JP2011095623A - Radiation-sensitive resin composition for liquid immersion exposure and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition for liquid immersion exposure having a large receding contact angle to a liquid for immersion exposure and giving a photoresist film less liable to cause development defects, and a pattern forming method using the same. <P>SOLUTION: The radiation-sensitive resin composition for liquid immersion exposure includes [A] a sulfonium salt having at least one phenyl group or naphthyl group having a hydroxyl group, [B] a polymer containing fluorine atoms of ≥5 mass%, and [C] a polymer having an acid dissociable group and containing fluorine atoms of <5 mass%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition for immersion exposure that provides a photoresist film that has a large receding contact angle with an immersion exposure solution and is less likely to cause development defects, and a pattern formation method using the same.

  In the field of microfabrication for manufacturing integrated circuit elements, in order to obtain a higher degree of integration, a lithography technique capable of microfabrication at a level of 0.10 μm or less is desired. However, in the conventional lithography technique, near ultraviolet rays such as i-rays are used as radiation, and micromachining at a level of 0.10 μm or less (sub-quarter micron level) is extremely difficult with this near ultraviolet rays. Therefore, in order to enable microfabrication at a level of 0.10 μm or less, development of a lithography technique using radiation having a shorter wavelength is being performed. Examples of radiation having a shorter wavelength include an emission line spectrum of a mercury lamp, far ultraviolet rays such as an excimer laser, an X-ray, and an electron beam. Among these, KrF excimer laser (wavelength 248 nm) and ArF excimer laser (wavelength 193 nm) are attracting attention.

  With the attention of excimer lasers, many materials for photoresist films for excimer lasers have been proposed. For example, it contains a component having an acid-dissociable functional group and a component that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”) (hereinafter referred to as “acid generator”), and these chemical amplification effects And the like (hereinafter referred to as “chemically amplified resist”). Specifically, a composition containing a resin having a tert-butyl ester group of carboxylic acid or a tert-butyl carbonate group of phenol and an acid generator has been reported as a chemically amplified resist. In this composition, the tert-butyl ester group or tert-butyl carbonate group present in the resin is dissociated by the action of an acid generated by exposure, and the resin has an acidic group composed of a carboxyl group or a phenolic hydroxyl group. To have. As a result, the exposed region of the photoresist film becomes readily soluble in an alkali developer, so that a desired resist pattern can be formed.

  However, in the field of microfabrication, it is desired to form a finer resist pattern (for example, a fine resist pattern having a line width of about 45 nm). In order to make it possible to form a finer resist pattern, for example, the light source wavelength of the exposure apparatus can be shortened, the numerical aperture (NA) of the lens can be increased, and the like. However, shortening the light source wavelength requires a new exposure apparatus, but such an apparatus is expensive. Further, when the numerical aperture of the lens is increased, the resolution and the depth of focus are in a trade-off relationship. Therefore, there is a problem that the depth of focus is lowered even if the resolution can be improved.

  Therefore, in recent years, a method called an immersion exposure (liquid immersion lithography) method has been reported as a lithography technique for solving such a problem. This method is a method in which a liquid for immersion exposure (for example, pure water, fluorine-based inert liquid, or the like) is interposed between the lens and the photoresist film (on the photoresist film) at the time of exposure. According to this method, the exposure optical path space that has been conventionally filled with an inert gas such as air or nitrogen is filled with an immersion exposure liquid having a refractive index (n) larger than that of air or the like. Even when the same exposure light source is used, the same effect as when the light source wavelength of the exposure apparatus is shortened, that is, high resolution can be obtained. Moreover, there is no reduction in the depth of focus.

  Therefore, according to such an immersion exposure method, it is possible to form a resist pattern that is low in cost, excellent in resolution, and also excellent in depth of focus, using a lens mounted on an existing apparatus. it can. Therefore, many compositions used for the immersion exposure method are disclosed (for example, refer patent documents 1-3).

International Publication No. 04/068242 JP 2005-173474 A JP 2006-48029 A

  However, even when the compositions disclosed in Patent Documents 1 to 3 are used, there is a problem in that defects derived from undissolved residues during development occur. This defect is a defect that is considered to be caused by aggregation of components in the photoresist film in the developing solution and re-adhesion on the pattern.

  The present invention provides a radiation-sensitive resin composition for immersion exposure that provides a photoresist film that has a large receding contact angle with the immersion exposure liquid and is less likely to cause development defects, and a pattern forming method using the same. Objective.

（式中、Ｒ^１は、相互に独立して、フッ素原子、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数１〜１０の直鎖状若しくは分岐状のアルコキシル基、炭素数２〜１１の直鎖状若しくは分岐状のアルコキシカルボニル基、又は、炭素数１〜１０の直鎖状、分岐状若しくは環状のアルカンスルホニル基であり、Ｒ^２は、相互に独立して、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、置換基を有してもよいフェニル基又は置換基を有してもよいナフチル基、或いは、２つのＲ^２が互いに結合して炭素数２〜１０の２価の基を形成しており且つ置換基を有してもよい基であり、Ｘ⁻はアニオンであり、ｋは０〜２の整数であり、ｒ_１は１〜８の整数であり、ｒ_２は０〜８の整数である。）
２．上記化合物［Ａ］の含有量が、上記重合体［Ｂ］及び上記重合体［Ｃ］の合計１００質量部に対して０．１〜２０質量部である上記１に記載の液浸露光用感放射線性樹脂組成物。
３．上記重合体［Ｂ］の含有量が、上記重合体［Ｃ］１００質量部に対して０．１〜２０質量部である上記１又は２に記載の液浸露光用感放射線性樹脂組成物。
４．上記重合体［Ｂ］が、下記一般式（２）で表される繰り返し単位、又は、下記一般式（３）で表される繰り返し単位を有する上記１乃至３のいずれかに記載の液浸露光用感放射線性樹脂組成物。

（式中、Ｒ^３は、水素原子、メチル基又はトリフルオロメチル基であり、Ｒ^４は、少なくとも１つの水素原子がフッ素原子で置換された炭素数１〜６の直鎖状若しくは分岐状のアルキル基、又は、少なくとも１つの水素原子がフッ素原子で置換された炭素数４〜２０の脂環式炭化水素基若しくはその誘導体基である。）

（式中、ｎは１〜３の整数であり、Ｒ^５は、水素原子、メチル基又はトリフルオロメチル基であり、Ｒ^６は、単結合、或いは、（ｎ＋１）価であって、炭素数１〜１０の、直鎖状、分岐状又は環状の飽和炭化水素基若しくは不飽和炭化水素基であり、Ｒ^７は、単結合、或いは、２価であって、炭素数１〜２０の、直鎖状、分岐状若しくは環状の飽和炭化水素基又は不飽和炭化水素基であり、Ｇ^１は、−ＣＨＦ−、−ＣＦ_２−、又は、炭素数２〜２０の直鎖状若しくは分岐状のフルオロアルキレン基であり、Ｇ^２は、単結合又は−ＣＯ−であり、Ｒ^８は、相互に独立して、水素原子又は酸解離性基である。）
５．上記１〜４のいずれか一項に記載の液浸露光用感放射線性樹脂組成物を用いて基板上にフォトレジスト膜を形成する工程と、上記フォトレジスト膜上に液浸露光用液体を配置し、上記液浸露光用液体を介して上記フォトレジスト膜を液浸露光する工程と、液浸露光された上記フォトレジスト膜を現像してレジストパターンを形成する工程と、を備えることを特徴とするレジストパターン形成方法。 The present invention is as follows.
1. [A] A compound represented by the following general formula (1), [B] a polymer containing 5 mass% or more of fluorine atoms, and [C] an acid-dissociable group and containing less than 5 mass% of fluorine atoms A radiation-sensitive resin composition for immersion exposure, comprising a polymer.

(In the formula, R ¹ is independently of each other a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxyl group having 1 to 10 carbon atoms, carbon, A linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms, or a linear, branched or cyclic alkanesulfonyl group having 1 to 10 carbon atoms, and R ² is a carbon atom independently of each other. the number 1 to 10 linear or branched alkyl group, a phenyl group which may have a substituent or substituents naphthyl group which may have a, or the number of carbon two R ² are bonded to each other Is a group that forms a divalent group of 2 to 10 and may have a substituent, X ⁻ is an anion, k is an integer of 0 to 2, and r ₁ is 1 to 8. is an integer, _{r 2} is an integer of 0-8.)
2. 2. The immersion exposure sensation according to 1 above, wherein the content of the compound [A] is 0.1 to 20 parts by mass with respect to a total of 100 parts by mass of the polymer [B] and the polymer [C]. Radiation resin composition.
3. The radiation-sensitive resin composition for immersion exposure according to 1 or 2 above, wherein the content of the polymer [B] is 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer [C].
4). The immersion exposure according to any one of 1 to 3 above, wherein the polymer [B] has a repeating unit represented by the following general formula (2) or a repeating unit represented by the following general formula (3). Radiation sensitive resin composition.

(Wherein R ³ is a hydrogen atom, a methyl group or a trifluoromethyl group, and R ⁴ is a linear or branched group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. An alkyl group, or an alicyclic hydrocarbon group having 4 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or a derivative group thereof.

(In the formula, n is an integer of 1 to 3, R ⁵ is a hydrogen atom, a methyl group or a trifluoromethyl group, and R ⁶ is a single bond or (n + 1) valence, 1 to 10, a straight-chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group, R ⁷ is a single bond or divalent, straight chain having 1 to 20 carbon atoms. A linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group, and G ¹ represents —CHF—, —CF ₂ —, or a linear or branched fluoro having 2 to 20 carbon atoms. An alkylene group, G ² is a single bond or —CO—, and R ⁸ is independently a hydrogen atom or an acid dissociable group.
5. The process of forming a photoresist film on a board | substrate using the radiation sensitive resin composition for liquid immersion exposure as described in any one of said 1-4, and arrange | positioning the liquid for liquid immersion exposure on the said photoresist film And a step of immersion exposure of the photoresist film through the immersion exposure liquid, and a step of developing the immersion exposed photoresist film to form a resist pattern. A resist pattern forming method.

According to the radiation sensitive resin composition for immersion exposure of the present invention, a photoresist film having a large receding contact angle with the immersion exposure liquid and hardly causing development defects can be provided.
Moreover, according to the pattern formation method of this invention, it is excellent in a depth of focus and can form a pattern of a favorable shape efficiently.

In the measurement of the elution amount of a photoresist film formed using the radiation-sensitive resin composition for immersion exposure according to the present invention, a state in which an 8-inch silicon wafer is placed on a silicon rubber sheet so that ultrapure water does not leak is schematically shown. FIG. It is sectional drawing in the measurement state of the elution amount of the photoresist film formed using the radiation sensitive resin composition for immersion exposure of this invention.

  Hereinafter, the present invention will be described in detail. In the following description, “(meth) acryl” means acryl and methacryl.

（式中、Ｒ^１は、相互に独立して、フッ素原子、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数１〜１０の直鎖状若しくは分岐状のアルコキシル基、炭素数２〜１１の直鎖状若しくは分岐状のアルコキシカルボニル基、又は、炭素数１〜１０の直鎖状、分岐状若しくは環状のアルカンスルホニル基であり、Ｒ^２は、相互に独立して、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、置換基を有してもよいフェニル基又は置換基を有してもよいナフチル基、或いは、２つのＲ^２が互いに結合して炭素数２〜１０の２価の基を形成しており且つ置換基を有してもよい基であり、Ｘ⁻はアニオンであり、ｋは０〜２の整数であり、ｒ_１は１〜８の整数であり、ｒ_２は０〜８の整数である。） 1. Radiation-sensitive resin composition for immersion exposure The radiation-sensitive resin composition for immersion exposure according to the present invention includes [A] a compound represented by the following general formula (1), [B] 5% by mass or more of fluorine atoms. And a polymer having a [C] acid dissociable group and containing less than 5% by mass of fluorine atoms.

(In the formula, R ¹ is independently of each other a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxyl group having 1 to 10 carbon atoms, carbon, A linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms, or a linear, branched or cyclic alkanesulfonyl group having 1 to 10 carbon atoms, and R ² is a carbon atom independently of each other. the number 1 to 10 linear or branched alkyl group, a phenyl group which may have a substituent or substituents naphthyl group which may have a, or the number of carbon two R ² are bonded to each other Is a group that forms a divalent group of 2 to 10 and may have a substituent, X ⁻ is an anion, k is an integer of 0 to 2, and r ₁ is 1 to 8. is an integer, _{r 2} is an integer of 0-8.)

  In the present invention, the compound [A] is a component that acts as a radiation-sensitive acid generator, and when the photoresist film formed by the composition of the present invention is exposed through the immersion exposure liquid, It is a component that generates an acid derived from the radiation-sensitive acid generator from the exposed portion. By the action of this acid, the acid dissociable functional group of the polymer [C] in the exposed area is dissociated from this polymer. The polymer from which the acid dissociable functional group is dissociated becomes readily soluble in an alkali developer. Then, the pattern which has a desired shape can be obtained by removing the unnecessary part of a photoresist film using an alkali developing solution. Since this compound [A] has an OH group, aggregation in the developer and the rinsing liquid is suppressed, and it is considered that this compound [A] is unlikely to become a defect nucleus. The composition of the present invention may use only the compound [A] as a radiation-sensitive acid generator, or the compound [A] and another radiation-sensitive acid generator (hereinafter referred to as “other acid generator”). It can be used in combination. Further, by using a composition containing the polymers [B] and [C], it has excellent depth of focus, is difficult to elute into an immersion exposure liquid such as water, and has a large receding contact angle with respect to the immersion exposure liquid, A photoresist film that hardly causes development defects is formed.

1-1. Compound [A]
In the compound [A] represented by the general formula (1), R ^{1 s} are each independently a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. A linear or branched alkoxyl group, a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms, or a linear, branched or cyclic alkanesulfonyl group having 1 to 10 carbon atoms. .

Examples of the linear and branched alkyl group having 1 to 10 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and tert-butyl. Group, n-pentyl group and the like. Of these, a methyl group, an ethyl group, an n-butyl group, and a tert-butyl group are preferable.

Examples of the linear and branched alkoxyl group having 1 to 10 carbon atoms represented by R ¹ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a 2-methylpropoxy group, Examples thereof include 1-methylpropoxy group and tert-butoxy group. Of these, a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group are preferable.

Examples of the linear and branched alkoxycarbonyl group having 2 to 11 carbon atoms represented by R ¹ include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, Examples include 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, tert-butoxycarbonyl group and the like. Of these, a methoxycarbonyl group, an ethoxycarbonyl group, and an n-butoxycarbonyl group are preferable.

Examples of the linear, branched and cyclic alkanesulfonyl groups having 1 to 10 carbon atoms represented by R ¹ include a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a tert. -A butanesulfonyl group, a cyclopentanesulfonyl group, a cyclohexanesulfonyl group, etc. are mentioned. Among these, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, and a cyclohexanesulfonyl group are preferable.

R ² is independently of each other a linear or branched alkyl group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or Two R ² are bonded to each other to form a divalent group having 2 to 10 carbon atoms and may have a substituent.

Examples of the linear and branched alkyl group having 1 to 10 carbon atoms represented by R ² include a methyl group, an ethyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and tert-butyl. Group, n-pentyl group and the like. Of these, a methyl group, an ethyl group, an n-butyl group, and a tert-butyl group are preferable.

The phenyl group having a substituent represented by R ² is an unsubstituted phenyl group or an alkyl-substituted phenyl group (the hydrogen atom in the phenyl group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms). Substituted with at least one of a halogen atom, hydroxyl group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group, carboxyl group, cyano group, nitro group, etc. And the like.

Substituents replacing hydrogen atoms in the unsubstituted phenyl group or alkyl-substituted phenyl group are as follows.
Examples of the alkoxyl group include linear, branched and cyclic alkoxyl groups having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, a tert-butoxy group, a cyclopentyloxy group and a cyclohexyloxy group. It is done.

  Examples of the alkoxyalkyl group include straight chain or branched chain having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group. And cyclic alkoxyalkyl groups and the like.

  Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, a 1-methylpropoxycarbonyl group, and a tert-butoxycarbonyl group. C2-C21 linear, branched and cyclic alkoxycarbonyl groups such as cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl.

  As alkoxycarbonyloxy group, methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxycarbonyloxy group, tert-butoxycarbonyloxy group, cyclopentyloxycarbonyl group, cyclohexyl Examples thereof include linear, branched and cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as oxycarbonyl.

In the general formula (1), R ² containing a phenyl group includes a phenyl group, a 4-hydroxyphenyl group, a 4-cyclohexylphenyl group, a 4-tert-butylphenyl group, a 4-methoxyphenyl group, a 4-tertphenyl group, and a 4-tertphenyl group. -A phenyl group having a substituent such as a butoxyphenyl group is preferred.

In the general formula (1), when R ² contains a naphthyl group, it may be an unsubstituted naphthyl group (1-naphthyl group, 2-naphthyl group) or a naphthyl group having a substituent. .
As a naphthyl group having a substituent, a hydrogen atom in an unsubstituted naphthyl group or an alkyl-substituted naphthyl group is a halogen atom, hydroxyl group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group, carboxyl group, cyano group And groups substituted by at least one of nitro groups and the like.
The alkyl-substituted naphthyl group is a group in which a hydrogen atom in a naphthyl group is substituted with a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and a 2-methyl-1-naphthyl group 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl- 1-naphthyl group, 8-methyl-1-naphthyl group, 2,3-dimethyl-1-naphthyl group, 2,4-dimethyl-1-naphthyl group, 2,5-dimethyl-1-naphthyl group, 2,6 -Dimethyl-1-naphthyl group, 2,7-dimethyl-1-naphthyl group, 2,8-dimethyl-1-naphthyl group, 3,4-dimethyl-1-naphthyl group, 3,5-dimethyl-1-naphthyl Group, 3,6-dimethyl-1-naphthyl 3,7-dimethyl-1-naphthyl group, 3,8-dimethyl-1-naphthyl group, 4,5-dimethyl-1-naphthyl group, 5,8-dimethyl-1-naphthyl group, 4-ethyl-1 -A naphthyl group 2-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl group, etc. are mentioned.

  Specific examples of substituents (alkoxyl groups, alkoxyalkyl groups, alkoxycarbonyl groups, alkoxycarbonyloxy groups, etc.) in place of hydrogen atoms in unsubstituted naphthyl groups or alkyl-substituted naphthyl groups include substitutions on unsubstituted phenyl groups or alkyl-substituted phenyl groups Substituents similar to those exemplified as the group can be used.

In the general formula (1), R ² containing a naphthyl group includes 1-naphthyl group, 1- (4-methoxynaphthyl) group, 1- (4-ethoxynaphthyl) group, 1- (4-n-propoxy). Naphthyl) group, 1- (4-n-butoxynaphthyl) group, 2- (7-methoxynaphthyl) group, 2- (7-ethoxynaphthyl) group, 2- (7-n-propoxynaphthyl) group and 2- A (7-n-butoxynaphthyl) group is preferred.

In R ² , when two R ² are bonded to each other to form a divalent group having 2 to 10 carbon atoms and may be substituted, the above 2 to 2 carbon atoms The valent group is preferably a group that forms a 5-membered or 6-membered ring with the sulfur atom in the compound represented by the general formula (1), and a group that forms a 5-membered ring (that is, a tetrahydrothiophene ring). Is more preferable.

  When the divalent group having 2 to 10 carbon atoms has a substituent, examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxyl group, an alkalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyl group. An oxy group etc. are mentioned.

In the general formula (1), R ² is preferably a methyl group, an ethyl group, a phenyl group, a 4-methoxyphenyl group, or a 1-naphthyl group. Moreover, it is also preferable that two R < ² > is mutually couple | bonded and it is a bivalent group which forms the tetrahydrothiophene ring structure with a sulfur atom.

（式中、Ｒ^１２は、相互に独立して、フッ素原子を有する炭素数１〜１０の直鎖状若しくは分岐状のアルキル基又は２つのＲ^１２が互いに結合してフッ素原子を有する炭素数２〜１０の２価の基を形成しており且つ置換基を有してもよい基である。また、Ｒ^１３は、相互に独立して、フッ素原子を有する炭素数１〜１０の直鎖状若しくは分岐状のアルキル基又は３つのうち２つのＲ^１３が互いに結合してフッ素原子を有する炭素数２〜１０の２価の基を形成しており且つ置換基を有してもよい基である。） Moreover, in the said General formula (1), X < ^- > is an anion, for example, the anion represented by the following general formula (6), (7), (8-1) and (8-2) is mentioned. .
R ¹⁰ C _n F _2n SO ₃ ⁻ (6)
(In the formula, R ¹⁰ is a hydrogen atom, a fluorine atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and n is an integer of 1 to 10).
R ¹¹ SO ₃ ^- (7)
(In the formula, R ¹¹ is a hydrogen atom, a fluorine atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.)

(In the formula, R ¹² is independently of each other a linear or branched alkyl group having 1 to 10 carbon atoms having a fluorine atom, or two R ¹² are bonded to each other to have 2 fluorine atoms. R ¹³ is a group which may form a divalent group of from 10 to 10 and may have a substituent, and R ¹³ , independently of each other, is a straight chain of 1 to 10 carbon atoms having a fluorine atom. It is the group which may have a divalent group forms a and substituent group having 2 to 10 carbon atoms having a fluorine atom or by branched alkyl groups or three of the two R ¹³ are bonded to each other .)

When X ⁻ is an anion represented by the general formula (6), “—C _n F _2n —” is a perfluoroalkylene group having n carbon atoms, and this group is linear Alternatively, it may be branched. Here, n is preferably 1, 2, 4 or 8.

In the general formula (6), when R ¹⁰ contains a hydrocarbon group having 1 to 12 carbon atoms, it is an unsubstituted hydrocarbon group (an alkyl group, a cycloalkyl group, a bridged alicyclic hydrocarbon group, etc.). The hydrogen atom in these hydrocarbon groups may be a substituent on at least one of hydroxyl group, carboxyl group, cyano group, nitro group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group and the like. It may be a group formed.
R ¹⁰ includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, norbornyl group, norbornylmethyl group, hydroxynorbornol. Nyl and adamantyl groups are preferred.

Further, X ^- is, if an anion represented by the above general formula (7), when R ¹¹ contains a hydrocarbon group having 1 to 12 carbon atoms, unsubstituted hydrocarbon group (alkyl group, cycloalkyl group Or a bridged alicyclic hydrocarbon group, etc., and the hydrogen atom in these hydrocarbon groups is a hydroxyl group, carboxyl group, cyano group, nitro group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group And a group formed by substitution with at least one kind such as an alkoxycarbonyloxy group.
R ¹¹ includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, norbornyl group, norbornylmethyl group, hydroxynorbornol. Nyl and adamantyl groups are preferred.

When X < ^- > is an anion represented by the above general formula (8-1), the linear and branched alkyl group having 1 to 10 carbon atoms and having a fluorine atom represented by R < ¹² > Examples thereof include a fluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a dodecafluoropentyl group, and a perfluorooctyl group.
In R ¹² , when two R ¹² are bonded to form a divalent group having 2 to 10 carbon atoms having a fluorine atom and may have a substituent, tetrafluoroethylene Group, hexafluoropropylene group, octafluorobutylene group, decafluoropentylene group, undecafluorohexylene group and the like.

When X ⁻ is an anion represented by the general formula (8-2), the linear and branched alkyl group having 1 to 10 carbon atoms and having a fluorine atom represented by R ¹³ is tri- Examples thereof include a fluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a dodecafluoropentyl group, and a perfluorooctyl group.
In R ¹³ , when two of the three R ¹³ are bonded to each other to form a divalent group having 2 to 10 carbon atoms having a fluorine atom and may be substituted. , Tetrafluoroethylene group, hexafluoropropylene group, octafluorobutylene group, decafluoropentylene group, undecafluorohexylene group and the like.

X ⁻ is preferably trifluoromethanesulfonate anion, perfluoro-n-butanesulfonate anion, perfluoro-n-octanesulfonate anion, 2-bicyclo [2.2.1] hept-2-yl-1,1, 2,2-tetrafluoroethanesulfonate anion, 2-bicyclo [2.2.1] hept-2-yl-1,1-difluoroethanesulfonate anion, and the following formulas (9-1) to (9-7) An anion represented.

In the said General formula (1), k is an integer of 0-2, Preferably it is 0 or 1. Moreover, _{r 1} is an integer from 1 to 8, preferably 1 to 3. r ₂ is an integer of 0-8, preferably 0-3.

  Examples of the compound represented by the general formula (1) include 4-hydroxyphenyldiphenylsulfonium trifluoromethanesulfonate, di-tert-butylphenyl 4-hydroxyphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyl-di-hydroxyphenylsulfonium trifluoro. L-methanesulfonate, 4-hydroxyphenyldi-4-methanesulfonylphenylsulfonium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, 1- (3,5-dimethyl-4- Hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate,

  4-hydroxyphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, di-tert-butylphenyl 4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyl-di-hydroxyphenylnonafluoro-n-butanesulfonate, 4-hydroxyphenyldi-4-methanesulfonylphenylsulfonium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, 1- (4-hydroxy Naphthyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate,

  4-hydroxyphenyldiphenylsulfonium perfluoro-n-octanesulfonate, di-tert-butylphenyl 4-hydroxyphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyl-di-hydroxyphenylperfluoro-n-octanesulfonate, 4-hydroxyphenyldi-4-methanesulfonylphenylsulfonium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) diphenylsulfonium perfluoro-n-octanesulfonate, 1- (4-hydroxy Naphthyl) tetrahydrothiophenium perfluoro-n-octanesulfonate,

  4-hydroxyphenyldiphenylsulfonium 2- (bicyclo [2.2.1] hepta-2'-yl) -1,1,2,2-tetrafluoroethanesulfonate, di-tert-butylphenyl 4-hydroxyphenylsulfonium 2 -(Bicyclo [2.2.1] hepta-2'-yl) -1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyl-di-hydroxyphenyl 2- (bicyclo [2.2.1 ] Hepta-2'-yl) -1,1,2,2-tetrafluoroethanesulfonate, 4-hydroxyphenyldi-4-methanesulfonylphenylsulfonium 2- (bicyclo [2.2.1] hepta-2'- Yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) Diphenylsulfonium 2- (bicyclo [2.2.1] hepta-2'-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-hydroxynaphthyl) tetrahydrothiophenium 2- ( Bicyclo [2.2.1] hepta-2′-yl) -1,1,2,2-tetrafluoroethanesulfonate,

  4-hydroxyphenyldiphenylsulfonium 2- (bicyclo [2.2.1] hepta-2'-yl) -1,1-difluoroethanesulfonate, di-tert-butylphenyl 4-hydroxyphenylsulfonium 2- (bicyclo [2. 2.1] Hepta-2'-yl) -1,1-difluoroethanesulfonate, 4-cyclohexylphenyl-di-hydroxyphenyl 2- (bicyclo [2.2.1] hepta-2'-yl) -1,1 -Difluoroethanesulfonate, 4-hydroxyphenyldi-4-methanesulfonylphenylsulfonium 2- (bicyclo [2.2.1] hepta-2'-yl) -1,1-difluoroethanesulfonate, 1- (3,5-dimethyl -4-hydroxyphenyl) diphenylsulfonium 2- (bicyclo [2.2. 1] Hepta-2'-yl) -1,1-difluoroethanesulfonate, 1- (4-hydroxynaphthyl) tetrahydrothiophenium 2- (bicyclo [2.2.1] hepta-2'-yl) -1, Examples include 1-difluoroethanesulfonate, compounds represented by the following formulas (10-1) to (10-15), and the like.

In the present invention, the compound [A] may be used alone or in combination of two or more.
The content of the compound [A] in the composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0 with respect to 100 parts by mass in total of the polymer [B] and the polymer [C]. 5 to 10 parts by mass. When the content of the compound [A] is within this range, the sensitivity and developability of the formed photoresist film can be maintained high. Furthermore, a radiation sensitive resin composition with few development defects can be obtained.

1-2. Other Acid Generators As mentioned above, the composition of the present invention may contain other acid generators.
As other acid generators, for example, compounds described in paragraphs [0080] to [0113] of JP2009-134088A can be used. Other acid generators may be used alone or in combination of two or more.
In the present invention, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert -Butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-tert-butylphenyl) iodonium perfluoro-n-octanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, tri Phenylsulfonium perfluoro-n-octane sulfonate, cyclohexyl 2-oxocyclohexyl Methylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (1 -Naphthylacetomethyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept -5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-e -2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxys Ximidononafluoro-n-butane sulfonate, N-hydroxysuccinimide perfluoro-n-octane sulfonate and 1,8-naphthalenedicarboxylic imide trifluoromethanesulfonate are preferred.

  When the composition of the present invention contains other acid generator, the content thereof is preferably 3 to 20 parts by mass with respect to 100 parts by mass in total of the polymer [B] and the polymer [C], More preferably, it is 5-15 mass parts.

1-3. Polymer [B]
The polymer [B] is not particularly limited as long as it contains 5% by mass or more of fluorine atoms when the entire polymer [B] is 100% by mass. The fluorine atom content is preferably 5 to 50% by mass, more preferably 5 to 40% by mass. The content ratio of the fluorine atom can be measured by ¹³ C-NMR.
The polymer [B] is a polymer having at least a repeating unit containing a fluorine atom (hereinafter referred to as “repeating unit (b1)”) and may have a repeating unit containing no fluorine atom.

  When a photoresist film is formed using a radiation-sensitive resin composition for immersion exposure containing the polymer [B] and a polymer [C] described later, it is attributed to the oil repellency of the polymer [B]. Thus, the distribution of the polymer [B] tends to be high on the surface of the photoresist film. That is, the polymer [B] is unevenly distributed on the surface of the photoresist film. Therefore, it is not necessary to separately form an upper layer film for the purpose of blocking the photoresist film from the immersion medium, and can be suitably used for the immersion exposure method.

（式中、Ｒ^３は、水素原子、メチル基又はトリフルオロメチル基であり、Ｒ^４は、少なくとも１つの水素原子がフッ素原子に置換された炭素数１〜６の直鎖状若しくは分岐状のアルキル基、又は、少なくとも１つの水素原子がフッ素原子に置換された炭素数４〜２０の脂環式炭化水素基若しくはその誘導体基である。）

（式中、ｎは１〜３の整数であり、Ｒ^５は、水素原子、メチル基又はトリフルオロメチル基であり、Ｒ^６は、単結合、或いは、（ｎ＋１）価であって、炭素数１〜１０の、直鎖状、分岐状又は環状の飽和炭化水素基若しくは不飽和炭化水素基であり、Ｒ^７は、単結合、或いは、２価であって、炭素数１〜２０の、直鎖状、分岐状若しくは環状の飽和炭化水素基又は不飽和炭化水素基であり、Ｇ^１は、−ＣＨＦ−、−ＣＦ_２−、又は、炭素数２〜２０の直鎖状若しくは分岐状のフルオロアルキレン基であり、Ｇ^２は、単結合又は−ＣＯ−であり、Ｒ^８は、相互に独立して、水素原子又は酸解離性基である。） 1-3-1. Repeating unit (b1)
Examples of the repeating unit (b1) include a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3).

(In the formula, R ³ is a hydrogen atom, a methyl group or a trifluoromethyl group, and R ⁴ is a linear or branched group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. An alkyl group, or an alicyclic hydrocarbon group having 4 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or a derivative group thereof.

(In the formula, n is an integer of 1 to 3, R ⁵ is a hydrogen atom, a methyl group or a trifluoromethyl group, and R ⁶ is a single bond or (n + 1) valence, 1 to 10, a straight-chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group, R ⁷ is a single bond or divalent, straight chain having 1 to 20 carbon atoms. A linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group, and G ¹ represents —CHF—, —CF ₂ —, or a linear or branched fluoro having 2 to 20 carbon atoms. An alkylene group, G ² is a single bond or —CO—, and R ⁸ is independently a hydrogen atom or an acid dissociable group.

In the above general formula (2), the linear and branched alkyl group having 1 to 6 carbon atoms and having at least one fluorine atom represented by R ⁴ includes a methyl group, an ethyl group, a 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 2- (2-methylpropyl) group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1 -(3-methylbutyl) group, 2- (2-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methyl Pentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methyl) Pentyl) group, 3- (2-methylpentyl) A group in which part or all of the hydrogen atoms contained in the linear and branched alkyl groups such as (l) group and 3- (3-methylpentyl) group are fluorinated.

Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms having at least one fluorine atom represented by R ⁴ and derivatives thereof include a cyclopentyl group, a cyclopentylmethyl group, and 1- (1-cyclopentyl). Ethyl) group, 1- (2-cyclopentylethyl) group, cyclohexyl group, cyclohexylmethyl group, 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, Groups in which part or all of hydrogen atoms contained in an alicyclic alkyl group such as a 1- (1-cycloheptylethyl) group, a 1- (2-cycloheptylethyl) group, and a 2-norbornyl group are fluorinated Is mentioned.

  Monomers that give the repeating unit (2) represented by the general formula (2) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, Fluoroethyl (meth) acrylic acid ester, perfluoro n-propyl (meth) acrylic acid ester, perfluoroisopropyl (meth) acrylic acid ester, perfluoro n-butyl (meth) acrylic acid ester, perfluoroisobutyl (meth) acrylic Acid ester, perfluoro tert-butyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl) (meth) acrylic acid ester, 1- (2,2,3, 3,4,4,5,5-octafluoropentyl) (meth) acrylic acid ester, perfluorocycle Hexylmethyl (meth) acrylic acid ester, 1- (2,2,3,3,3-pentafluoropropyl) (meth) acrylic acid ester, 1- (3,3,4,4,5,5,6, 6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl) (meth) acrylic acid ester, 1- (1-trifluoromethyl-3,3,4,4,5) , 6,6,6-octafluorohexyl) (meth) acrylic acid ester and the like.

Next, in the above general formula (3), the (n + 1) -valent linear, branched and cyclic saturated hydrocarbon group and unsaturated hydrocarbon group represented by R ^{6 and} having 1 to 10 carbon atoms. As methane, ethane, n-propane, 2-propane, n-butane, 2-methylpropane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane, decane, etc. And a linear or branched hydrocarbon group having a structure in which (n + 1) hydrogen atoms are removed from the chain hydrocarbon having 1 to 10 carbon atoms.

Examples of the (n + 1) -valent cyclic saturated and unsaturated hydrocarbon group represented by R ⁶ include groups derived from alicyclic hydrocarbons and aromatic hydrocarbons having 3 to 10 carbon atoms. Cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, And cycloalkanes such as tricyclo [3.3.1.1 ^3,7 ] decane. Examples of the aromatic hydrocarbon include benzene and naphthalene.
R ⁶ is preferably a divalent to tetravalent group.

Examples of the divalent, divalent C1-C20 linear and branched saturated hydrocarbon group and unsaturated hydrocarbon group represented by R ⁷ include methane, ethane, n-propane, and 2-propane. , N-butane, 2-methylpropane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane, decane, etc., hydrogen atoms in C1-C20 chain hydrocarbons And hydrocarbon groups derived from linear and branched alkyl groups and alkenyl groups having a structure in which two are removed.

Examples of the divalent cyclic saturated hydrocarbon group and unsaturated hydrocarbon group represented by R ⁷ include groups derived from alicyclic hydrocarbons and aromatic hydrocarbons having 3 to 20 carbon atoms. Cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, Tricyclo [3.3.1.1 ^3,7 ] decane, tetracyclo [6.2.1.1 ^3,6 . And cycloalkanes such as 0 ^2,7 ] dodecane. Examples of the aromatic hydrocarbon include benzene and naphthalene.

When R ⁷ is a saturated hydrocarbon group or an unsaturated hydrocarbon group, at least one of the hydrogen atoms is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a 2-methylpropyl group. A linear, branched and cyclic alkyl group having 1 to 12 carbon atoms such as 1-methylpropyl group and tert-butyl group, hydroxyl group, cyano group, hydroxyalkyl group having 1 to 10 carbon atoms, carboxyl group, It may be a group substituted by an oxygen atom or the like.

（各式中、ｎは、相互に独立して、１〜４の整数である。） In the above general formula (3), G ¹ is —CHF—, —CF ₂ —, or a linear or branched fluoroalkylene group having 2 to 20 carbon atoms, and specific examples thereof are represented by the following formula ( G1-1) and (G1-2).

(In each formula, n is an integer of 1 to 4 independently of each other.)

In the general formula (3), R ⁸ is a hydrogen atom or an acid dissociable group. The acid dissociable group refers to a group that substitutes a hydrogen atom in a polar functional group such as a hydroxyl group, a carboxyl group, and a sulfonic acid group, and dissociates in the presence of an acid.
Examples of the acid dissociable group include tert-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, (thiotetrahydropyranylsulfanyl) methyl group, (thiotetrahydrofuranylsulfanyl) methyl group, alkoxy-substituted methyl group, alkylsulfanyl-substituted methyl group. Groups and the like. In addition, as an alkoxyl group (substituent) in an alkoxy substituted methyl group, a C1-C4 alkoxyl group is mentioned. In addition, examples of the alkyl group (substituent) in the alkylsulfanyl-substituted methyl group include alkyl groups having 1 to 4 carbon atoms. Further, the acid dissociable group may be a group represented by —C (R ²⁶ ) ₃ which is a part of the structure in the general formula (4) described later.

In the general formula (3), when n is 2 or 3, R ⁸ is independently a hydrogen atom or an acid dissociable group, and at least one R ⁸ is an acid dissociable group. is there. And ^- in the ^{(R 7 -G 1 -G 2 -O} -R 8) n, a plurality of ^{R 7} may or may be the same or different. The same applies to G ¹ , G ² and R ⁸ .

（式中、ｎは１〜３の整数であり、Ｒ^５は、水素原子、メチル基又はトリフルオロメチル基であり、Ｒ^６は、単結合、或いは、２価であって、炭素数１〜１０の、直鎖状、分岐状又は環状の飽和炭化水素基若しくは不飽和炭化水素基であり、Ｇ^１は、−ＣＨＦ−、−ＣＦ_２−、又は、炭素数２〜２０の直鎖状若しくは分岐状のフルオロアルキレン基であり、Ｒ^８は、相互に独立して、水素原子又は酸解離性基である。） Examples of the repeating unit represented by the general formula (3) include repeating units represented by the following general formulas (3-1) to (3-3).

(In the formula, n is an integer of 1 to 3, R ⁵ is a hydrogen atom, a methyl group or a trifluoromethyl group, and R ⁶ is a single bond or a divalent group having 1 to 1 carbon atoms. 10 is a linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group, and G ¹ is —CHF—, —CF ₂ —, or a straight chain having 2 to 20 carbon atoms, or A branched fluoroalkylene group, and R ^{8 s} independently of each other are a hydrogen atom or an acid dissociable group.)

（式中、Ｒ^５は、水素原子、メチル基又はトリフルオロメチル基であり、Ｒ^８は酸解離性基であり、一般式（３−１５）において、Ｒ^８は、相互に独立して、水素原子又は酸解離性基である。） Examples of the monomer that gives the repeating unit represented by the general formula (3) include the following general formulas (3-11) to (3-16).

(In the formula, R ⁵ is a hydrogen atom, a methyl group or a trifluoromethyl group, R ⁸ is an acid-dissociable group, and in general formula (3-15), R ⁸ are independently of each other; It is a hydrogen atom or an acid dissociable group.)

The repeating unit (b1) constituting the polymer [B] may consist only of the repeating unit represented by the general formula (2), or the repeating unit represented by the general formula (3). It may consist of only the repeating unit represented by the above general formulas (2) and (3).
Moreover, the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) constituting the polymer [B] may be only one kind each. Two or more kinds may be used.
Furthermore, the polymer [B] may be a polymer composed of the repeating unit (b1) and other repeating units described later.

  In the present invention, the lower limit of the content of the repeating unit (b1) in the polymer [B] is preferably 20 mol%, more preferably 40 mol%, more preferably 100 mol% in total of all repeating units. Preferably it is 60 mol%. On the other hand, the upper limit is preferably 100 mol%, more preferably 80 mol%, still more preferably 70 mol%, particularly preferably 60 mol%. When the polymer [B] contains the repeating unit (b1) in the above ratio, the polymer [B] is unevenly distributed on the outermost surface when a photoresist film is formed using the composition of the present invention. In the immersion exposure, it is possible to suppress the dissolution of the resist component in the immersion exposure liquid. In addition, it is possible to achieve both of ensuring water repellency after coating and increasing the contact angle with respect to the developer after PEB.

1-3-2. Other Repeating Units The polymer [B] is a repeating unit having an acid dissociable group as another repeating unit (excluding the repeating unit (b1); hereinafter referred to as “repeating unit (b2)”). And a repeating unit having an alkali-soluble group (hereinafter referred to as “repeating unit (b3)”) and a repeating unit having an alkali-reactive group (hereinafter referred to as “repeating unit (b4)”).

（式中、Ｒ^２５は、水素原子、メチル基、トリフルオロメチル基又はヒドロキシメチル基であり、Ｒ^２６は、相互に独立して、炭素数１〜４の直鎖状若しくは分岐状のアルキル基、又は、炭素数４〜２０の脂環式炭化水素基若しくはその誘導体基、或いは、３つのＲ^２６のうちいずれか２つが互いに結合して形成された、２価であって、炭素数４〜２０の脂環式炭化水素基若しくはその誘導体基であり、且つ、残りの１つのＲ^２６が、炭素数１〜４の直鎖状若しくは分岐状のアルキル基又は炭素数４〜２０の脂環式炭化水素基若しくはその誘導体基である。） 1-3-2-1. Repeating unit (b2)
As said repeating unit (b2), the repeating unit represented by following General formula (4) is mentioned.

(In the formula, R ²⁵ is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and R ²⁶ is independently a linear or branched alkyl group having 1 to 4 carbon atoms. Or an alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative group thereof, or divalent formed by bonding any two of three R ²⁶ to each other, and having 4 to 20 alicyclic hydrocarbon group or a derivative group thereof, and the remaining one R ²⁶ is a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic group having 4 to 20 carbon atoms. It is a hydrocarbon group or a derivative group thereof.)

In the general formula (4), examples of the alkyl group having 1 to 4 carbon atoms represented by R ²⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-methylpropyl group, Examples thereof include a 1-methylpropyl group and a tert-butyl group.
Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ²⁶ include a cyclopentyl group, a cyclopentylmethyl group, a 1- (1-cyclopentylethyl) group, and a 1- (2-cyclopentylethyl) group. Cyclohexyl group, cyclohexylmethyl group, 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, 1- (1-cycloheptylethyl) group, 1- And alicyclic alkyl groups such as a (2-cycloheptylethyl) group and a 2-norbornyl group.

In addition, any two of the three R ^{26 s} formed by bonding to each other, which is a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative group thereof includes an adamantane skeleton and a norbornane skeleton. Groups having a bridged skeleton such as a tricyclodecane skeleton and a tetracyclododecane skeleton, and a cycloalkane skeleton such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane; a hydrogen atom contained in these groups Linear, branched or cyclic having 1 to 10 carbon atoms such as a group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, tert-butyl group, etc. And groups having an alicyclic skeleton such as a group substituted with one or more alkyl groups.

（式中、Ｒ^２５は、水素原子、メチル基、トリフルオロメチル基又はヒドロキシメチル基であり、Ｒ^２７は、炭素数１〜４の直鎖状又は分岐状のアルキル基であり、ｋは１〜４の整数である。） The repeating unit (b2) is preferably a repeating unit represented by the following general formula (4-1).

(Wherein R ²⁵ is a hydrogen atom, methyl group, trifluoromethyl group or hydroxymethyl group, R ²⁷ is a linear or branched alkyl group having 1 to 4 carbon atoms, and k is 1) It is an integer of ~ 4.)

In the general formula (4-1), examples of the alkyl group having 1 to 4 carbon atoms represented by R ²⁷ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, tert-butyl group and the like.

The repeating unit (b2) constituting the polymer [B] may be only one type or a combination of two or more types.
When the polymer [B] contains the repeating unit (b2), the difference between the advancing contact angle and the receding contact angle in the photoresist film can be reduced, and the scan speed during the immersion exposure can be increased. be able to.

Examples of the monomer that gives the repeating unit (b2) include (meth) acrylic acid 2-methyladamantan-2-yl ester, (meth) acrylic acid 2-methyl-3-hydroxyadamantan-2-yl ester, (meth) ) Acrylic acid 2-ethyladamantan-2-yl ester, (meth) acrylic acid 2-ethyl-3-hydroxyadamantan-2-yl ester, (meth) acrylic acid 2-n-propyladamantan-2-yl ester, ( (Meth) acrylic acid 2-isopropyladamantan-2-yl ester, (meth) acrylic acid-2-methylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-2-ethylbicyclo [2] 2.1] hept-2-yl ester, (meth) acrylic acid-8-methyltricyclo [5.2.1.0 ^{2 , 6} ] decan-8-yl ester, (meth) acrylic acid-8-ethyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl ester, (meth) acrylic acid-4-methyltetra Cyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl ester, (meth) acrylic acid-4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl ester,

(Meth) acrylic acid 2- (bicyclo [2.2.1] hept-2-yl) -2-methylethyl ester, (meth) acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl) -2-methyl ethyl ester, (meth) acrylic acid 2- (tetracyclo ^[6.2.1.1 3,6 ^{.0 2,7]} dodecane-4-yl) -2-methylethyl Ester, (meth) acrylic acid 2- (adamantan-2-yl) -2-methylethyl ester, (meth) acrylic acid 2- (3-hydroxyadamantan-2-yl) -2-methylethyl ester, (meth) 1,2-dicyclohexylethyl esteryl acrylate, 1,2-di (bicyclo [2.2.1] hept-2-yl) ethyl ester, (meth) acrylic acid 1,2-di (meth) acrylate Torishi B [5.2.1.0 ^2,6] decan-8-yl) ethyl ester, (meth) acrylic acid 1,2-di (tetracyclo ^[6.2.1.1 3,6 ^{.0 2,7} ] Dodecan-4-yl) ethyl ester, (meth) acrylic acid 1,2-di (adamantan-2-yl) ethyl ester, (meth) acrylic acid 2-methyl-2-cyclopentyl ester, (meth) acrylic acid 2 -Ethyl-2-cyclopentyl ester, (meth) acrylic acid 2-isopropyl-2-cyclopentyl ester, (meth) acrylic acid 2-methyl-2-cyclohexyl ester, (meth) acrylic acid 2-ethyl-2-cyclohexyl ester, Examples include (meth) acrylic acid 2-ethyl-2-cyclooctyl ester.

  Examples of the monomer that gives the repeating unit (b2) include (meth) acrylic acid 2-methyl-2-cyclopentyl ester, (meth) acrylic acid 2-ethyl-2-cyclopentyl ester, and (meth) acrylic acid 2-isopropyl. 2-cyclopentyl ester, (meth) acrylic acid 2-methyl-2-cyclohexyl ester, (meth) acrylic acid 2-ethyl-2-cyclohexyl ester and (meth) acrylic acid 2-ethyl-2-cyclooctyl ester are preferred. .

1-3-2-2. Repeating unit (b3)
The alkali-soluble group contained in the repeating unit (b3) is preferably a functional group having a hydrogen atom having a pKa of 4 to 11 from the viewpoint of improving solubility in a developer. Examples of the functional group include groups represented by the following general formulas (13) and (14).
—NHSO ₂ R ³⁰ (13)
-COOH (14)

In the general formula (13), R ³⁰ is a hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, preferably a trifluoromethyl group.

  The main chain portion of the repeating unit (b3) preferably includes a structure derived from a (meth) acryloyl group, an α-trifluoroacryloyl group, and the like. And it is preferable that the said alkali-soluble group has couple | bonded directly or indirectly with -COO etc. in these principal chain parts.

（式中、Ｒ^２８は、水素原子、メチル基又はトリフルオロメチル基であり、Ｒ^２９は、単結合、或いは、２価であって、炭素数１〜２０の、直鎖状、分岐状若しくは環状の飽和炭化水素基又は不飽和炭化水素基であり、Ｒ^３０は、少なくとも１つの水素原子がフッ素原子で置換された炭素数１〜１０の炭化水素基である。） As said repeating unit (b3), the repeating unit represented by the following general formula (13-1) and (14-1) is mentioned.

(In the formula, R ²⁸ is a hydrogen atom, a methyl group or a trifluoromethyl group, and R ²⁹ is a single bond or a divalent group having 1 to 20 carbon atoms, linear, branched or A cyclic saturated hydrocarbon group or an unsaturated hydrocarbon group, and R ³⁰ is a hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.)

In the above general formulas (13-1) and (14-1), the divalent divalent C 1-20 linear and branched saturated hydrocarbon group and unsaturated carbon represented by R ²⁹ As the hydrogen group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, Examples thereof include hydrocarbon groups derived from linear and branched alkyl groups having 1 to 20 carbon atoms such as hexyl group, heptyl group, octyl group, nonyl group and decyl group, and alkenyl groups.

Examples of the divalent cyclic saturated hydrocarbon group and unsaturated hydrocarbon group represented by R ²⁹ include groups derived from alicyclic hydrocarbons and aromatic hydrocarbons having 3 to 20 carbon atoms. Cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, Tricyclo [3.3.1.1 ^3,7 ] decane, tetracyclo [6.2.1.1 ^3,6 . And cycloalkanes such as 0 ^2,7 ] dodecane. Examples of the aromatic hydrocarbon include benzene and naphthalene.

When R ²⁹ is a saturated hydrocarbon group or an unsaturated hydrocarbon group, at least one of the hydrogen atoms is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a 2-methylpropyl group. A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms such as 1-methylpropyl group and tert-butyl group, hydroxyl group, cyano group, hydroxyalkyl group having 1 to 10 carbon atoms, carboxyl group, It may be a group substituted by an oxygen atom or the like.

The above description is applied to R ³⁰ in the general formula (13-1).

The repeating unit (b3) constituting the polymer [B] may be only one type or a combination of two or more types.
When the said polymer [B] contains a repeating unit (b3), the solubility with respect to a developing solution can be improved.

1-3-2-3. Repeating unit (b4)
As the repeating unit (b4), a repeating unit having a lactone skeleton (hereinafter referred to as “repeating unit (b4-1)”) and a repeating unit having a cyclic carbonate skeleton (hereinafter referred to as “repeating unit (b4-2)”). Said).

（式中、Ｒ^３１は、水素原子又はメチル基であり、Ｒ^３２は、水素原子又は炭素数１〜４の置換基を有してもよいアルキル基であり、Ｒ^３３は、水素原子又はメトキシ基であり、Ａは、単結合、エーテル基、エステル基、カルボニル基、炭素数１〜３０の２価の鎖状炭化水素基、炭素数３〜３０の２価の脂環式炭化水素基、炭素数６〜３０の２価の芳香族炭化水素基又はこれらの誘導体基であり、Ｂは、酸素原子又はメチレン基であり、ｌは１〜３の整数であり、ｍは０又は１である。） (1) Repeating unit (b4-1)
As said repeating unit (b4-1), the repeating unit represented by the following general formula (16-1)-(16-6) is mentioned.

(In the formula, R ³¹ is a hydrogen atom or a methyl group, R ³² is a hydrogen atom or an alkyl group which may have a substituent having 1 to 4 carbon atoms, and R ³³ is a hydrogen atom or a methoxy group. A is a single bond, an ether group, an ester group, a carbonyl group, a divalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, A bivalent aromatic hydrocarbon group having 6 to 30 carbon atoms or a derivative group thereof; B is an oxygen atom or a methylene group; l is an integer of 1 to 3; and m is 0 or 1. .)

In the general formula (16-1), R ³² is a hydrogen atom or an alkyl group which may have a substituent having 1 to 4 carbon atoms, and examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, Examples include ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, tert-butyl group and the like. When R ³² is an alkyl group having a substituent, at least one of the hydrogen atoms contained in the alkyl group having 1 to 4 carbon atoms is a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a phenyl group , Groups substituted with an acetoxy group, an alkoxy group, and the like.

In the general formulas (16-1) and (16-2), the divalent chain hydrocarbon group having 1 to 30 carbon atoms represented by A includes a methylene group, an ethylene group, and a 1,2-propylene group. 1,3-propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecacene Linear alkylene groups such as a methylene group, a pentadecamethylene group, a hexadecamethylene group, a heptacamethylene group, an octadecamethylene group, a nonadecamethylene group, an icosalen group; 1-methyl-1,3-propylene group, 2 -Methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl 1,4-butylene group, an ethylidene group, 1-propylidene group, and branched alkylene groups such as 2-propylidene group.
Examples of the divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms include 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1,4-cyclohexylene group, 1,5-cyclohexane. A monocyclic cycloalkylene group having 3 to 30 carbon atoms such as octylene group; 1,4-norbornylene group, 2,5-norbornylene group, 1,5-adamantylene group, 2,6-adamantylene group, etc. Examples thereof include a cyclic cycloalkylene group.
Furthermore, examples of the divalent aromatic hydrocarbon group having 6 to 30 carbon atoms include arylene groups such as a phenylene group, a tolylene group, a naphthylene group, a phenanthrylene group, and an anthrylene group.

As a monomer that gives the repeating unit (b4-1), (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl ester, (Meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl ester, (meth) acrylic acid-5-oxo-4 -Oxa-tricyclo [5.2.1.0 ^3,8 ] dec-2-yl ester, (meth) acrylic acid-10-methoxycarbonyl-5-oxo-4-oxa-tricyclo [5.2.1. 0 ^3,8 ] non-2-yl ester, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl ester, (meth) acrylic acid-4-methoxy Carbonyl-6-oxo-7 Oxa-bicyclo [3.2.1] oct-2-yl ester, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] non-2-yl ester, (meth) acrylic Acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] non-2-yl ester, (meth) acrylic acid-2-oxotetrahydropyran-4-yl ester, (meth) Acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl ester, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran-4-yl ester, (meth) acrylic acid-4-propyl-2 -Oxotetrahydropyran-4-yl ester, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-2,2- Dimethyl-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl ester, (Meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-5,5-dimethyl-2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid- 2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl ester, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl ester, (Meth) acrylic acid-4,4-dimethyl-5-oxo Tetrahydrofuran-2-yl methyl ester.

（式中、Ｒ^３５は、水素原子、メチル基又はトリフルオロメチル基であり、Ｒ^３６は、相互に独立して、水素原子又は炭素数１〜５の鎖状炭化水素基であり、Ｄは、単結合、炭素数１〜３０の２価若しくは３価の鎖状炭化水素基、炭素数３〜３０の２価若しくは３価の脂環式炭化水素基、又は、炭素数６〜３０の２価若しくは３価の芳香族炭化水素基（但し、Ｄが３価の場合、Ｄに含まれる炭素原子と環状炭酸エステルを構成する炭素原子とが結合して、環構造が形成される）であり、ｎは２〜４の整数である。） (2) Repeating unit (b4-2)
Moreover, as said repeating unit (b4-2), the repeating unit represented by following General formula (18) is mentioned.

(Wherein R ³⁵ is a hydrogen atom, a methyl group or a trifluoromethyl group, R ³⁶ is independently a hydrogen atom or a chain hydrocarbon group having 1 to 5 carbon atoms, and D is A single bond, a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent or trivalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, or 2 having 6 to 30 carbon atoms A divalent or trivalent aromatic hydrocarbon group (provided that when D is trivalent, a carbon atom contained in D and a carbon atom constituting a cyclic carbonate are combined to form a ring structure) , N is an integer of 2-4.)

  In the said General formula (18), n is an integer of 2-4. Accordingly, the cyclic carbonate structure is a 5-membered ring structure when n = 2 (ethylene group), a 6-membered ring structure when n = 3 (propylene group), and a 7-membered ring when n = 4 (butylene group). It becomes a structure.

In the general formula (18), the chain hydrocarbon group having 1 to 5 carbon atoms represented by R ³⁶ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec- Examples include a butyl group, a tert-butyl group, an n-pentyl group, and a neopentyl group.

  In the general formula (18), when D is a single bond, the oxygen atom derived from the (meth) acrylic acid moiety constituting the main chain of the polymer and the carbon atom forming the cyclic carbonate structure are directly bonded. Will be.

  In the general formula (18), the chain hydrocarbon group represented by D refers to a hydrocarbon group composed of only a chain structure without including a cyclic structure in the main chain. Moreover, an alicyclic hydrocarbon group means the hydrocarbon group which contains only the structure of an alicyclic hydrocarbon in a ring structure, and does not contain an aromatic ring structure. However, the alicyclic hydrocarbon group does not need to be composed only of the structure of the alicyclic hydrocarbon, and a part thereof may include a chain structure. Furthermore, the aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring structure in the ring structure. However, this aromatic hydrocarbon group does not need to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure.

  Examples of the divalent chain hydrocarbon group having 1 to 30 carbon atoms represented by D include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a tetramethylene group, a pentamethylene group, Hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptacamethylene group Group, octadecamethylene group, nonadecamethylene group, icosalen group and other linear alkylene groups; 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1, 2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4-butylene group, ethylidene group, 1-propylene Den groups, such as branched alkylene group such as 2-propylidene group. Examples of the trivalent chain hydrocarbon group having 1 to 30 carbon atoms include a group in which one hydrogen atom is eliminated from these linear or branched alkylene groups.

  Examples of the divalent alicyclic hydrocarbon group represented by D include 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1,4-cyclohexylene group, 1,5-cyclooctylene group. A monocyclic cycloalkylene group having 3 to 10 carbon atoms such as 1,4-norbornylene group, 2,5-norbornylene group, 1,5-adamantylene group, 2,6-adamantylene group, etc. An alkylene group etc. are mentioned. Examples of the trivalent alicyclic hydrocarbon group include a group in which one hydrogen atom is eliminated from these monocyclic or polycyclic cycloalkylene groups.

  Examples of the divalent aromatic hydrocarbon group represented by D include arylene groups such as a phenylene group, a tolylene group, a naphthylene group, a phenanthrylene group, and an anthrylene group. Examples of the trivalent aromatic hydrocarbon group include groups obtained by removing one hydrogen atom from these arylene groups.

  When D is a chain hydrocarbon group, it is preferably a linear alkyl group having 1 to 5 carbon atoms, and the structure in the general formula (18) at this time constitutes the main chain of this repeating unit ( An oxygen atom derived from the (meth) acrylic acid moiety and a carbon atom forming a cyclic carbonate structure are bonded via this linear alkyl group, and the following general formulas (18-1) to ( 18-6). The chain hydrocarbon group may have a structure having a substituent (specifically, a repeating unit represented by the following general formula (18-16)).

In the general formula (18), a carbon atom contained in D and a carbon atom forming a cyclic carbonate structure may be bonded to form a ring structure. In other words, the cyclic carbonate structure may constitute a part of a bridged ring, a condensed ring, or a spiro ring. For example, when the ring structure includes two carbon atoms in the cyclic carbonate structure, a bridged ring or a condensed ring is formed, and when only one carbon atom in the cyclic carbonate is included, a spiro ring Is formed. As a repeating unit in which a condensed ring (5 to 6-membered ring) containing a carbon atom contained in D and two carbon atoms forming a cyclic carbonate structure is formed, the following general formula (18-7), And repeating units represented by (18-9), (18-11), (18-12), (18-15), and (18-17) to (18-22).
On the other hand, as a repeating unit in which a spiro ring is formed by the carbon atom contained in D and one carbon atom forming a cyclic carbonate structure, the following general formulas (18-10) and (18-14) are used. The repeating unit represented is mentioned. The ring structure may be, for example, a heterocycle containing a heteroatom such as an oxygen atom (O) or a nitrogen atom (N). Specific examples include repeating units represented by the following general formulas (18-17) to (18-22).
On the other hand, as a repeating unit in which a bridged ring including two carbon atoms contained in D and two carbon atoms forming a cyclic carbonate structure is formed, the following general formulas (18-8) and (18 -13).

When D is an alicyclic hydrocarbon group, the structure in the general formula (18) includes an oxygen atom derived from the (meth) acrylic acid moiety constituting the main chain of the repeating unit, and a cyclic carbonate. Are bonded to each other through a norbornylene group (specifically, a repeating unit represented by the following general formula (18-10)) bonded via a cyclopentylene group. Repeating units (specifically, repeating units represented by the following general formulas (18-10) and (18-12)), repeating units bonded via a substituted tetradecahydrophenanthryl group ( Specifically, a repeating unit represented by the following general formula (18-14)) and the like can be mentioned.
In addition, as a repeating unit in which a condensed ring (4- to 5-membered ring) containing a carbon atom contained in D and two carbon atoms constituting a cyclic carbonate is formed, the following general formula (18-10) ) And the repeating unit represented by (18-12).
On the other hand, as a repeating unit in which a spiro ring is formed by the carbon atom contained in D and one carbon atom constituting the cyclic carbonate, the following general formulas (18-10) and (18-14) are used. The repeating unit represented is mentioned.

  Further, when D is an aromatic hydrocarbon group, the structure in the general formula (18) includes an oxygen atom derived from the (meth) acrylic acid moiety constituting the main chain of the repeating unit, and a cyclic carbonate. Examples thereof include a repeating unit in which the constituent carbon atom is bonded via a benzylene group (specifically, a repeating unit represented by the following general formula (18-15)).

（式中、Ｒ^３５は、水素原子、メチル基又はトリフルオロメチル基である。）

(In the formula, R ³⁵ represents a hydrogen atom, a methyl group or a trifluoromethyl group.)

  Monomers that give the repeating unit represented by the general formula (18) are described in, for example, Tetrahedron Letters, Vol. 27, no. 32 p. 3741 (1986), Organic Letters, Vol. 4, no. 15 p. 2561 (2002) and the like, and can be synthesized by a known method.

（式中、ｎは１〜３の整数であり、Ｅは、−Ｏ−、−ＣＯ−Ｏ−＊、又は、−ＣＯ−ＮＨ−＊（但し、「＊」はＲ^３８に結合する結合手を示す。）であり、Ｒ^３７は、水素原子、メチル基又はトリフルオロメチル基であり、Ｒ^３８は、単結合、或いは、炭素数１〜２０の炭化水素基を含む（ｎ＋１）価の基であり、Ｒ^３９は、単結合、或いは、２価であって、炭素数１〜２０の、直鎖状、分岐状若しくは環状の飽和炭化水素基又は不飽和炭化水素基であり、Ｇ^３は、単結合、−ＣＨＦ−、−ＣＦ_２−又は炭素数２〜２０の直鎖状若しくは分岐状のフルオロアルキレン基であり、Ｇ^４は、酸素原子、イミノ基、−ＣＯ−Ｏ−＊、又は、−ＳＯ_２−Ｏ−＊（但し、「＊」はＲ^４０に結合する結合手を示す。）であり、Ｒ^４０は、アルカリ解離性基である。） (3) Repeating unit (b4-3)
The repeating unit (b4-3) is preferably a repeating unit represented by the following general formula (19). When the polymer [B] contains the repeating unit (b4-3), the water repellency on the surface of the photoresist film can be lowered during development. This is considered to be because the polymer [B] reacts with the developer to generate a polar group. As a result, the radiation-sensitive resin composition for immersion exposure of the present invention can improve the hydrophilicity during alkali development while ensuring the hydrophobicity during immersion exposure, and can eliminate development defects in unexposed areas. Can be suppressed.

(In the formula, n is an integer of 1 to 3, and E is —O—, —CO—O— *, or —CO—NH— * (where “*” is a bond bonded to R ^38. R ³⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group, and R ³⁸ is a single bond or a (n + 1) -valent group containing a hydrocarbon group having 1 to 20 carbon atoms. R ³⁹ is a single bond or a divalent, straight-chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and G ³ is , A single bond, —CHF—, —CF ₂ —, or a linear or branched fluoroalkylene group having 2 to 20 carbon atoms, and G ⁴ represents an oxygen atom, an imino group, —CO—O— *, or , _-SO 2 -O - * (. However, "*" is to represents a bond that binds to ^{R 40) is, R 40} is an alkali It is away group.)

In the above general formula (19), E is —O—, —CO—O— *, or —CO—NH— * (wherein * represents a bond bonded to R ³⁸ ); -CO-O- * is preferable.

R ³⁸ represents may be an (n + 1) valent group containing a hydrocarbon group having 1 to 20 carbon atoms. If R ³⁸ is a (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, methane, ethane, n- propane, 2-propane, n- butane, 2-methylpropane, n- pentane, 2-methylbutane , 2,2-dimethylpropane, hexane, heptane, octane, nonane, decane, etc., hydrocarbon groups having a chain structure in which (n + 1) hydrogen atoms have been removed, and cyclobutane, cyclopentane , Cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [3.3.1.1 ^3,7 ] A hydrocarbon group having a cyclic structure in which (n + 1) hydrogen atoms have been removed from an alicyclic hydrocarbon such as decane or an aromatic hydrocarbon such as benzene or naphthalene. It can be.

（但し、Ｒは、炭素数１〜２０の（ｎ＋１）価の炭化水素基であり、＊は、Ｒ^３９に結合する結合手を示す。−（ＮＨ−＊）等の基は、Ｒにおける同一の炭素原子に結合してよいし、異なる炭素原子に結合してもよい。） In addition, when R ³⁸ is a (n + 1) -valent group containing a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group “—R—” having the above chain structure or cyclic structure is used. It can be a group represented by the formula.

(However, R is an (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and * represents a bond bonded to R ^39. Groups such as-(NH- *) are the same as those in R. And may be bonded to different carbon atoms.)

R ³⁹ is divalent and can be a linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 20 carbon atoms. In these hydrocarbon groups, hydrogen atoms may be substituted with oxygen atoms, hydroxyl groups, cyano groups, carboxyl groups, and the like.
Examples of linear and branched saturated hydrocarbon groups and unsaturated hydrocarbon groups include methane, ethane, n-propane, 2-propane, n-butane, 2-methylpropane, n-pentane, 2-methylbutane, 2 , 2-dimethylpropane, hexane, heptane, octane, nonane, decane and other chain hydrocarbons.
Examples of the cyclic saturated hydrocarbon group and unsaturated hydrocarbon group include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, and tricyclo [5.2. 1.0 ^2,6 ] decane, tricyclo [3.3.1.1 ^3,7 ] decane, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] an alicyclic hydrocarbon such as dodecane; a group derived from an aromatic hydrocarbon such as benzene or naphthalene.

（式中、Ｒｆは、相互に独立して、水素原子、フッ素原子又は炭素数１〜１０のパーフルオロアルキル基であり、ｐは２〜４の整数である。但し、全てのＲｆが水素原子であることはない。） Examples of the linear and branched fluoroalkylene group having 2 to 20 carbon atoms represented by G ³ include a group represented by the following general formula (20).

(In the formula, Rf is independently of each other a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 10 carbon atoms, and p is an integer of 2 to 4, provided that all Rf are hydrogen atoms. Never.)

G ⁴ is an oxygen atom, an imino group, —CO—O— *, or —SO ₂ —O— * (where “*” represents a bond bonded to R ⁴⁰ ). , Oxygen atom and -CO-O- * are preferred.

R ⁴⁰ is an alkali dissociable group. The “alkali dissociable group” refers to a group that substitutes a hydrogen atom in a polar functional group such as a hydroxyl group, a carboxyl group, and a sulfonic acid group, and dissociates in the presence of an alkali. That, -G ⁴ -R ⁴⁰ in formula (19) is a hydroxyl group, an amino group, a carboxyl group or sulfoxyl group, is one that has been modified by alkaline dissociable group.

（式中、Ｒ^４０１は、炭素数１〜２０の炭化水素基に含まれる水素原子の少なくとも１つがフッ素原子に置換されてなる基である。） The alkali dissociable group is not particularly limited as long as it exhibits the above properties. In the general formula (19), when G ⁴ is an oxygen atom or an imino group, examples of the alkali dissociable group R ⁴⁰ include groups represented by the following general formula (22).

(In the formula, R ⁴⁰¹ is a group in which at least one of the hydrogen atoms contained in the hydrocarbon group having 1 to 20 carbon atoms is substituted with a fluorine atom.)

R ⁴⁰¹ in the general formula (22) is a linear or branched group in which all or part of the hydrogen atoms contained in the alkyl group having 1 to 10 carbon atoms are substituted with fluorine atoms, and carbon. A group in which all or a part of the hydrogen atoms contained in the alicyclic hydrocarbon group of the number 3 to 20 are substituted with fluorine atoms is preferred.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 2- (2-methylpropyl) group, and 1-pentyl. Group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (2-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (2 -Methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2-methylpentyl) group, 3- (3-methylpentyl) group and the like.
Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopentyl group, cyclopentylmethyl group, 1- (1-cyclopentylethyl) group, 1- (2-cyclopentylethyl) group, cyclohexyl group, and cyclohexylmethyl group. 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, 1- (1-cycloheptylethyl) group, 1- (2-cycloheptylethyl) Group, 2-norbornyl group and the like.

R ⁴⁰¹ is more preferably a linear or branched perfluoroalkyl group in which all of the hydrogen atoms contained in the alkyl group having 1 to 10 carbon atoms are substituted with fluorine atoms, particularly a trifluoromethyl group. preferable.

When the alkali dissociable group R ⁴⁰ is a group represented by the general formula (22), it can be formed by fluoroacylating an alcohol, amine or carboxylic acid by a conventionally known method. A specific method is shown below.
(1) Method of condensing alcohol and fluorocarboxylic acid in the presence of an acid for esterification (2) Method of condensing alcohol and fluorocarboxylic acid halide in the presence of a base for esterification

（一般式（Ｔ１）中、Ｒ^４２は、ハロゲン原子又は炭素数１〜１０のアルキル基、アルコキシル基、アシル基若しくはアシロキシ基であり、ｍ_１は０〜５の整数である。一般式（Ｔ２）中、Ｒ^４３は、ハロゲン原子又は炭素数１〜１０のアルキル基、アルコキシル基、アシル基若しくはアシロキシ基であり、ｍ_２は０〜４の整数である。一般式（Ｔ３）中、Ｒ^４４は、相互に独立して、ハロゲン原子又は炭素数１〜１０のアルキル基、アルコキシル基、アシル基若しくはアシロキシ基であり、２つのＲ^４４が互いに結合して形成された、炭素数４〜２０の脂環式構造であってもよい。） In the above general formula (19), when G ⁴ is —CO—O— * (where “*” represents a bond bonded to R ⁴⁰ ), R ⁴⁰ is represented by the following general formula (T1 ) To (T3).

(In General Formula (T1), R ⁴² represents a halogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an acyl group, or an acyloxy group, and m ₁ is an integer of 0 to 5. General Formula (T2 R ⁴³ is a halogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an acyl group or an acyloxy group, and m ₂ is an integer of 0 to 4. In the general formula (T3), R ⁴⁴ Are independently a halogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an acyl group, or an acyloxy group, and formed by bonding two R ⁴⁴ to each other, and having 4 to 20 carbon atoms (It may be an alicyclic structure.)

In the general formulas (T1) and (T2), examples of the halogen atom represented by R ⁴² and R ⁴³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, fluorine atoms are preferred.

In the general formulas (T1) and (T2), examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁴² and R ⁴³ include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, 1- Butyl group, 2-butyl group, 2- (2-methylpropyl) group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group , 2- (2-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- ( 3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- ( 2-methylpentyl) group, 3- (3-methyl) Pentyl) group and the like.

In the general formulas (T1) and (T2), examples of the alkoxyl group having 1 to 10 carbon atoms represented by R ⁴² and R ⁴³ include a methoxy group, an ethoxy group, an n-butoxy group, a tert-butoxy group, and a propoxy group. And isopropoxy group.

In the general formula (T1) and ^(T2), expressed by ^{R 42} and ^{R 43,} the acyl group having 1 to 10 carbon atoms, an acetyl group, an ethylcarbonyl group, a propyl carbonyl group.

In the general formulas (T1) and (T2), the acyloxy group having 1 to 10 carbon atoms represented by R ⁴² and R ⁴³ includes an acetoxy group, an ethylyloxy group, a butyryloxy group, a tert-butyryloxy group, and a tert-amylyloxy group. , N-hexane carbonyloxy group, n-octane carbonyloxy group and the like.

In the general formula (T3), the alkyl group having 1 to 10 carbon atoms, the alkoxyl group, the acyl group, and the acyloxy group represented by R ⁴⁴ include R ⁴² in the general formulas (T1) and (T2), and It can be the same group applied to R ⁴³ .

In the general formula (T3), two R ⁴⁴ bonded formed together, the alicyclic structure having 4 to 20 carbon atoms, cyclopentyl, cyclopentylmethyl group, 1- (1-cyclopentylethyl) group 1- (2-cyclopentylethyl) group, cyclohexyl group, cyclohexylmethyl group, 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, 1- ( 1-cycloheptylethyl) group, 1- (2-cycloheptylethyl) group, 2-norbornyl group and the like.

  Examples of the group represented by the general formula (T3) include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2-methylpentyl) group etc. are mentioned. Of these, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl and 2-butyl are preferred.

In the said General formula (19), n is an integer of 1-3. When n is 2 or 3, in any case, a plurality of R ³⁹ , G ³ , G ⁴ and R ⁴⁰ may be the same as or different from each other. That is, when n is 2 or 3, a plurality of-(R ³⁹ -G ³ -G ⁴ -R ⁴⁰ ) bonded to R ³⁸ may be the same as or different from each other. Further, a plurality of ^{- (R 39 -G 3 -G 4} -R 40) ^may or be attached to the same carbon atom in ^{R 38,} it may be bonded to different carbon atoms.

（式中、ｎは１〜３の整数であり、Ｒ^３７は、水素原子、メチル基又はトリフルオロメチル基であり、Ｒ^３８は、単結合、或いは、炭素数１〜２０の炭化水素基を含む（ｎ＋１）価の基であり、Ｒ^３９は、単結合、或いは、２価であって、炭素数１〜２０の、直鎖状、分岐状若しくは環状の飽和炭化水素基又は不飽和炭化水素基であり、Ｇ^３は、単結合、−ＣＨＦ−、−ＣＦ_２−又は炭素数２〜２０の直鎖状若しくは分岐状のフルオロアルキレン基であり、Ｇ^４は、酸素原子、イミノ基、−ＣＯ−Ｏ−＊、又は、−ＳＯ_２−Ｏ−＊（但し、「＊」はＲ^４０に結合する結合手を示す。）であり、Ｒ^４０は、アルカリ解離性基である。） As the above repeating unit (b4-3), in the general formula (19), R ³⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group, and E is —CO—O— * (the following general formula (19-1), hereinafter referred to as “repeat unit (b4-3-1)”).

(In the formula, n is an integer of 1 to 3, R ³⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group, and R ³⁸ is a single bond or a hydrocarbon group having 1 to 20 carbon atoms. An (n + 1) -valent group, R ³⁹ is a single bond or a divalent, straight-chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon having 1 to 20 carbon atoms G ³ is a single bond, —CHF—, —CF ₂ —, or a linear or branched fluoroalkylene group having 2 to 20 carbon atoms, G ⁴ is an oxygen atom, an imino group, — CO—O— * or —SO ₂ —O— * (where “*” represents a bond bonded to R ⁴⁰ ), and R ⁴⁰ is an alkali dissociable group.)

（式中、ｎは１〜３の整数であり、Ｒ^３７、Ｒ^３８、Ｒ^３９及びＲ^４０１は、上記説明が適用される。）

（式中、Ｒ^３７、Ｒ^３８及びＲ^３９は、上記説明が適用される。Ｒ^４１は、上記式（Ｔ１）〜（Ｔ３）で表される基から選ばれた基である。） (3-1) Repeating unit (b4-3-1)
The repeating unit (b4-3-1) represented by the general formula (19-1) is a repeating unit represented by the following general formula (19-1a) (hereinafter referred to as “repeating unit (b4-3-1x)”. And a repeating unit represented by the following formula (19-1b) (hereinafter referred to as “repeating unit (b4-3-1y)”).

(In the formula, n is an integer of 1 to 3, and the above explanation is applied to R ³⁷ , R ³⁸ , R ³⁹ and R ^401. )

(In the formula, the above explanation is applied to R ³⁷ , R ³⁸ and R ^39. R ⁴¹ is a group selected from the groups represented by the above formulas (T1) to (T3).)

（式中、Ｒ^３７、Ｒ^３９及びＲ^４０１は、上記説明が適用される。Ｒｆは、相互に独立して、フッ素原子又は炭素数１〜１０のパーフルオロアルキル基であり、ｎ１は、相互に独立して、０〜４の整数である。一般式（１９−１ａ−１）において、Ｒ^３８は、炭素数１〜２０の炭化水素基を含む２価の基であり、一般式（１９−１ａ−２）において、Ｒ^３８は、炭素数１〜２０の炭化水素基を含む３価の基である。） (3-1-1) Repeating unit (b4-3-1x)
As the repeating unit (b4-3-1x) represented by the general formula (19-1a), the repeating unit represented by the following general formula (19-1a-1) and the following general formula (19-1a) -2).

(In the formula, the above explanation is applied to R ³⁷ , R ³⁹ and R ^401. Rf is independently a fluorine atom or a C 1-10 perfluoroalkyl group, and n 1 is Each independently represents an integer of 0 to 4. In the general formula (19-1a-1), R ³⁸ is a divalent group containing a hydrocarbon group having 1 to 20 carbon atoms, and the general formula (19 -1a-2 ^{in), R 38} is a trivalent group containing a hydrocarbon group having 1 to 20 carbon atoms.)

In the general formulas (19-1a-1) and (19-1a-2), Rf is preferably a fluorine atom or a trifluoromethyl group.
Moreover, in the repeating unit represented by the general formulas (19-1a-1) and (19-1a-2), when the polymer [B] in which n1 is 1 to 4 is used, B] and an aqueous alkali solution produce an OH group having a fluorine atom or a perfluoroalkyl group at the α-position. Such an OH group has a low pKa value as compared with an alcoholic OH group, and thus is preferable from the viewpoint of improving hydrophilicity during alkali development.

R ³⁸ in the general formula (19-1a-1) is a divalent group containing a hydrocarbon group having 1 to 20 carbon atoms, and includes methane, ethane, n-propane, 2-propane, n-butane, 2 -Hydrocarbon having a chain structure in which two hydrogen atoms are removed from chain hydrocarbons such as methylpropane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane, decane, etc. Groups, as well as cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [3. 3.1.1 ^3,7] alicyclic hydrocarbons decane, or benzene, a hydrogen atom in the aromatic hydrocarbons such as naphthalene, removing two, have a cyclic structure That the hydrocarbon group may be a group containing a.

R ³⁸ in the general formula (19-1a-2) is a trivalent group containing a hydrocarbon group having 1 to 20 carbon atoms, and includes methane, ethane, n-propane, 2-propane, and n-butane. 2-chain propane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane, decane, etc. Hydrocarbon groups, and cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [ 3.3.1.1 ^{3, 7]} alicyclic hydrocarbons decane, or benzene, a hydrogen atom in the aromatic hydrocarbons such as naphthalene, removing two, annular structure Hydrocarbon radical, having a can be a group containing a. The hydrocarbon group is preferably a linear or branched hydrocarbon group having 1 to 10 carbon atoms and a cyclic hydrocarbon group having 4 to 20 carbon atoms. In addition, the terminal on the R ² side in R ³⁸ may have an oxygen atom, a sulfur atom, a carbonyl group or an imino group.

In formula ^(19-1a-2), 2 two ^{R 39} that binds to ^{R 38 are,} may be attached to the same carbon atom in ^{R 38,} may be bonded to different carbon atoms.

（式中、Ｒ^３７及びＲ^４０１は、上記説明が適用される。） Examples of the repeating unit represented by the general formula (19-1a-1) include repeating units represented by the following general formulas (19-1a-1a) to (19-1a-1d).

(In the formula, the above description applies to R ³⁷ and R ^401. )

（式中、Ｒ^３７及びＲ^４０１は、上記説明が適用される。） Examples of the repeating unit represented by the general formula (19-1a-2) include repeating units represented by the following general formulas (19-1a-2a) to (19-1a-2b).

(In the formula, the above description applies to R ³⁷ and R ^401. )

（式中、ｎ２は、０〜４の整数であり、Ｒ^３８は、２価であって、炭素数１〜２０の炭化水素基を含む基であり、Ｒ^３７、Ｒｆ及びＲ^４１は、上記説明が適用される。）

（式中、ｎ２は、０〜４の整数であり、Ｒ^４６は、２価であって、炭素数１〜２０の炭化水素基であり、Ｒ^３７、Ｒ^３８、Ｒ^３９、Ｒｆ及びＲ^４１は、上記説明が適用される。） (3-1-2) Repeating unit (b4-3-1y)
In addition, as the repeating unit (b4-3-1y) represented by the general formula (19-1b), in the general formula (19-1b), R ³⁹ is a single bond, and G ³ is a single bond. , —CHF—, —CF ₂ — or a repeating unit which is a linear or branched fluoroalkylene group having 2 to 20 carbon atoms (see the following general formula (19-1b-1)), and the above general formula ( 19-1b), R ³⁸ is (—R ⁴⁶ —O—CO—), and G ³ is a single bond, —CHF—, —CF ₂ — or a linear or branched group having 2 to 20 carbon atoms. The repeating unit which is a fluoroalkylene group (see the following general formula (19-1b-2)).

(In the formula, n2 is an integer of 0 to 4, R ³⁸ is a divalent group containing a hydrocarbon group having 1 to 20 carbon atoms, and R ³⁷ , Rf and R ⁴¹ are the above-mentioned groups. Explanation applies.)

(In the formula, n2 is an integer of 0 to 4, R ⁴⁶ is a divalent hydrocarbon group having 1 to 20 carbon atoms, R ³⁷ , R ³⁸ , R ³⁹ , Rf and R ^41. The above description applies.)

In the general formula (19-1b-1), Rf is preferably a fluorine atom and a trifluoromethyl group. ^R38 is preferably a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, and a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms.
In the general formula (19-1b-2), Rf is preferably a fluorine atom or a trifluoromethyl group. R ⁴⁶ is preferably a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, and a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms.

  In general formula (19-1b-1) and general formula (19-1b-2), when n2 is 1 to 4, it has a fluorine atom or a perfluoroalkyl group at the α-position of the carbonyloxy group, It is thought that the reactivity with respect to alkaline aqueous solution becomes high. Moreover, the pKa of the COOH group generated by hydrolysis of the alkali dissociable group is also low, which is preferable from the viewpoint of improving hydrophilicity during alkali development.

（式中、Ｒ^３７及びＲ^４１は、上記説明が適用される。） Examples of the repeating unit represented by the general formula (19-1b-1) include repeating units represented by the following general formulas (19-1b-1a) to (19-1b-1d).

(In the formula, the above description applies to R ³⁷ and R ^41. )

The repeating unit (b4) constituting the polymer [B] may be only one type or a combination of two or more types.
When the said polymer [B] contains a repeating unit (b4), the solubility with respect to a developing solution can be improved.

When the said polymer [B] contains another repeating unit, the content is shown below.
The content of the repeating unit (b2) is preferably 80 mol% or less, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol%, based on 100 mol% in total of all repeating units. . When the content ratio of the repeating unit (b2) is in the above range, the difference between the advancing contact angle and the receding contact angle can be reduced.
Content of the said repeating unit (b3) becomes like this. Preferably it is 50 mol% or less, More preferably, it is 5-30 mol%, More preferably, it is 5-20 mol%. When the content ratio of the repeating unit (b3) is in the above range, it is possible to achieve both ensuring water repellency after coating and increasing the contact angle with respect to the developer after PEB.
Content of the said repeating unit (b4) becomes like this. Preferably it is 50 mol% or less, More preferably, it is 5-30 mol%, More preferably, it is 5-20 mol%. When the content ratio of the repeating unit (b4) is in the above range, it is possible to achieve both ensuring water repellency after coating and increasing the contact angle with respect to the developer after PEB.

  The weight average molecular weight (hereinafter referred to as “Mw”) of the polymer [B] is preferably 1,000 to 50,000, more preferably 1,000 in terms of polystyrene by gel permeation chromatography (GPC). -40,000, more preferably 1,000-30,000. If Mw is less than 1,000, a photoresist film having a sufficient receding contact angle may not be obtained. On the other hand, if Mw exceeds 50,000, the developability of the photoresist film may deteriorate.

  Moreover, the ratio (Mw / Mn) obtained using the number average molecular weight (hereinafter referred to as “Mn”) in terms of polystyrene by GPC and Mw is preferably 1 to 5, more preferably 1 to 4. is there.

  The composition of this invention may contain the said polymer [B] individually by 1 type or in combination of 2 or more types.

Next, the manufacturing method of the said polymer [B] is demonstrated.
The polymer [B] is a repeating unit in a solvent to which a radical polymerization initiator (hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, etc.) is added in the presence of a chain transfer agent, for example. It can manufacture by polymerizing the monomer containing the compound which will form (b1).

  Examples of the solvent include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; cycloalkanes such as cyclohexane, cycloheptane and cyclooctane; decalin, norbornane and the like Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylene dibromide, chlorobenzene; ethyl acetate, acetic acid saturated carboxylic acid esters such as n-butyl, isobutyl acetate and methyl propionate; ketones such as acetone, 2-butanone, 4-methyl-2-pentanone and 2-heptanone; tetrahydrofuran, dimethoxyethane, diethoxyethane and the like Ethers; methanol, ethanol Nord, 1-propanol, 2-propanol, alcohols such as 4-methyl-2-pentanol. These solvents may be used alone or in combination of two or more.

The polymerization temperature is preferably 40 ° C to 150 ° C, more preferably 50 ° C to 120 ° C. Moreover, reaction time becomes like this. Preferably it is 1-48 hours, More preferably, it is 1-24 hours.
In addition, the said polymer [B] is so preferable that there is little content of impurities, such as a halogen and a metal. When the content of such impurities is small, the sensitivity, resolution, process stability, pattern shape and the like of the photoresist film can be further improved. Therefore, as a purification method of the polymer [B], chemical purification methods such as washing with water, liquid-liquid extraction and the like, and these chemical purification methods and physical purification methods such as ultrafiltration and centrifugation are combined. Methods and the like.

  Solvents used for liquid-liquid extraction include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane; methanol, ethanol, 1-propanol, 2-propanol, 4 -Alcohols such as methyl-2-pentanol; ketones such as acetone, 2-butanone, 4-methyl-2-pentanone and 2-heptanone. Of these, n-hexane, n-heptane, methanol, ethanol, acetone and 2-butanone are preferred.

  In the composition of the present invention, the content of the polymer [B] is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the polymer [C]. Part. When the content of the polymer [B] is within this range, a photoresist film having a sufficient receding contact angle can be formed, and acid generators such as the compound [A] are hardly eluted. A photoresist film can be obtained. In addition, when the content of the polymer [B] is less than 0.1 parts by mass, a photoresist film in which the receding contact angle of the formed photoresist film is insufficient or the acid generator or the like is not easily eluted is obtained. It may not be possible. On the other hand, when the content of the polymer [B] is more than 20 parts by mass, when a line and space pattern is formed, the depth of focus of the isolated line (line part) becomes small or development defects occur. Sometimes.

1-3. Polymer [C]
The polymer [C] is not particularly limited as long as it has an acid-dissociable group and contains less than 5 mass% of fluorine atoms when the entire polymer [C] is 100 mass%. The fluorine atom content is preferably 0 to 4.9% by mass, and more preferably 0 to 4% by mass. The polymer [C] may be a polymer containing no fluorine atom. The content ratio of the fluorine atom can be measured by ¹³ C-NMR.
The polymer [C] is preferably an alkali-insoluble or alkali-insoluble polymer that becomes alkali-soluble by the action of an acid. Here, “alkali-insoluble or hardly soluble in alkali” means that the photoresist film under the alkali development conditions employed when a resist pattern is formed from the photoresist film formed using the composition of the present invention. When a film formed using only the polymer [C] instead of is developed, it means that 50% or more of the initial film thickness of this film remains after development.

  The polymer [C] can be a polymer having a repeating unit (b2) that can be contained in the polymer [B]. Hereinafter, this repeating unit will be described as “repeating unit (c1)”.

1-3-1. Repeating unit (c1)
The repeating unit (c1) constituting the polymer [C] may be only one type or a combination of two or more types.

  In the present invention, the content of the repeating unit (c1) in the polymer [C] is preferably 5 to 85 mol%, more preferably 10 to 70 mol% with respect to 100 mol% in total of all repeating units. More preferably, it is 15 to 60 mol%. If the content of the repeating unit (c1) is less than 5 mol%, developability and exposure margin may be deteriorated. On the other hand, when the content ratio exceeds 85 mol%, the solubility of the polymer [C] in the solvent may deteriorate or the resolution may deteriorate.

1-3-2. Repeating unit (c2)
The polymer [C] may contain a repeating unit having a lactone skeleton (hereinafter referred to as “repeating unit (c2)”). This repeating unit (c2) can apply the repeating unit (b4) which can be contained in the said polymer [B], and is represented by said general formula (16-1)-(16-6). Repeating units can be used.
The repeating unit (c2) constituting the polymer [C] may be only one type or a combination of two or more types.

  In the present invention, the content of the repeating unit (c2) in the polymer [C] is preferably 10 to 70 mol%, more preferably 15 to 60 mol%, based on 100 mol% in total of all repeating units. More preferably, it is 20-50 mol%. If the content of the repeating unit (c1) is less than 10 mol%, the resolution as a resist may be lowered. On the other hand, when the content ratio exceeds 70 mol%, developability and exposure margin may be deteriorated.

1-3-3. Other Repeating Units The polymer [C] may include a repeating unit derived from an alicyclic compound, a repeating unit derived from an aromatic compound, or the like as another repeating unit.

1-3-4. Type of polymer The polymer [C] is obtained by copolymerizing a norbornene derivative and maleic anhydride with a polymer having an alicyclic skeleton such as a norbornane ring in the main chain obtained by polymerizing a norbornene derivative or the like. A polymer having a norbornane ring and a maleic anhydride derivative in the main chain, a polymer having a norbornane ring and a (meth) acryl skeleton mixed in the main chain obtained by copolymerizing the norbornene derivative and a (meth) acrylic compound, a norbornene derivative Obtained by copolymerizing a (meth) acrylic compound, a polymer in which a norbornane ring, a maleic anhydride derivative and a (meth) acrylic skeleton are mixed in the main chain obtained by copolymerization of maleic anhydride and (meth) acrylic compound Examples thereof include a polymer having a (meth) acryl skeleton as the main chain.
The composition of this invention may contain the said polymer [C] individually by 1 type or in combination of 2 or more types.

1-3-5. Physical property Mw of the polymer [C] is preferably from 1,000 to 100,000, more preferably from 1,000 to 30,000, still more preferably 1, in terms of polystyrene by gel permeation chromatography (GPC). 000 to 20,000. If the Mw is less than 1,000, the heat resistance of the photoresist film may decrease. On the other hand, if Mw exceeds 100,000, the developability of the photoresist film may deteriorate.

  Moreover, the ratio (Mw / Mn) obtained by GPC is preferably 1 to 5, more preferably 1 to 3.

1-3-6. Production method of polymer [C] The production method of polymer [C] can be the same as the production method of polymer [B].

1-4. Other Components In addition to the above essential components, the composition of the present invention may contain a solvent, an acid diffusion inhibitor, a surfactant, a sensitizer, an alicyclic additive, and the like.

1-4-1. Solvent This solvent is preferably one that can dissolve the polymers [B] and [C] to bring the composition of the present invention into a solution state.
Examples of the solvent include linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, and γ-butyrolactone. It is done. In addition, the said solvent may be used independently and may be used in combination of 2 or more type.

The amount of the solvent used is such that the total solid concentration of the composition of the present invention is preferably 1 to 50% by mass, more preferably 1 to 25% by mass.
The composition of the present invention can be used as a composition solution, for example, by filtration using a filter having a pore size of about 0.2 μm.

1-4-2. Acid Diffusion Inhibitor This acid diffusion inhibitor controls the phenomenon of acid diffusion in the photoresist film caused by the acid generator containing the above compound [A] by immersion exposure, and undesired chemical reaction in non-exposed areas. It is a component having an inhibitory action. By blending this acid diffusion inhibitor, the storage stability of the resulting composition can be improved. In addition, the resolution can be further improved, and a change in the line width of the resist pattern due to fluctuations in the holding time (PED) from exposure to heat treatment after exposure can be suppressed. As a result, the process stability is extremely excellent.

  Examples of the acid diffusion inhibitor include tertiary amine compounds, amine compounds other than tertiary amine compounds (other amine compounds), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.

  Tertiary amine compounds include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n-butylamine, di- Di (cyclo) such as n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine Alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n -Nonylamine, tri-n-decylamine, cyclohexyldimethyl Tri (cyclo) alkylamines such as amine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as 2,2 ′, 2 ″ -nitrotriethanol; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline is mentioned.

  Other amine compounds include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4 '-Diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4- Aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1- Methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benze , Bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinol, N, N, N ′, N ′ -Tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine and the like.

  Examples of the amide group-containing compound include N-tert-butoxycarbonyldi-n-octylamine, N-tert-butoxycarbonyldi-n-nonylamine, N-tert-butoxycarbonyldi-n-decylamine, and N-tert-butoxycarbonyl. Dicyclohexylamine, N-tert-butoxycarbonyl-1-adamantylamine, N-tert-butoxycarbonyl-2-adamantylamine, N-tert-butoxycarbonyl-N-methyl-1-adamantylamine, (S)-(−) -1- (tert-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (tert-butoxycarbonyl) -2-pyrrolidinemethanol, N-tert-butoxycarbonyl-4-hydroxypiperidine, N -Tert Butoxycarbonylpyrrolidine, N-tert-butoxycarbonylpiperazine, N-tert-butoxycarbonylpiperidine, N, N-di-tert-butoxycarbonyl-1-adamantylamine, N, N-di-tert-butoxycarbonyl-N-methyl -1-adamantylamine, N-tert-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-tert-butoxycarbonylhexamethylenediamine, N, N, N ′, N′-tetra-tert- Butoxycarbonylhexamethylenediamine, N, N′-di-tert-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-tert-butoxycarbonyl-1,8-diaminooctane, N, N′-di -Tert-butoxycarbonyl-1 9-diaminononane, N, N′-di-tert-butoxycarbonyl-1,10-diaminodecane, N, N′-di-tert-butoxycarbonyl-1,12-diaminododecane, N, N′-di-tert N- such as -butoxycarbonyl-4,4′-diaminodiphenylmethane, N-tert-butoxycarbonylbenzimidazole, N-tert-butoxycarbonyl-2-methylbenzimidazole, N-tert-butoxycarbonyl-2-phenylbenzimidazole, etc. In addition to tert-butoxycarbonyl group-containing amino compounds, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- Examples include methylpyrrolidone, N-acetyl-1-adamantylamine, and isocyanuric acid tris (2-hydroxyethyl).

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n-butylthiourea. Can be mentioned.

  Examples of the nitrogen-containing heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-methyl- Imidazoles such as 1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine , Nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, pyridines such as 2,2 ′: 6 ′, 2 ″ -terpyridine; piperazine, 1- (2-hydroxyethyl) In addition to piperazines such as piperazine, pyrazine, Razole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- ( N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like.

  The acid diffusion control agents may be used alone or in combination of two or more.

  When the composition of the present invention contains an acid diffusion controller, the content thereof is preferably 15 parts by mass or less, more preferably with respect to 100 parts by mass in total of the polymers [B] and [C]. It is 10 mass parts or less, More preferably, it is 5 mass parts or less. When there is too much content of the said acid diffusion control agent, the sensitivity of a photoresist film may fall. If the content is less than 0.001 part by mass, the pattern shape and dimensional fidelity may be reduced depending on the process conditions.

2. Resist Pattern Forming Method The resist pattern forming method of the present invention is a step of forming a photoresist film on a substrate using the above-described radiation-sensitive resin composition for immersion exposure of the present invention (hereinafter referred to as “first step”). ), An immersion exposure liquid disposed on the photoresist film, the photoresist film being subjected to immersion exposure via the immersion exposure liquid (hereinafter referred to as “second process”), and a liquid. A step of developing the immersion-exposed photoresist film to form a resist pattern (hereinafter referred to as “third step”).

The first step is a step of forming a photoresist film on a substrate using the radiation-sensitive resin composition for immersion exposure according to the present invention. Examples of the method for applying the composition include spin coating, cast coating, roll coating, and the like. Examples of the substrate include a silicon wafer and a wafer coated with aluminum.
A specific example of the first step is a method of volatilizing the solvent in the coating film by applying the composition so that the obtained photoresist film has a predetermined thickness and then pre-baking (PB). . Thereby, a uniform photoresist film is formed.
The thickness of the photoresist film is not particularly limited, but is usually 0.05 to 0.40 μm.
Moreover, although the conditions of prebaking are suitably selected by the structure of a composition, Preferably they are 30 degreeC-200 degreeC, More preferably, they are 50 degreeC-170 degreeC. It is.

  In the present invention, in order to maximize the potential of the radiation-sensitive resin composition for immersion exposure, it is disclosed in, for example, Japanese Patent Publication No. 6-12452 (Japanese Patent Laid-Open No. 59-93448). As described above, an organic or inorganic antireflection film can be formed on the substrate to be used. In order to prevent the influence of basic impurities contained in the environmental atmosphere, a protective film can be provided on the photoresist film as disclosed in, for example, Japanese Patent Laid-Open No. 5-188598. Further, in order to prevent the acid generator and the like from flowing out of the photoresist film, an immersion protective film may be provided on the photoresist film as disclosed in, for example, JP-A-2005-352384. it can. These techniques can be used in combination.

  The second step is a step in which an immersion exposure liquid is disposed on the photoresist film, and the photoresist film is subjected to immersion exposure via the immersion exposure liquid. In this step, the surface of the photoresist film is usually irradiated, that is, exposed to the radiation illustrated below through a photomask having a mask pattern for forming a desired pattern. Thereby, the radiation passes through the opening of the photomask, further passes through the exposure lens, and reaches the photoresist film. The exposed portion in the photoresist film is removed by the third step.

  As the immersion exposure liquid, pure water, a long chain or cyclic aliphatic compound, or the like can be used. Further, radiation is used as exposure light for immersion exposure. The radiation can be appropriately selected according to the type of the acid generator in the composition. For example, visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like can be used. Among these, far ultraviolet rays represented by ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm) are preferable, and ArF excimer laser (wavelength 193 nm) is particularly preferable. In addition, exposure conditions, such as an exposure amount, can be suitably selected according to the composition of the composition, the type when an additive is contained, and the like.

After the second step, a step of baking the exposed film (hereinafter referred to as “PEB”) may be provided as necessary. By this step, the cross-linking reaction of the polymer contained in the exposed portion can proceed smoothly.
The heating conditions for PEB are appropriately selected depending on the composition of the composition, but are preferably 30 ° C. to 200 ° C., more preferably 50 ° C. to 170 ° C., from the viewpoint of facilitating the crosslinking reaction.

  The third step is a step of developing a photoresist film subjected to immersion exposure to form a resist pattern. In this step, by using the developer, the unexposed portion in the second step is removed, and a pattern reflecting the pattern of the exposed portion, that is, the opening of the photomask, is left and formed.

  As the developer, an alkaline aqueous solution obtained by dissolving an alkaline compound in water is usually used. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyl Dimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and the like. These may be used alone or in combination of two or more. Of the above compounds, tetramethylammonium hydroxide is preferred. The concentration of the alkaline compound is usually 10% by mass or less. If this concentration is too high, the exposed area may also be dissolved in the developer.

The developer may be a solution containing only the alkaline compound or a composition containing an organic solvent, a surfactant and the like.
Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, alcohols such as n-butyl alcohol, tert-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; ethyl acetate, n-acetate Examples include esters such as butyl and isoamyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone, and dimethylformamide. These organic solvents may be used alone or in combination of two or more.

When the developer contains an organic solvent, the content thereof is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. When there is too much content of this organic solvent, developability may fall and the image development residue of an unexposed part may increase.
After the third step, the pattern remaining on the substrate is usually washed with water and dried.

  By providing the above steps, a pattern having a good shape can be formed.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

The GPC measurement method and ¹³ C-NMR measurement method of the polymer obtained by the following synthesis example are as follows.
(1) GPC measurement The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer are GPC columns “G2000HXL2”, “G3000HXL1” and “G4000HXL1” (above, trade names) manufactured by Tosoh Corporation. The measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the conditions of a flow rate of 1.0 mL / min and a column temperature of 40 ° C. using tetrahydrofuran as an elution solvent. The degree of dispersion (Mw / Mn) was calculated from these measurement results.
(2) ¹³ C-NMR analysis Measurement was performed using “JNM-EX270” (model name) manufactured by JEOL Ltd.

1. Polymers [B] and [C]
Monomers (M-1) to (M-15) used for the production of the polymers [B] and [C] are shown below.

Production Example 1 (Synthesis of polymer (B-1))
As shown in Table 1, 35.01 g (208 mmol) of compound (M-2) and 14.99 g (89 mmol) of compound (M-13) were dissolved in 100 g of 2-butanone, and then dimethyl 2,2′-azobis. 3.91 g of (2-methylpropionate) was added to prepare a monomer solution.
A 500 mL three-necked flask was charged with 30 g of 2-butanone, purged with nitrogen gas for 30 minutes, and then heated to 80 ° C. with stirring. Next, the monomer solution was dropped over 3 hours using a dropping funnel. The polymerization reaction was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water to cool to 30 ° C. or lower, and the polymerization solution was transferred to a 2 L separatory funnel.
To the above separatory funnel, 150 g of methanol was added to dilute the polymerization solution, and then 600 g of n-hexane was added and shaken (mixed). Thereafter, 30 g of distilled water was added, and the mixture was further shaken (mixed) and allowed to stand for 30 minutes. Next, the lower layer containing the polymer (B-1) was recovered, and solvent substitution was performed to obtain a propylene glycol monomethyl ether acetate solution.
The yield of the polymer (B-1) was 71%, and Mw = 7,100 and Mw / Mn = 1.3 were obtained by GPC measurement. As a result of ¹³ C-NMR analysis, the content ratios of the repeating units derived from the compound (M-2) and the compound (M-13) were 69.8 mol% and 30.2 mol%, respectively ( (See Table 2).

Production Examples 2 to 8 (Synthesis of polymers (B-2) to (B-8))
Polymers (B-2) to (B-8) were obtained in the same manner as in Production Example 1 except that the monomers were used in accordance with the formulation described in Table 1. The results of GPC measurement and ¹³ C-NMR analysis are shown in Table 2.

Production Example 9 (Synthesis of polymer (C-1))
As shown in Table 1, 16.4 g (975 mmol) of the compound (M-1), 5.73 g (244 mmol) of the compound (M-4) and 21.74 g (975 mmol) of the compound (M-7) were converted into 2-butanone. After dissolving in 100 g, 2.01 g of dimethyl 2,2′-azobis (2-methylpropionate) was added to prepare a monomer solution.
A 500 mL three-necked flask was charged with 50 g of 2-butanone and 6.07 g (244 mmol) of the compound (M-5), purged with nitrogen gas for 30 minutes, and then heated to 80 ° C. with stirring. Next, the monomer solution was dropped over 3 hours using a dropping funnel. The polymerization reaction was carried out for 6 hours with the start of dropping as the polymerization start time. After the completion of the polymerization, the polymerization solution was cooled to 30 ° C. or lower by water cooling.
Next, the polymerization solution was put into 1,000 g of methanol, and a polymer (white powder) was precipitated and separated by filtration. Thereafter, the collected white powder was dispersed in 200 g of methanol and washed in the form of a slurry. The operation of washing the white powder was performed twice. The recovered polymer was vacuum dried at 60 ° C. for 17 hours. The yield of the polymer (C-1) was 39 g, and the yield was 78%. Mw = 6100 and Mw / Mn = 1.4 were obtained by GPC measurement of the polymer (C-1). In addition, as a result of ¹³ C-NMR analysis, the content ratios of the repeating units derived from the compound (M-1), the compound (M-4), the compound (M-5), and the compound (M-7) were 42 respectively. And 2 mol%, 8.1 mol%, 8.4 mol%, and 41.3 mol% (see Table 2).

2. Production and Evaluation of Radiation Sensitive Resin Composition for Immersion Exposure The raw material components of the composition are shown below.
2-1. Compound [A]
The following compounds (A-1) to (A-3) were used.

2-2. Acid diffusion control agent [D]
The following compound (N-tert-butoxycarbonyl-4-hydroxypiperidine) was used.

2-3. Solvent [E]
(1) E-1
Propylene glycol monomethyl ether acetate was used.
(2) E-2
Cyclohexanone was used.

Example 1
9.9 parts of compound (A-1), 5 parts of polymer (B-1), 100 parts of polymer (C-1), 1.5 parts of acid diffusion controller, and solvent (E-1) 1,800 parts and 770 parts of solvent (E-2) were mixed to produce a radiation sensitive resin composition (composition solution) for immersion exposure (see Table 3).

Examples 2-12 and Comparative Examples 1-4
A radiation-sensitive resin composition for immersion exposure (composition solution) was produced in the same manner as in Example 1 except that the raw material components were used in accordance with the formulation described in Table 3 (see Table 3).

About each composition, the following items were evaluated. These results are shown in Table 4.
(1) Elution amount of compound [A] As shown in FIG. 1, hexamethyldisilazane (HMDS) treatment (100 ° C.) in advance with a coater / developer “CLEAN TRACK ACT8” (model name, manufactured by Tokyo Electron). , 60 seconds), a silicon rubber sheet 2 (made by Kureha Elastomer Co., Ltd., thickness: 1.0 mm, shape) in which a central portion is cut into a circular shape with a diameter of 11.3 cm at the center on an 8-inch silicon wafer 1 : Square with a side of 30 cm) (reference numeral 11 in FIG. 1 indicates a hexamethyldisilazane-treated layer). Next, 10 mL of ultrapure water 3 was filled in the hollowed portion at the center of the silicon rubber sheet 2 using a 10 mL hole pipette.
Next, a radiation sensitive resin for immersion exposure is formed on the surface of the lower antireflection film 41 of the silicon wafer 4 on which a lower antireflection film (trade name “ARC29A”, manufactured by Brewer Science) 41 having a film thickness of 77 nm is previously formed. The composition was spin coated with the above coater / developer. Thereafter, the photoresist film 42 having a film thickness of 110 nm was formed by baking at 120 ° C. for 60 seconds. Then, as shown in FIG. 2, the silicon wafer with the photoresist film is made of silicon so that the surface of the photoresist film 42 comes into contact with the ultrapure water 3 and the ultrapure water 3 does not leak from the silicon rubber sheet 2. It was placed on the rubber sheet 2. Next, after maintaining the state for 10 seconds, the silicon wafer 4 was removed, and the ultrapure water 3 was collected with a glass syringe, which was used as a sample for analysis. The recovery rate of ultrapure water 3 was 95% or more.

The collected ultrapure water was subjected to liquid chromatography mass spectrometry (LC-MS). And the elution amount of compound [A] was calculated | required in the following ways.
The analytical apparatus is “SERIES1100” (model name) manufactured by AGILENT as the LC section, and Perceptive Biosystems, Inc. as the MS section. “Mariner” (model name) manufactured by the company was used. The measurement conditions are as follows.
By this measurement, an anion of compound [A] in ultrapure water was obtained from a calibration curve prepared using each peak intensity, which was previously determined from 1 mass ppb, 10 mass ppb and 100 mass ppb aqueous solution of compound [A]. The peak intensity of the part was determined, and the elution amount was derived. The case where the elution amount is 5.0 × 10 ⁻¹² mol / (cm ² · sec) or more is “bad”, and the case where the elution amount is less than 5.0 × 10 ⁻¹² mol / (cm ² · sec) It was determined as “good”.

[Measurement condition]
Column: One “CAPCELL PAK MG” (trade name, manufactured by Shiseido Co., Ltd.) Eluent: Water / methanol (mass ratio 3/7) with 0.1% formic acid added Flow rate: 0.2 mL / min Measurement temperature : 35 ° C

(2) Receding contact angle The receding contact angle was measured by using a contact angle meter (trade name “DSA-10”) manufactured by KRUS to form a photoresist film with a radiation-sensitive resin composition for immersion exposure. After preparing the substrate (wafer), the receding contact angle was measured immediately by the following procedure under the conditions of a temperature of 23 ° C., a humidity of 45% and atmospheric pressure. The photoresist film is a radiation-sensitive resin composition for immersion exposure on a 12-inch silicon wafer on which a lower antireflection film (“ARC66”, manufactured by Nissan Chemical Industries, Ltd.) is previously formed by “CLEAN TRACK ACT12”. Is a film obtained by forming a film with a thickness of 110 nm using, and then soft baking (SB) the film at 120 ° C. for 60 seconds.

  First, the wafer stage position of the contact angle meter is adjusted, and the substrate is set on the adjusted stage. Next, water is injected into the needle, and the position of the needle is finely adjusted to an initial position where water droplets can be formed on the set substrate. Thereafter, water is discharged from the needle to form a 25 μL water droplet on the substrate. The needle is once withdrawn from the water droplet, and the needle is pulled down to the initial position again and placed in the water droplet. Subsequently, a water droplet is sucked with a needle at a speed of 10 μL / min for 90 seconds, and at the same time, the contact angle between the liquid surface and the substrate is measured once per second (90 times in total). Among these, the average value for the contact angle for 20 seconds from the time when the measured value of the contact angle was stabilized was calculated as the receding contact angle.

(3) Development defects A radiation-sensitive resin composition for immersion exposure was used on a 12-inch silicon wafer on which a lower antireflection film (“ARC66”, manufactured by Nissan Chemical Industries, Ltd.) was previously formed by “CLEAN TRACK ACT12”. Then, a film having a thickness of 110 nm was formed, and then this film was soft baked (SB) at 120 ° C. for 60 seconds. Next, the coating film was rinsed with pure water for 90 seconds. Next, this coating film was passed through a mask pattern using an ArF excimer laser immersion exposure apparatus (“NSR S306C”, manufactured by NIKON) under the conditions of NA = 0.75, σ = 0.85, 1 / 2Annular. And exposed. After the exposure, the substrate was rinsed again with pure water for 90 seconds, and post-baked (PEB) at 100 ° C. for 60 seconds. Thereafter, the resist film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 30 seconds, washed with water, and dried to form a positive resist pattern. At this time, the exposure amount for forming a hole pattern having a width of 1,000 nm was determined as the optimum exposure amount. A hole pattern having a width of 1000 nm was formed on the entire surface of the wafer with this optimum exposure amount, and a defect inspection wafer was obtained. Note that a scanning electron microscope (“S-9380”, manufactured by Hitachi High-Technologies Corporation) was used for length measurement.

Thereafter, the number of defects on the defect inspection wafer was measured using “KLA2351” manufactured by KLA-Tencor. Furthermore, the defects measured by “KLA2351” were observed using a scanning electron microscope (“S-9380”, manufactured by Hitachi High-Technologies Corporation), and the defects determined to be derived from the coating and the foreign matters derived from the outside Classified. After classification, the total number of defects (number of defects) determined to be derived from the coating was obtained. And it evaluated by the following reference | standard.
×: The number of defects is 500 / wafer or more Δ: The number of defects is 100 / wafer or more and less than 500 wafers ○: The number of defects is less than 100 / wafer

(4) Rinse defect A film formed of a radiation-sensitive resin composition for immersion exposure on a 12-inch silicon wafer on which a lower antireflection film (“ARC66”, manufactured by Nissan Chemical Industries, Ltd.) was previously formed by “CLEAN TRACK ACT12”. A film having a thickness of 110 nm was formed, and then the film was soft baked (SB) at 120 ° C. for 60 seconds. Next, the wafer was rinsed with pure water for 15 seconds and dried by shaking off the liquid at 2,000 rpm. This was used as a rinse defect evaluation wafer.

Thereafter, the number of defects on the rinse defect evaluation wafer was measured using “KLA2810” manufactured by KLA-Tencor. Furthermore, the defects measured by “KLA2810” were classified into those determined to be derived from the coating and those derived from the outside. After classification, the total number of defects (number of defects) determined to be derived from the coating was obtained. And it evaluated by the following reference | standard.
×: The number of defects is 500 / wafer or more Δ: The number of defects is 100 / wafer or more and less than 500 wafers ○: The number of defects is less than 100 / wafer

  The radiation-sensitive resin composition for immersion exposure according to the present invention can be used in a lithography process using deep ultraviolet rays, X-rays, electron beams or the like as a light source. In particular, it can be suitably used as a composition for forming a photoresist film used for immersion exposure.

  DESCRIPTION OF SYMBOLS 1; Silicon wafer, 11; Hexamethyldisilazane processing layer, 2; Silicon rubber sheet, 3; Ultrapure water, 4; Silicon wafer, 41; Antireflection film, 42;

Claims (5)

[A] A compound represented by the following general formula (1), [B] a polymer containing 5 mass% or more of fluorine atoms, and [C] an acid-dissociable group and containing less than 5 mass% of fluorine atoms A radiation-sensitive resin composition for immersion exposure, comprising a polymer.

(In the formula, R ¹ is independently of each other a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxyl group having 1 to 10 carbon atoms, carbon, A linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms, or a linear, branched or cyclic alkanesulfonyl group having 1 to 10 carbon atoms, and R ² is a carbon atom independently of each other. the number 1 to 10 linear or branched alkyl group, a phenyl group which may have a substituent or substituents naphthyl group which may have a, or the number of carbon two R ² are bonded to each other Is a group that forms a divalent group of 2 to 10 and may have a substituent, X ⁻ is an anion, k is an integer of 0 to 2, and r ₁ is 1 to 8. is an integer, _{r 2} is an integer of 0-8.)   2. The immersion exposure according to claim 1, wherein the content of the compound [A] is 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the polymer [B] and the polymer [C]. Radiation sensitive resin composition.   The radiation sensitive resin composition for immersion exposure according to claim 1 or 2, wherein the content of the polymer [B] is 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer [C]. . The liquid immersion according to any one of claims 1 to 3, wherein the polymer [B] has a repeating unit represented by the following general formula (2) or a repeating unit represented by the following general formula (3). Radiation sensitive resin composition for exposure.

(Wherein R ³ is a hydrogen atom, a methyl group or a trifluoromethyl group, and R ⁴ is a linear or branched group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. An alkyl group, or an alicyclic hydrocarbon group having 4 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or a derivative group thereof.

(In the formula, n is an integer of 1 to 3, R ⁵ is a hydrogen atom, a methyl group or a trifluoromethyl group, and R ⁶ is a single bond or (n + 1) valence, 1 to 10, a straight-chain, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group, R ⁷ is a single bond or divalent, straight chain having 1 to 20 carbon atoms. A linear, branched or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group, and G ¹ represents —CHF—, —CF ₂ —, or a linear or branched fluoro having 2 to 20 carbon atoms. An alkylene group, G ² is a single bond or —CO—, and R ⁸ is independently a hydrogen atom or an acid dissociable group.   A step of forming a photoresist film on a substrate using the radiation-sensitive resin composition for immersion exposure according to any one of claims 1 to 4, and a liquid for immersion exposure on the photoresist film. And a step of immersion exposure of the photoresist film through the immersion exposure liquid, and a step of developing the photoresist film subjected to immersion exposure to form a resist pattern. A resist pattern forming method.

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