a result of intensive studies, the present inventors have found that a chemically amplified positive resist composition containing a resin having a specific polymerization unit and an acid generator has good resist performance such as resolution. In particular, it has been found that it provides improved sensitivity, and the present invention has been completed.

（式中、Ｒ¹は、水素原子又はメチル基を表す。Ｒ²は、メチル基又はエチル基を表す。ｍは、０〜３の整数を表す。式（Ｉａ）において、ｍが２以上のとき、複数のＲ²は、互いに同一でも異なってもよい。式（Ｉｂ）において、ｍが２以上のとき、複数のＲ²は、互いに同一でも異なってもよい。）

（式中、Ｒ¹は、水素原子又はメチル基を表す。Ｒ³、Ｒ⁴は、互いに独立に、炭素数１〜２のアルキル基を表す。Ｒ⁵は、メチル基、ハロゲン原子又はヒドロキシル基を表す。ｎは、０〜１４の整数を表す。ｎが２以上のとき、複数のＲ^５は、互いに同一でも異なってもよい。） That is, the present invention relates to [1] a polymer unit derived from 3-hydroxy-1-adamantyl (meth) acrylate, a polymer unit derived from 3, methacrylic acid 3,5-dihydroxy-1-adamantyl, and a lactone ring. At least one selected from the group consisting of a polymer unit derived from (meth) acryloyloxy-γ-butyrolactone optionally substituted with alkyl, a polymer unit represented by the following formula (Ia), and a polymer unit represented by (Ib) A resin containing a polymer unit of a seed and further having a polymer unit represented by the following formula (II), and the resin itself is insoluble or hardly soluble in an alkaline aqueous solution, but becomes soluble in an alkaline aqueous solution by the action of an acid It is related to.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a methyl group or an ethyl group. M represents an integer of 0 to 3. In the formula (Ia), m is 2 or more. The plurality of R ² may be the same or different from each other.In Formula (Ib), when m is 2 or more, the plurality of R ² may be the same or different from each other.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ³ and R ⁴ each independently represent an alkyl group having 1 to 2 carbon atoms. R ⁵ represents a methyl group, a halogen atom or a hydroxyl group. N represents an integer of 0 to 14. When n is 2 or more, the plurality of R ⁵ may be the same as or different from each other.

  The present invention also relates to [2] a chemically amplified positive resist composition containing the resin described in [1] above and an acid generator.

（式中、Ｒ¹は、水素原子又はメチル基を表す。Ｒ²は、メチル基又はエチル基を表す。ｍは、０〜３の整数を表す。式（Ｉａ’）において、ｍが２以上のとき、複数のＲ²は、互いに同一でも異なってもよい。式（Ｉｂ’）において、ｍが２以上のとき、複数のＲ²は、互いに同一でも異なってもよい。）

（式中、Ｒ¹は、水素原子又はメチル基を表す。Ｒ³、Ｒ⁴は、互いに独立に、炭素数１〜２のアルキル基を表す。Ｒ⁵は、メチル基、ハロゲン原子又はヒドロキシル基を表す。ｎは、０〜１４の整数を表す。ｎが２以上のとき、複数のＲ^５は、互いに同一でも異なってもよい。） In the present invention, [3] 3-hydroxy-1-adamantyl (meth) acrylate, (meth) acrylic acid 3, 5-dihydroxy-1-adamantyl, and the lactone ring may be substituted with alkyl (meta) ) At least one monomer selected from the group consisting of a monomer derived from acryloyloxy-γ-butyrolactone, a monomer represented by the following formula (Ia ′) and a monomer represented by (Ib ′), and the following formula (II ′) The method for producing a resin according to the above [1], wherein the monomer is polymerized with a monomer represented by

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a methyl group or an ethyl group. M represents an integer of 0 to 3. In the formula (Ia ′), m is 2 or more. when a plurality of R ^2, in each other may be the same or different. formula (Ib '), when m is 2 or more, plural R ² may be the same or different.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ³ and R ⁴ each independently represent an alkyl group having 1 to 2 carbon atoms. R ⁵ represents a methyl group, a halogen atom or a hydroxyl group. N represents an integer of 0 to 14. When n is 2 or more, the plurality of R ⁵ may be the same as or different from each other.

  The chemically amplified positive resist composition of the present invention provides improved sensitivity and good resist performance such as resolution. Therefore, this composition is suitable for excimer laser lithography such as ArF and KrF, thereby giving a high performance resist pattern.

The composition containing the resin of the present invention and an acid generator is suitably used as a chemically amplified positive resist composition.
The resin of the present invention is a polymer unit derived from 3-hydroxy-1-adamantyl (meth) acrylate, a polymer unit derived from 3, methacrylic acid 3,5-dihydroxy-1-adamantyl, and a lactone ring substituted with alkyl. At least one selected from the group consisting of a polymer unit derived from (meth) acryloyloxy-γ-butyrolactone, a polymer unit represented by the formula (Ia) and a polymer unit represented by (Ib) It has a polymerization unit and further has a polymerization unit represented by the above formula (II).
And although this resin itself is insoluble or hardly soluble in an alkaline aqueous solution, it becomes soluble in an alkaline aqueous solution by the action of an acid. Specifically, some groups are cleaved by the action of an acid, After cleavage, it becomes soluble in an alkaline aqueous solution.

In the method for producing the resin of the present invention, 3-hydroxy-1-adamantyl (meth) acrylate, 3, methacrylic acid 3,5-dihydroxy-1-adamantyl, and the lactone ring may be substituted with alkyl (meta) ) At least one monomer selected from the group consisting of a monomer derived from acryloyloxy-γ-butyrolactone, a monomer represented by the formula (Ia ′) and a monomer represented by (Ib ′), and the above formula ( It is characterized in that it is polymerized with a monomer represented by II ′).
(Meth) acrylic acid 3-hydroxy-1-adamantyl, (meth) acrylic acid 3,5-dihydroxy-1-adamantyl are commercially available. For example, the corresponding hydroxyadamantane is converted to (meth) acrylic acid or a halide thereof. It can also be produced by reacting.
In addition, (meth) acryloyloxy-γ-butyrolactone is obtained by reacting α- or β-bromo-γ-butyrolactone in which the lactone ring may be substituted with alkyl with acrylic acid or methacrylic acid, or the lactone ring is alkyl. It can be produced by reacting an optionally substituted α- or β-hydroxy-γ-butyrolactone with an acrylic acid halide or methacrylic acid halide.
Specific examples of the monomer for leading to the polymerization units represented by the formulas (Ia) and (Ib) include, for example, (meth) acrylic acid esters of alicyclic lactones having the following hydroxyl groups, and mixtures thereof. Can be mentioned. These esters can be produced, for example, by a reaction between an alicyclic lactone having a corresponding hydroxyl group and (meth) acrylic acids (for example, JP-A No. 2000-26446).

  Polymer unit derived from (meth) acrylic acid 3-hydroxy-1-adamantyl, (meth) acrylic acid 3, 5-dihydroxy-1-adamantyl, polymer unit derived from α- (meth) acryloyloxy-γ-butyrolactone, β -A polymer unit derived from (meth) acryloyloxy-γ-butyrolactone, a polymer unit represented by formulas (Ia) and (Ib) is present in a resin substrate containing any of them in the resin. This not only improves the adhesion of the resist, but also contributes to the improvement of the resolution of the resist.

  Here, as (meth) acryloyloxy-γ-butyrolactone, for example, α-acryloyloxy-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, α-acryloyloxy-β, β-dimethyl-γ-butyrolactone, α- Methacryloyloxy-β, β-dimethyl-γ-butyrolactone, α-acryloyloxy-α-methyl-γ-butyrolactone, α-methacryloyloxy-α-methyl-γ-butyrolactone, β-acryloyloxy-γ-butyrolactone, β- Examples include methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-α-methyl-γ-butyrolactone, and the like.

Examples of the alkyl group having 1 to 4 carbon atoms which may be branched represented by R ³ and R ⁴ in the formula (II) include a methyl group and an ethyl group. Specific examples of the monomer that leads to the polymerization unit represented by the formula (II) include the following monomers.

Examples of the polymerization in the method for producing a resin of the present invention include radical polymerization, anionic polymerization, and coordination polymerization, among which radical polymerization is preferable.
The polymerization initiator used here is a known one, and is not particularly limited, but is preferably one that generates radicals efficiently by heat. Examples of such a polymerization initiator include 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl- Azo compounds such as 2,2′-azobisisobutyrate, organic peroxides such as 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, t-hexylperoxypivalate, etc. These may be used alone or in combination of two or more initiators.
Furthermore, chain transfer agents such as 1-butanethiol, 2-butanethiol, 1-octanethiol, 1-decanethiol, 1-tetradecanethiol, cyclohexanethiol, 2-methyl-1-propanethiol can be used in combination.
The organic solvent used for the polymerization is preferably a solvent that can dissolve both the monomer, the initiator, and the resulting copolymer. Examples of such organic solvents include hydrocarbons such as toluene, 1,4-dioxane, tetrahydrofuran, methyl isobutyl ketone, isopropyl alcohol, γ-butyrolactone, propylene glycol monomethyl ether acetate, ethyl lactate, and the like. Two or more kinds of solvents may be mixed and used.
The reaction temperature in the manufacturing method of this invention is the range of 0-150 degreeC, Preferably it is the range of 40-100 degreeC.

Moreover, in this invention, you may use together the other monomer which has an acid unstable group conventionally known as needed.
Specific examples of conventionally known acid-labile groups include various esters of carboxylic acid, for example, alkyl esters represented by methyl ester and tert-butyl ester; methoxymethyl ester, ethoxymethyl ester, 1-ethoxyethyl ester, 1-isobutoxyethyl ester, 1-isopropoxyethyl ester, 1-ethoxypropyl ester, 1- (2-methoxyethoxy) ethyl ester, 1- (2-acetoxyethoxy) ethyl ester, 1- Acetal type esters such as [2- (1-adamantyloxy) ethoxy] ethyl ester, 1- [2- (1-adamantanecarbonyloxy) ethoxy] ethyl ester, tetrahydro-2-furyl ester and tetrahydro-2-pyranyl ester Isobornyl Examples thereof include steric and alicyclic esters such as 2-alkyl-2-adamantyl ester and 1- (1-adamantyl) -1-alkylalkyl ester.

（式中、Ｒ¹は、水素原子又はメチル基を表す。Ｒ³は、炭素数１〜２のアルキル基を表す。）
式（ＩＩＩ）で示される重合単位に導くモノマーとして、次のものが挙げられる。

The resin of the present invention may further have a polymerization unit represented by the following formula (III) as necessary.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ³ represents an alkyl group having 1 to 2 carbon atoms.)
Examples of the monomer leading to the polymerization unit represented by the formula (III) include the following.

（式中、Ｒ¹は、水素原子又はメチル基を表す。Ｒ⁶、Ｒ⁷は、互いに独立に、炭素数１〜４の分岐していてもよいアルキル基を表す。） Moreover, the resin of this invention may have a polymer unit shown by the following Formula (IV) as needed.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 4 carbon atoms which may be branched.)

Examples of the alkyl group having 1 to 4 carbon atoms which may be branched represented by R ⁶ and R ⁷ in formula (IV) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group. Can be mentioned. Specific examples of the monomer that leads to the polymerization unit represented by the formula (IV) include monomers represented by the following formula.

The resin of the present invention may contain other polymerized units that are not cleaved or hardly cleaved by the action of an acid in addition to the polymerized units having an acid-labile group as described above. Examples of other polymer units that can be contained include polymer units of monomers having a free carboxylic acid group such as acrylic acid and methacrylic acid, and aliphatic unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. Polymerization units, 2-norbornene polymerization units, (meth) acrylonitrile polymerization units, various (meth) acrylic acid ester polymerization units, and the like.
In the case of ArF exposure, light absorption is large, which is not preferable. However, in the case of KrF exposure, there is no problem of light absorption, so that a polymerized unit of hydroxystyrene can be used.

  Moreover, since the resin containing the polymerization unit of 2-norbornene has an alicyclic group directly in the main chain, it has a sturdy structure and exhibits excellent dry etching resistance. The polymer unit of 2-norbornene can be introduced into the main chain by radical polymerization using, in addition to the corresponding 2-norbornene, an aliphatic unsaturated dicarboxylic acid anhydride such as maleic anhydride or itaconic anhydride. Therefore, the polymer unit of 2-norbornene is formed by opening a double bond thereof and can be represented by the formula (VIII). Further, the polymerization unit of maleic anhydride, which is a polymerization unit of an aliphatic unsaturated dicarboxylic acid anhydride, and the polymerization unit of itaconic anhydride are formed by opening their double bonds, and are each represented by formula (IX) And (X).

Here, R ⁸ and R ⁹ in formula (VIII) are each independently a hydrogen atom, alkyl having 1 to 3 carbon atoms, hydroxyalkyl having 1 to 3 carbon atoms, carboxyl, cyano, or a group —COOZ (Z is Which is an alcohol residue), or R ⁸ and R ⁹ can be combined to form a carboxylic acid anhydride residue represented by —C (═O) OC (═O) —.
Specific examples of when R ⁸ and / or R ⁹ are alkyl include methyl, ethyl, propyl and the like, and specific examples of the case where R ⁸ and / or R ⁹ are also hydroxyalkyl include hydroxymethyl, 2-hydroxyethyl and the like. It is done.
When R ⁸ and / or R ⁹ is a group —COOZ, carboxyl is an ester, and the alcohol residue corresponding to Z is, for example, about 1 to 8 carbon atoms that may be substituted. Alkyl, 2-oxooxolan-3- or -4-yl, and the like. Examples of the alkyl substituent include a hydroxyl group and an alicyclic hydrocarbon residue.
Thus, specific examples of R ⁸ and / or R ⁹ being a carboxylate residue represented by —COOZ include methoxycarbonyl, ethoxycarbonyl, 2-hydroxyethoxycarbonyl, tert-butoxycarbonyl, 2-oxooxo Lan-3-yloxycarbonyl, 2-oxooxolan-4-yloxycarbonyl, 1,1,2-trimethylpropoxycarbonyl, 1-cyclohexyl-1-methylethoxycarbonyl, 1- (4-methylcyclohexyl) -1 -Methylethoxycarbonyl, 1- (1-adamantyl) -1-methylethoxycarbonyl and the like.

  Specific examples of the monomer for leading to the polymerization unit represented by the formula (VIII) include the following compounds.

2-norbornene,
2-hydroxy-5-norbornene,
5-norbornene-2-carboxylic acid,
Methyl 5-norbornene-2-carboxylate,
5-norbornene-2-carboxylic acid-t-butyl,
1-cyclohexyl-1-methylethyl 5-norbornene-2-carboxylate,
1- (4-methylcyclohexyl) -1-methylethyl 5-norbornene-2-carboxylate,
1- (4-hydroxycyclohexyl) -1-methylethyl 5-norbornene-2-carboxylate,
1-methyl-1- (4-oxocyclohexyl) ethyl 5-norbornene-2-carboxylate,
1- (1-adamantyl) -1-methylethyl 5-norbornene-2-carboxylate,
1-methylcyclohexyl 5-norbornene-2-carboxylate,
2-methyl-2-adamantyl 5-norbornene-2-carboxylate,
2-ethyl-2-adamantyl 5-norbornene-2-carboxylate,
2-hydroxy-1-ethyl 5-norbornene-2-carboxylate,
5-norbornene-2-methanol,
5-norbornene-2,3-dicarboxylic anhydride and the like.

  The resin according to the present invention preferably has a weight average molecular weight of 1,000 to 100,000, particularly 5,000 to 20,000.

The resin of the present invention varies depending on the type of radiation for patterning exposure and the type of acid-labile group, but generally, the total polymerization unit of the resin is 3-hydroxy- (meth) acrylate. Polymerized units derived from 1-adamantyl, (meth) acrylic acid 3, polymerized units derived from 5-dihydroxy-1-adamantyl, derived from (meth) acryloyloxy-γ-butyrolactone in which the lactone ring may be substituted with alkyl It is preferable to contain at least one polymer unit selected from the group consisting of a polymer unit to be used, a polymer unit represented by the following formula (Ia) and a polymer unit represented by (Ib) in the range of 90 to 20 mol%. The polymerization unit represented by the formula (II) is preferably contained in the range of 10 to 80 mol%, and the former polymerization unit is contained in the range of 85 to 20 mol%. More preferably contribute, it is further preferable that the latter polymerized units containing in the range of 15 to 80 mol%.
In addition to these polymerized units, other polymerized units that are not easily cleaved by the action of an acid, for example, polymerized units represented by the formula (VIII), polymerized units derived from aliphatic unsaturated dicarboxylic acid anhydrides. When polymerized units derived from maleic anhydride represented by the formula (IX) and polymerized units derived from itaconic anhydride represented by the formula (X) are present, the total of these polymerized units is the total polymerization of the resin. It is preferable to be in the range of 2 to 70 mol% with respect to the unit.

  In addition, when 2-norbornenes and aliphatic unsaturated dicarboxylic acid anhydrides are used as copolymerization monomers, they tend to be difficult to polymerize. Therefore, in consideration of this point, it is preferable to use them excessively. .

The chemical amplification type positive resist composition of the present invention is characterized by containing the resin and an acid generator.
As the acid generator constituting the resist composition of the present invention, the substance is decomposed by the action of radiation such as light or electron beam on the substance itself or on the resist composition containing the substance. Is generated. The acid generated from the acid generator acts on the resin and cleaves the group that is cleaved by the action of the acid present in the resin.

（式中、Ｐ¹〜Ｐ³は、互いに独立に、水酸基、炭素数１〜６のアルキル基又は炭素数１〜６のアルコキシ基を表す。ｐ、ｑ、ｒは、それぞれ独立に０〜３の整数である。ｐが２以上のとき、複数のＰ¹は、互いに同一でも異なってもよい。ｑが２以上のとき、複数のＰ²は、互いに同一でも異なってもよい。ｒが２以上のとき、複数のＰ³は、互いに同一でも異なってもよい。Ｚ⁻は、対イオンを表す。）

（式中、Ｐ^４、Ｐ^５は、互いに独立に、水素原子、水酸基、炭素数１〜６のアルキル基又は炭素数１〜６のアルコキシ基を表す。ｓ、ｔは、互いに独立に、０〜１の整数である。Ｚ⁻は、対イオンを表す。）

（式中、Ｐ^６、Ｐ^７は、互いに独立に、炭素数１〜６のアルキル基、炭素数３〜１０のシクロアルキル基、又はＰ^６とＰ^７とが結合して炭素数３〜７の二価の脂肪族炭化水素基を表し、隣接するＳ^＋とともに環を形成する。該脂肪族炭化水素基の少なくとも１個の−ＣＨ₂−がカルボニル基、酸素原子もしくは硫黄原子に置換されていてもよい。Ｐ^８が水素原子を表し、Ｐ^９が炭素数１〜６のアルキル基、炭素数３〜１０のシクロアルキル基もしくは置換されていても良い芳香環基を表すか、又はＰ^８とＰ^９とが結合して二価の脂肪族炭化水素基を表し、隣接する−ＣＨＣＯ−とともに環を形成する。Ｚ⁻は、対イオンを表す。） Examples of the acid generator in the present invention include the following formula (Va), (Vb), or (Vc).

(Wherein, P ¹ to P ³ is 0-3 independently of one another, hydroxyl, .p represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms having 1 to 6 carbon atoms, q, r are each independently When p is 2 or more, the plurality of P ¹ may be the same or different from each other, and when q is 2 or more, the plurality of P ² may be the same or different from each other, r is 2 In the above, a plurality of P ³ may be the same or different from each other, Z ⁻ represents a counter ion.)

(Wherein P ⁴ and P ⁵ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. S and t are each independently 0 (It is an integer of ˜1. Z ⁻ represents a counter ion.)

(Wherein P ⁶ and P ⁷ are independently of each other an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or P ⁶ and P ⁷ bonded to each other to form 3 to 7 carbon atoms. And forms a ring with adjacent S ⁺ , wherein at least one —CH ₂ — of the aliphatic hydrocarbon group is substituted with a carbonyl group, an oxygen atom or a sulfur atom. P ⁸ represents a hydrogen atom and P ⁹ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or an optionally substituted aromatic ring group, or P ⁸ And P ⁹ bind to each other to represent a divalent aliphatic hydrocarbon group and form a ring together with the adjacent —CHCO—, and Z ⁻ represents a counter ion.

When P ¹ , P ² , and P ³ in formula (Va) are an alkyl group or an alkoxy group, they may be linear or branched when they have 3 or more carbon atoms.
When P ⁴ and P ⁵ in Formula (Vb) are an alkyl group or an alkoxy group, they may be linear or branched when they have 3 or more carbon atoms.
Examples of specific alkyl groups of P ¹ , P ² , P ³ , P ⁴ and P ⁵ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

In the formula (Vc), when P ⁶ and P ⁷ are bonded to each other to represent a C 3-7 divalent aliphatic hydrocarbon group, at least one —CH of the aliphatic hydrocarbon group _2- may be substituted with a carbonyl group, an oxygen atom or a sulfur atom.
When P ⁶ , P ⁷ and P ⁹ are alkyl groups, specific examples include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, and hexyl groups. In the case of a cycloalkyl group, specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

  Specific examples of the cation in the formulas (Va), (Vb), and (Vc) include the following.

（式中、Ｑ¹、Ｑ²、Ｑ³、Ｑ⁴及びＱ⁵は、互いに独立に、水素原子、炭素数１〜１６個の分岐していてもよいアルキル基、炭素数１〜１６個の分岐していてもよいアルコキシ基、ハロゲン原子、炭素数１〜８個のハロゲン化アルキル基、炭素数６〜１２個のアリール基、炭素数７〜１２のアラルキル基、シアノ基、炭素数１〜４個のアルキルチオ基、炭素数１〜４個のアルキルスルホニル基、ヒドロキシ基、ニトロ基又は下式（ＶＩ’）で示される基を表す。ただし、Ｑ¹、Ｑ²、Ｑ³、Ｑ⁴及びＱ⁵のうち少なくとも一つは、下式（ＶＩ’）で示される基である。

式中、Ｘは、酸素原子又は硫黄原子を含んでも良い直鎖アルキレン基を表し、Ｃｙ^１は、炭素数３〜２０個の脂環式炭化水素基を表す。）
炭素数１〜１６の分岐していてもよいアルキル基の例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、ヘキサデシル基などが挙げられる。
炭素数１〜１６の分岐していてもよいアルコキシ基の例としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、tert−ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、イソペンチルオキシ基、デシルオキシ基、ドデシルオキシ基、ヘキサデシルオキシ基などが挙げられる。
ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。
炭素数６〜１２個のアリール基としては、フェニル基、トリル基、メトキシフェニル基、ナフチル基などが挙げられる。
炭素数７〜１２のアラルキル基としては、ベンジル基、クロロベンジル基、メトキシベンジル基などが挙げられる。 Examples of the counter ion Z ⁻ of the acid generator in the present invention include anions represented by the following formula (VI).

(In the formula, Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms which may be branched, or a group having 1 to 16 carbon atoms. An optionally branched alkoxy group, halogen atom, halogenated alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 12 carbon atoms, aralkyl group having 7 to 12 carbon atoms, cyano group, 1 to carbon atoms 4 alkylthio groups, an alkylsulfonyl group having 1 to 4 carbon atoms, a hydroxy group, a nitro group, or a group represented by the following formula (VI ′), provided that Q ¹ , Q ² , Q ³ , Q ⁴ and At least one of Q ⁵ is a group represented by the following formula (VI ′).

In the formula, X represents a linear alkylene group that may contain an oxygen atom or a sulfur atom, and Cy ¹ represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms. )
Examples of the alkyl group having 1 to 16 carbon atoms which may be branched include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and decyl group. , Dodecyl group, hexadecyl group and the like.
Examples of the alkoxy group having 1 to 16 carbon atoms which may be branched include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, isopentyl Examples thereof include an oxy group, a decyloxy group, a dodecyloxy group, and a hexadecyloxy group.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a chlorobenzyl group, and a methoxybenzyl group.

In addition, when two or more groups represented by formula (VI ′) are included among Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ , X and Cy ^{1 of the} group are each independently You can choose.

上記式において、好ましくは（ａ-１）〜（ａ-７）の直鎖アルキレン基が挙げられる。 Examples of X include the following.

In the above formula, preferably, a linear alkylene group of (a-1) to (a-7) is used.

上記式において、好ましくはシクロヘキシル基（ｂ−４）、２−ノルボルニル基（ｂ−２１）、１−アダマンチル基（ｂ−２４）、２−アダマンチル基（ｂ−２３）が挙げられる。 Examples of Cy ¹ include the following.

In said formula, Preferably a cyclohexyl group (b-4), 2-norbornyl group (b-21), 1-adamantyl group (b-24), 2-adamantyl group (b-23) is mentioned.

Specific examples of the anion represented by the formula (VI) include the following.

（式中、Ｑ⁶は、炭素数１〜２０の分岐していてもよいパーフルオロアルキル基又は炭素数１０〜２０の置換されていてもよいナフチル基及びアントリル基を表す。） Moreover, the anion represented by the following Formula (VIIa) is mentioned as counter ion Z < ^- > in an acid generator.

(Wherein, Q ⁶ represents a branched good perfluoro also be an alkyl group or an optionally substituted naphthyl group or an anthryl group having 10 to 20 carbon atoms having 1 to 20 carbon atoms.)

Examples of the anion represented by the formula (VIIa) include the following, but these are examples and do not represent all of them.

（式中、Ｑ⁷、Ｑ⁸は、互いに独立に、炭素数１〜２０の分岐していてもよいパーフルオロアルキル基又は炭素数６〜２０の置換されていてもよい芳香環基を表す。） Moreover, the anion represented by the following Formula (VIIb) is mentioned as counter ion Z < ^- > in an acid generator.

(In formula, Q < ⁷ >, Q < ⁸ > represents the C1-C20 perfluoroalkyl group which may be branched, or the C6-C20 optionally substituted aromatic ring group mutually independently. )

Examples of the anion represented by the formula (VIIb) include the following, but these are examples and do not represent all of them.

The counter ion Z ⁻ of the acid generator may be an anion of a halogen compound, an anion of a sulfone compound, or an anion of a sulfonate compound. Specific examples include hexafluoroantimonate, tetrafluoroborate, hexafluorophosphate, and the like.

  Further, in the chemically amplified positive resist of the present invention, by adding a basic nitrogen-containing compound as a quencher, it is possible to improve performance deterioration due to acid deactivation accompanying holding after exposure. Specific examples of such basic nitrogen-containing compounds include amines represented by the following formulas.

In the formula, R ¹² , R ¹³ and R ¹⁸ each independently represent a hydrogen atom, alkyl, cycloalkyl or aryl. The alkyl, cycloalkyl, or aryl may be each independently substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms. The alkyl preferably has about 1 to 6 carbon atoms, the cycloalkyl preferably has about 5 to 10 carbon atoms, and the aryl preferably has about 6 to 10 carbon atoms.
R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom, alkyl, cycloalkyl, aryl or alkoxy. The alkyl, cycloalkyl, aryl, or alkoxy may be each independently substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms. In addition, the alkyl preferably has about 1 to 6 carbon atoms, the cycloalkyl preferably has about 5 to 10 carbon atoms, the aryl preferably has about 6 to 10 carbon atoms, and the alkoxy has 1 to about carbon atoms. About 6 is preferable.
R ¹⁷ represents alkyl or cycloalkyl. The alkyl or cycloalkyl may each independently be substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms. The alkyl preferably has about 1 to 6 carbon atoms, and the cycloalkyl preferably has about 5 to 10 carbon atoms.
A represents alkylene, carbonyl, imino, sulfide or disulfide. The alkylene preferably has about 2 to 6 carbon atoms.
Further, in R ^{12 to} R ¹⁸ , any of those that can take both a linear structure and a branched structure may be used.
However, none of R ¹² , R ¹³ and R ¹⁸ in the compound of the formula [3] is a hydrogen atom.
R ^{19 to} R ²¹ may be the same or different and are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or 6 Represents -20 substituted or unsubstituted aryl groups, wherein R ¹⁹ and R ²⁰ may be bonded to each other to form a ring;

  Specific examples of such compounds include hexylamine, heptylamine, octylamine, nonylamine, decylamine, aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, 1- or 2-naphthylamine, and ethylenediamine. Tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'- Diethyldiphenylmethane, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N-methylaniline, piperidine, diphenylamine, triethylamine, trimethylamine, tripropylamine, tributylamine , Tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine , Methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, N, N-dimethylaniline, 2,6-isopropylaniline, imidazole, pyridine, -Methylpyridine, 4-methylimidazole, bipyridine, 2,2'-dipyridylamine, di-2-pyridyl ketone, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,3-di (4-pyridyl) propane, 1,2-bis (2-pyridyl) ethylene, 1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridyloxy) ethane, 4 , 4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicolylamine, 3,3'-dipicolylamine, tetramethylammonium hydroxide Tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetra-n-hexylammonium hydroxide, tetra-n- Examples thereof include octylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, choline, N-methylpyrrolidone, and dimethylimidazole.

  Furthermore, a hindered amine compound having a piperidine skeleton as disclosed in JP-A-11-52575 can be used as a quencher.

The resist composition of the present invention preferably contains 80 to 99.9% by weight of the resin and 20 to 0.1% by weight of the acid generator with respect to the total weight of the resin and the acid generator.
In the composition of the present invention, when a basic nitrogen-containing compound is used, it is in the range of 0.001 to 1 part by weight, more preferably in the range of 0.01 to 0.3 part by weight with respect to 100 parts by weight of the resin. It is preferable to contain.
The composition of the present invention can contain small amounts of various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, and dyes as necessary.

The resist composition of the present invention is usually made into a resist solution composition in a state where each of the above components is dissolved in a solvent, and is applied on a substrate such as a silicon wafer according to a conventional method such as spin coating. The solvent used here may be any solvent that dissolves each component, has an appropriate drying rate, and gives a uniform and smooth coating film after the solvent evaporates, and a solvent generally used in this field is used. Yes.
For example, glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; acetone, methyl isobutyl ketone, 2-heptanone And ketones such as cyclohexanone; cyclic esters such as γ-butyrolactone. These solvents can be used alone or in combination of two or more.

The resist film coated and dried on the substrate is subjected to an exposure process for patterning, followed by a heat treatment for promoting a deprotecting group reaction, and then developed with an alkali developer. The alkaline developer used here may be various alkaline aqueous solutions used in this field, but generally an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline) is used. Often used.
While the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and further includes meanings equivalent to the description of the claims and all modifications within the scope.

EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples. In the examples, “%” and “part” representing the content or amount used are based on weight unless otherwise specified.
The weight average molecular weight is a value obtained by gel permeation chromatography using polystyrene as a standard product.
Furthermore, the actual composition ratio of the resin was calculated by measuring the NMR spectrum of the resin or a decomposition product obtained by decomposing the resin with hydrogen iodide using a gas chromatograph, and quantifying this by a normal internal standard method. .

Example 1
[Synthesis of Resin A1]
Charge 8.50 g of 2-isopropyl-2-adamantyl methacrylate, 4.80 g of 3-hydroxy-1-adamantyl acrylate, and 11.24 g of 5-acryloyloxy-2,6-norbornenelactone (molar ratio 30:20). : 50), 2.6 weight times dioxane of all monomers was added to make a solution. 3 mol% of azobisisobutyronitrile as an initiator was added thereto as the initiator, and the mixture was heated at 85 ° C. for about 5 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times for precipitation. As a result, a copolymer having a weight average molecular weight of about 10,000 was obtained in a yield of 76%. This copolymer has each structural unit of the following formula, and this is designated as resin A1. The actual composition ratio of the obtained resin was almost the same as the preparation ratio.

Example 2
[Synthesis of Resin A2]
8.50 g of 2-ethyl-2-adamantyl methacrylate, 5.07 g of 3-hydroxy-1-adamantyl acrylate, and 11.87 g of 5-acryloyloxy-2,6-norbornenelactone (molar ratio 30:20) : 50), 2.6 weight times dioxane of all monomers was added to make a solution. 3 mol% of azobisisobutyronitrile as an initiator was added thereto as the initiator, and the mixture was heated at 85 ° C. for about 5 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times for precipitation. As a result, a copolymer having a weight average molecular weight of about 10,000 was obtained in a yield of 82%. This copolymer has each structural unit of the following formula, and this is designated as resin A2. The actual composition ratio of the obtained resin was almost the same as the preparation ratio.

Examples 3-5, Comparative Examples 1-3
The following components were mixed and dissolved, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist solution as shown in Table 1.

<Acid generator>
B1: 2-oxo-2-phenylethyl thiacyclopentanium perfluorobutanesulfonate 0.215 parts B2: p-tolyldiphenylsulfonium perfluoro-N-[(perfluoroethyl) sulfonyl] -1-ethanesulfonamidate 0.26 parts <Resin>
Types listed in Table 1: 10 parts <quencher>
2,6-diisopropylaniline 0.0075 part <solvent>
Propylene glycol monomethyl ether acetate 33.25 parts 2-heptanone 33.25 parts γ-butyrolactone 3.5 parts

A silicon wafer was coated with “ARC-29A-8”, an organic antireflective coating composition manufactured by Brewer, and baked at 215 ° C. for 60 seconds to form an organic antireflective coating having a thickness of 780 mm. Then, the above resist solution was spin-coated thereon so that the film thickness after drying was 0.27 μm. After applying the resist solution, pre-baking was performed on a direct hot plate at a temperature indicated in the column “PB” in Table 1 for 60 seconds. Using the ArF excimer stepper (“NSR ArF” manufactured by Nikon Corporation, NA = 0.55 2/3 Annual) on each wafer on which the resist film is thus formed, the exposure amount is changed stepwise to form a line and space pattern. Exposed.
After exposure, post-exposure baking is performed for 60 seconds on the hot plate at the temperature shown in the column of “PEB” in Table 1, and further paddle development is performed for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution. It was.
The bright field pattern after development on the organic antireflection film substrate was observed with a scanning electron microscope, and the results are shown in Table 2. The bright field pattern here is a chrome layer (light-shielding layer) on the outer frame, and a chrome layer (light-shielding layer) is formed in a line on the inside of the frame with the glass surface (translucent part) as a base. The pattern is obtained by exposure and development through a reticle. Therefore, after exposure and development, the resist layer around the line and space pattern is removed, and a resist layer corresponding to the outer frame is left outside.

  Effective sensitivity: 0.13 μm line-and-space pattern was displayed at an exposure amount of 1: 1.

[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example No. Resin Acid generator Quencher PB PEB
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 3 A1 / 10 part B1 / 0.215 part C1 / 0.01 part 130 ° C 90 ° C
B2 / 0.26 part Example 4 A1 / 10 part B1 / 0.215 part C1 / 0.01 part 130 ° C 100 ° C
B2 / 0.26 part Example 5 A1 / 10 part B1 / 0.215 part C1 / 0.01 part 130 ° C 110 ° C
B2 / 0.26 parts

Comparative Example 1 A2 / 10 part B1 / 0.215 part C1 / 0.01 part 130 ° C 90 ° C
B2 / 0.26 part comparative example 2 A2 / 10 part B1 / 0.215 part C1 / 0.01 part 130 ℃ 100 ℃
B2 / 0.26 part Comparative Example 3 A2 / 10 part B1 / 0.215 part C1 / 0.01 part 130 ° C 110 ° C
B2 / 0.26 part━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[Table 2]
━━━━━━━━━━━━━━━━━━━━━━━
Example No. Effective sensitivity Resolution
(mJ / cm ² ) (μm)
━━━━━━━━━━━━━━━━━━━━━━━
Example 3 29 0.13
Example 4 15 0.13
Example 5 8 0.13

Comparative Example 1 44> 0.20
Comparative Example 2 19 0.13
Comparative Example 3 10 0.13
━━━━━━━━━━━━━━━━━━━━━━━

Since the chemically amplified positive resist composition of the present invention maintains various resist performances such as resolution and provides particularly improved sensitivity, it is suitably used for excimer laser lithography such as ArF and KrF. . The resin of the present invention is suitably used as a component of the chemically amplified positive resist composition, and the method for producing the resin is industrially useful.

Claims (13)

The polymer unit derived from 3-hydroxy-1-adamantyl (meth) acrylate, the polymer unit derived from 3, methacrylic acid 3,5-dihydroxy-1-adamantyl, and the lactone ring may be substituted with alkyl ( A polymer unit derived from (meth) acryloyloxy-γ-butyrolactone, at least one polymer unit selected from the group consisting of a polymer unit represented by the following formula (Ia) and a polymer unit represented by (Ib): A resin having a polymerization unit represented by formula (II), wherein the resin itself is insoluble or hardly soluble in an alkaline aqueous solution, but becomes soluble in an alkaline aqueous solution by the action of an acid.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a methyl group or an ethyl group. M represents an integer of 0 to 3. In the formula (Ia), m is 2 or more. The plurality of R ² may be the same or different from each other.In Formula (Ib), when m is 2 or more, the plurality of R ² may be the same or different from each other.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ³ and R ⁴ each independently represent an alkyl group having 1 to 2 carbon atoms. R ⁵ represents a methyl group, a halogen atom or a hydroxyl group. N represents an integer of 0 to 14. When n is 2 or more, the plurality of R ⁵ may be the same as or different from each other.   The resin according to claim 1, wherein the content of the polymer unit represented by the formula (II) in all the polymer units of the resin is 10 to 80 mol%.   The resin according to any one of claims 1 to 2, wherein the resin further comprises a polymer unit derived from 2-norbornene and a polymer unit derived from an aliphatic unsaturated dicarboxylic acid anhydride. The resin according to any one of claims 1 to 3, wherein the resin further has a polymer unit represented by the following formula (III).

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ³ represents an alkyl group having 1 to 2 carbon atoms.) The resin according to any one of claims 1 to 4, wherein the resin further has a polymerization unit represented by the following formula (IV).

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 4 carbon atoms which may be branched.)   A chemically amplified positive resist composition comprising the resin according to any one of claims 1 to 5 and an acid generator. The composition according to claim 6, wherein the acid generator is represented by the following formula (Va), (Vb) or (Vc).

(Wherein, P ¹ to P ³ is 0-3 independently of one another, hydroxyl, .p represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms having 1 to 6 carbon atoms, q, r are each independently When p is 2 or more, the plurality of P ¹ may be the same or different from each other, and when q is 2 or more, the plurality of P ² may be the same or different from each other, r is 2 In the above, a plurality of P ³ may be the same or different from each other, Z ⁻ represents a counter ion.)

(Wherein P ⁴ and P ⁵ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. S and t are each independently 0 (It is an integer of ˜1. Z ⁻ represents a counter ion.)

(Wherein P ⁶ and P ⁷ are independently of each other an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or P ⁶ and P ⁷ bonded to each other to form 3 to 7 carbon atoms. And forms a ring with adjacent S ⁺ , wherein at least one —CH ₂ — of the aliphatic hydrocarbon group is substituted with a carbonyl group, an oxygen atom or a sulfur atom. P ⁸ represents a hydrogen atom, and P ⁹ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an optionally substituted aromatic ring group, or P ⁸ And P ⁹ bind to each other to represent a divalent aliphatic hydrocarbon group and form a ring together with the adjacent —CHCO—, and Z ⁻ represents a counter ion. The composition according to claim 7, wherein the counter ion Z ⁻ in the acid generator is represented by the following formula (VI).

(In the formula, Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms which may be branched, or a group having 1 to 16 carbon atoms. An optionally branched alkoxy group, halogen atom, halogenated alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 12 carbon atoms, aralkyl group having 7 to 12 carbon atoms, cyano group, 1 to carbon atoms 4 alkylthio groups, an alkylsulfonyl group having 1 to 4 carbon atoms, a hydroxy group, a nitro group, or a group represented by the following formula (VI ′), provided that Q ¹ , Q ² , Q ³ , Q ⁴ and At least one of Q ⁵ is a group represented by the following formula (VI ′).

In the formula, X represents a linear alkylene group that may contain an oxygen atom or a sulfur atom, and Cy ¹ represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ) The composition of claim 7 which is characterized in that it is a following formula (VIIa) or (VIIb) ^- pairs in the acid-generating agent ions Z.

(Wherein, Q ⁶ represents a branched good perfluoro also be an alkyl group or an optionally substituted naphthyl group and an anthryl group having 10 to 20 carbon atoms having 1 to 20 carbon atoms.)

(In formula, Q < ⁷ >, Q < ⁸ > represents the C1-C20 perfluoroalkyl group which may be branched, or the C6-C20 optionally substituted aromatic ring group mutually independently. )   The composition according to any one of claims 7 to 9, comprising a resin in a range of 80 to 99.9% by weight and an acid generator in a range of 20 to 0.1% by weight based on the total weight of the resin and the acid generator. Stuff.   Furthermore, the composition in any one of Claims 7-10 which contains a basic nitrogen-containing compound as a quencher.   The composition of Claim 11 which contains a basic nitrogen-containing compound in 0.001-1 weight part with respect to 100 weight part of resin. (Meth) acrylic acid 3-hydroxy-1-adamantyl, (meth) acrylic acid 3,5-dihydroxy-1-adamantyl, derived from (meth) acryloyloxy-γ-butyrolactone, the lactone ring of which may be substituted with alkyl A monomer, at least one monomer selected from the group consisting of a monomer represented by the following formula (Ia ′) and a monomer represented by (Ib ′), and a monomer represented by the following formula (II ′) are further polymerized The method for producing a resin according to claim 1.

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a methyl group or an ethyl group. M represents an integer of 0 to 3. In the formula (Ia ′), m is 2 or more. when a plurality of R ^2, in each other may be the same or different. formula (Ib '), when m is 2 or more, plural R ² may be the same or different.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ³ and R ⁴ each independently represent an alkyl group having 1 to 2 carbon atoms. R ⁵ represents a methyl group, a halogen atom or a hydroxyl group. N represents an integer of 0 to 14. When n is 2 or more, the plurality of R ⁵ may be the same as or different from each other.