JP2010271686A - Radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition which is a material for resists having excellent resolution, etc. <P>SOLUTION: The radiation-sensitive resin composition comprises (A) a compound represented by general formula (1): X<SP>+</SP>Z<SP>-</SP>(X<SP>+</SP>is a cation represented by general formula (1-1) or (1-2), and Z<SP>-</SP>is an anion such as OH<SP>-</SP>), (B) a resin comprising repeating units represented by general formula (2) and repeating units represented by general formula (3), and (C) a radiation-sensitive acid generator. In the general formulae (1-1), (1-2), (2) and (3), R<SP>2</SP>-R<SP>7</SP>are H or the like; R<SP>8</SP>is an alicyclic hydrocarbon group or the like; A is a single bond or the like; and R<SP>9</SP>is a monovalent organic group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition used in the production of semiconductors such as ICs, the production of circuit boards such as liquid crystals and thermal heads, and other processes using photolithography technology. More specifically, the present invention relates to a radiation-sensitive resin composition used in a photolithography technique using an exposure light source having a wavelength of 220 nm or less, such as an ArF excimer laser or an electron beam.

  Conventionally, a photolithography technique using a chemically amplified radiation-sensitive resin composition has been used in the manufacture of semiconductors such as ICs and the manufacture of circuit boards such as liquid crystals and thermal heads. And this chemically amplified radiation sensitive resin composition is irradiated with radiation such as far ultraviolet light represented by KrF excimer laser or ArF excimer laser, so that a portion (exposed portion) irradiated with radiation is irradiated. It is a composition for forming a resist pattern on a substrate by generating an acid and changing the dissolution rate of an exposed area and an unexposed area in a developer by a reaction using this acid as a catalyst.

  In recent years, a short-wavelength light source such as an ArF excimer laser (wavelength: 193 nm) has been used for the purpose of forming a finer resist pattern among radiations such as far ultraviolet light. And when using an ArF excimer laser, the radiation sensitive resin composition suitable for ArF excimer laser, ie, the radiation sensitive resin composition containing the compound which has an aromatic ring which shows a big absorption in the wavelength range of ArF excimer laser Things are used. As such a radiation sensitive resin composition, for example, one containing a resin having an alicyclic hydrocarbon skeleton is known. Moreover, what contains the repeating unit which has a lactone skeleton, for example as a resin which has the said alicyclic hydrocarbon skeleton has been reported (for example, refer patent documents 1-4). It has been reported that the performance as a resist, specifically, the resolution performance is remarkably improved by containing such a repeating unit.

  Specifically, Patent Documents 1 and 2 describe a radiation-sensitive resin composition using a resin containing a repeating unit having a mevalonic lactone skeleton or a γ-butyrolactone skeleton. Patent Documents 3 and 4 describe a radiation-sensitive resin composition using a resin containing a repeating unit having an alicyclic lactone skeleton.

  However, in a lithography process (a step using a photolithography technique), it is required to form a finer resist pattern (for example, a fine resist pattern having a line width of about 45 nm). In order to achieve the formation of such a fine resist pattern, recently, at the time of exposure, a liquid high refractive index medium such as pure water or a fluorine-based inert liquid is interposed between the lens and the resist film to emit radiation. An irradiation method, that is, a method called an immersion exposure (liquid immersion lithography) method has been reported.

JP 2001-109154 A JP 2002-308866 A JP 2002-371114 A JP 2003-270787 A

  By using the immersion exposure method, the resist pattern can be miniaturized even with the compositions described in Patent Documents 1 to 4, but resolution performance, low line width roughness (Line Width Roughness, hereinafter) , “LWR” in some cases), it is very difficult to satisfy each performance such as pattern formability and pattern collapse resistance. Therefore, development of a material (radiation sensitive resin composition) that satisfies these various required performances is required.

  The present invention has been made in order to solve the above-described problems of the prior art, and in addition to excellent resolution performance, the LWR is small, and the chemical amplification type is excellent in pattern formability and pattern collapse resistance. It aims at providing the radiation sensitive resin composition which is a material of a resist.

  The present invention provides the following radiation-sensitive resin composition.

[1] (A) a compound represented by the following general formula (1), (B) a repeating unit represented by the following general formula (2), and a repeating unit represented by the following general formula (3) The radiation sensitive resin composition containing resin which has and (C) radiation sensitive acid generator.
X ⁺ Z ^- ··· (1)
(However, in the general formula (1), X ⁺ is a cation represented by the following general formula (1-1) or (1-2). Z ⁻ is OH ^{− or} a general formula (1-3). ) An anion represented by R ¹ —COO ^— or an anion represented by general formula (1-4) R ¹ —SO ₃ ^— (provided that the above general formulas (1-3) and (1-4) And R ¹ is an optionally substituted alkyl group, alicyclic hydrocarbon group or aryl group))

（但し、前記一般式（１−１）中、Ｒ^２〜Ｒ^４は、相互に独立に、水素原子、アルキル基、アルコキシル基、水酸基、またはハロゲン原子であり、前記一般式（１−２）中、Ｒ^５およびＲ^６は、相互に独立に、水素原子、アルキル基、アルコキシル基、水酸基、またはハロゲン原子である）

(However, in said general formula (1-1), R < ² > -R < ⁴ > is a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom mutually independently, and said general formula (1-2) R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom)

（但し、前記一般式（２）および（３）中、Ｒ^７は、相互に独立に、水素原子またはメチル基である。前記一般式（２）中、各Ｒ^８は、相互に独立に、炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体、または、炭素数１〜４の直鎖状若しくは分岐状のアルキル基であって、複数のＲ^８の少なくとも一つが前記脂環式炭化水素基またはその誘導体であるか、或いは、いずれか２つのＲ^８が相互に結合して、それぞれが結合する炭素原子とともに炭素数４〜２０の２価の脂環式炭化水素基またはその誘導体を形成し、残りの１つのＲ^８が炭素数１〜４の直鎖状若しくは分岐状のアルキル基または炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体である。前記一般式（３）中、Ａは、単結合または炭素数１〜４の２価の炭化水素基であり、Ｒ^９は、ラクトン環構造を有する１価の有機基である）

(In the general formula (2) and (3), R ⁷ are independently of each other, is a hydrogen atom or a methyl group. In formula (2), each R ⁸ is, independently of each other, A monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, wherein at least one of a plurality of R ⁸ is the above-mentioned fat. A cyclic hydrocarbon group or a derivative thereof, or any two R ⁸ 's bonded to each other, and each of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atom to which each is bonded, or The derivative is formed, and the remaining one R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof. In the general formula (3), A is a single bond or 2 having 1 to 4 carbon atoms. A hydrocarbon group, R ⁹ is a monovalent organic group having a lactone ring structure)

[2] The radiation-sensitive resin composition according to [1], wherein Z ⁻ in the general formula (1) is an anion represented by the following formula (1a) or an anion represented by the following formula (1b). object.

[3] The above [1] or [2], wherein the repeating unit represented by the general formula (2) is at least one selected from the group consisting of the following general formulas (2-1) to (2-8) The radiation sensitive resin composition described in 1.

（但し、前記一般式（２−１）〜（２−８）中、Ｒ^１０は、相互に独立に、水素原子またはメチル基である。Ｒ^１１は、相互に独立に、炭素数１〜４の直鎖状若しくは分岐状のアルキル基または炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体である）

(In the general formula ^{(2-1) ~ (2-8),} R 10 are independently of each other, ^{.R 11} is a hydrogen atom or a methyl group, independently of each other, 1 to 4 carbon atoms A linear or branched alkyl group or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof)

[4] The repeating unit represented by the general formula (3) is at least one of a repeating unit represented by the following general formula (3-1) and a repeating unit represented by the following general formula (3-2). The radiation sensitive resin composition according to any one of the above [1] to [3].

（但し、前記一般式（３−１）および（３−２）中、Ｒ^１２は、相互に独立に、水素原子またはメチル基である）

(In the general formulas (3-1) and (3-2), R ¹² is independently a hydrogen atom or a methyl group)

  The radiation-sensitive resin composition of the present invention has an effect that it is a chemically amplified resist material having a small LWR and an excellent resistance to pattern formation and pattern collapse in addition to excellent resolution performance.

  Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to the following embodiment. That is, it is understood that modifications and improvements as appropriate to the following embodiments are also within the scope of the present invention based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should be.

[1] Radiation sensitive resin composition:
The radiation sensitive resin composition of the present invention comprises (A) a compound represented by the following general formula (1) (hereinafter sometimes referred to as “compound (A)”), and (B) the following general formula (2). ) (Hereinafter sometimes referred to as “repeat unit (2)”) and a repeat unit represented by the following general formula (3) (hereinafter referred to as “repeat unit (3)”) A resin (which may be referred to as “resin (B)” hereinafter) and (C) a radiation sensitive acid generator (hereinafter referred to as “acid generator (C)”). And containing.

X ⁺ Z ^- ··· (1)
(However, in the general formula (1), X ⁺ is a cation represented by the following general formula (1-1) or (1-2). Z ⁻ is OH ^{− or} a general formula (1-3). ) An anion represented by R ¹ —COO ^— or an anion represented by general formula (1-4) R ¹ —SO ₃ ^— (provided that the above general formulas (1-3) and (1-4) And R ¹ is an optionally substituted alkyl group, alicyclic hydrocarbon group or aryl group))

（但し、前記一般式（１−１）中、Ｒ^２〜Ｒ^４は、相互に独立に、水素原子、アルキル基、アルコキシル基、水酸基、またはハロゲン原子であり、前記一般式（１−２）中、Ｒ^５およびＲ^６は、相互に独立に、水素原子、アルキル基、アルコキシル基、水酸基、またはハロゲン原子である）

(However, in said general formula (1-1), R < ² > -R < ⁴ > is a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom mutually independently, and said general formula (1-2) R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom)

（但し、前記一般式（２）および（３）中、Ｒ^７は、相互に独立に、水素原子またはメチル基である。前記一般式（２）中、各Ｒ^８は、相互に独立に、炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体、または、炭素数１〜４の直鎖状若しくは分岐状のアルキル基であって、複数のＲ^８の少なくとも一つが前記脂環式炭化水素基またはその誘導体であるか、或いは、いずれか２つのＲ^８が相互に結合して、それぞれが結合する炭素原子とともに炭素数４〜２０の２価の脂環式炭化水素基またはその誘導体を形成し、残りの１つのＲ^８が炭素数１〜４の直鎖状若しくは分岐状のアルキル基または炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体である。前記一般式（３）中、Ａは、単結合または炭素数１〜４の２価の炭化水素基であり、Ｒ^９は、ラクトン環構造を有する１価の有機基である）

(In the general formula (2) and (3), R ⁷ are independently of each other, is a hydrogen atom or a methyl group. In formula (2), each R ⁸ is, independently of each other, A monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, wherein at least one of a plurality of R ⁸ is the above-mentioned fat. A cyclic hydrocarbon group or a derivative thereof, or any two R ⁸ 's bonded to each other, and each of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atom to which each is bonded, or The derivative is formed, and the remaining one R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof. In the general formula (3), A is a single bond or 2 having 1 to 4 carbon atoms. A hydrocarbon group, R ⁹ is a monovalent organic group having a lactone ring structure)

  Such a radiation-sensitive resin composition can form a chemically amplified resist (resist film) having low LWR and excellent pattern formability and pattern collapse resistance in addition to excellent resolution performance. it can.

  The radiation-sensitive resin composition of the present invention can be used in a lithography process using an ArF excimer laser as a light source, and is used as a material for a chemically amplified resist capable of forming a fine pattern having a line width of 90 nm or less. be able to. Furthermore, the radiation-sensitive resin composition of the present invention can be used in the immersion exposure process, and even when used in the immersion exposure process, it has excellent performance (resolution performance, LWR, pattern formability). , And pattern collapse resistance) can be formed.

[1-1] Compound (A):
The compound (A) is used as an acid diffusion controlling agent that decomposes upon exposure and loses acid diffusion controllability. By containing this compound (A), the acid diffuses in the exposed area, and the acid diffusion is controlled in the unexposed area, so that the contrast between the exposed area and the unexposed area is excellent (that is, the exposed area and the unexposed area). Therefore, among the above effects of the present invention, good LWR, pattern formability, and pattern collapse resistance are achieved.

[1-1-1] X ⁺ :
X ⁺ in the general formula (1) is a cation represented by the general formula (1-1) or (1-2) as described above. R ^{2 to} R ⁴ in the general formula (1-1) are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom, and among these, the compound (A) of A hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom are preferred because of the effect of reducing the solubility in the developer. R ⁵ and R ⁶ in the general formula (1-2) are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom. Among these, a hydrogen atom, an alkyl group, A halogen atom is preferred.

[1-1-2] Z ⁻ :
Z ⁻ in the general formula (1) is represented by OH ⁻ , an anion represented by the general formula (1-3) R ¹ —COO ^— , or a general formula (1-4) R ¹ —SO ₃ ^—. An anion. However, R ¹ in the general formulas (1-3) and (1-4) is an optionally substituted alkyl group, alicyclic hydrocarbon group or aryl group, and among these, the compound (A) Therefore, an alicyclic hydrocarbon group or an aryl group is preferable because of the effect of reducing the solubility in a developer.

  Examples of the optionally substituted alkyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. C1-C4 hydroxyalkyl groups such as butyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n- C1-C4 alkoxyl groups such as butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group; cyano group; cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl Examples include groups having one or more substituents such as C2-C5 cyanoalkyl groups such as groups. Kill. Among these, a hydroxymethyl group, a cyano group, and a cyanomethyl group are preferable.

  Examples of the optionally substituted alicyclic hydrocarbon group include cycloalkane skeletons such as hydroxycyclopentane, hydroxycyclohexane, and cyclohexanone; 1,7,7-trimethylbicyclo [2.2.1] heptane-2- Examples thereof include monovalent groups derived from alicyclic hydrocarbons such as a bridged alicyclic skeleton such as on (camphor). Among these, a group derived from 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one is preferable.

  Examples of the optionally substituted aryl group include a phenyl group, a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylcyclohexyl group. These compounds are substituted with a hydroxyl group, a cyano group, or the like. Can be mentioned. Among these, a phenyl group, a benzyl group, and a phenylcyclohexyl group are preferable.

Z ⁻ in the general formula (1) is an anion represented by the following formula (1a) (that is, an anion represented by the general formula (1-3) in which R ¹ is a phenyl group) or the following formula: An anion represented by (1b) (that is, R ¹ is a group derived from 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one, represented by general formula (1-4)) An anion).

  The compound (A) is represented by the general formula (1), and specifically, is a sulfonium salt compound or an iodonium salt compound that satisfies the above conditions.

  Examples of the sulfonium salt compound include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenylsulfonium acetate, diphenyl-4- Examples thereof include hydroxyphenylsulfonium salicylate, triphenylsulfonium 10-camphor sulfonate, 4-t-butoxyphenyl diphenylsulfonium 10-camphor sulfonate, and the like. In addition, these sulfonium salt compounds can be used individually by 1 type or in combination of 2 or more types.

  Examples of the iodonium salt compound include bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butylphenyl-4-hydroxyphenyliodonium hydroxide, 4-t-butylphenyl-4-hydroxy Phenyliodonium acetate, 4-t-butylphenyl-4-hydroxyphenyliodonium salicylate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium 10-camphor And the like can be given sulfonates. In addition, these iodonium salt compounds can be used individually by 1 type or in combination of 2 or more types.

  The compounding amount of the compound (A) is preferably 0.5 to 8.0 parts by mass and more preferably 1.0 to 5.0 parts by mass with respect to 100 parts by mass of the resin (B). . If the blending amount is less than 0.5 parts by mass, the acid diffusion may not be controlled and the acid may be diffused in the unexposed area. On the other hand, if it exceeds 8.0 parts by mass, the resulting resist pattern may be scummed or skirted, or the resist pattern may be tapered.

[1-2] Resin (B):
The resin (B) has a repeating unit represented by the general formula (2) and a repeating unit represented by the general formula (3). That is, this resin (B) contains an acid dissociable group and becomes alkali-soluble by dissociation of this acid dissociable group.

[1-2-1] Repeating unit (2):
R ⁷ in the general formula (2) is independently a hydrogen atom or a methyl group, and among these, a methyl group is preferable. In the general formula (2), the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms of R ⁸ preferably has 5 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms. preferable. Examples of such monovalent alicyclic hydrocarbon groups are derived from alicyclic hydrocarbons such as norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. The group to do can be mentioned. Among these, groups derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane, and cyclohexane, or those obtained by substituting these groups with alkyl groups are preferable. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, and 1 -A methylpropyl group, a t-butyl group, etc. can be mentioned. Among these, a methyl group and an ethyl group are preferable.

In addition, “a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed by any two R ^{8 s} bonded to each other and bonded to each other” has 5 to 15 carbon atoms. It is preferable that it has 6 to 10 carbon atoms. Examples of such monovalent alicyclic hydrocarbon groups are derived from alicyclic hydrocarbons such as norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. A group having a carbon number of 1 to 1 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc. And a group substituted with one or more of 4 linear, branched, or cyclic alkyl groups. Among these, groups derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane, and cyclohexane, and those obtained by substituting these groups with alkyl groups are preferable. Further, among the remaining R ⁸ , examples of the linear or branched alkyl group having 1 to 4 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 -Methylpropyl group, 1-methylpropyl group, t-butyl group and the like can be mentioned. Among these, a methyl group and an ethyl group are preferable, and among the remaining R ⁸ , the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms is preferably 4 to 10 carbon atoms, and 5 to 5 carbon atoms. More preferably, it is 8. Examples of such a monovalent alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  The repeating unit (2) is preferably at least one repeating unit selected from the group consisting of the following general formulas (2-1) to (2-8).

（但し、前記一般式（２−１）〜（２−８）中、Ｒ^１０は、相互に独立に、水素原子またはメチル基である。Ｒ^１１は、相互に独立に、炭素数１〜４の直鎖状若しくは分岐状のアルキル基または炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体である）

(In the general formula ^{(2-1) ~ (2-8),} R 10 are independently of each other, ^{.R 11} is a hydrogen atom or a methyl group, independently of each other, 1 to 4 carbon atoms A linear or branched alkyl group or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof)

R ¹⁰ in the general formulas (2-1) to (2-8) is independently a hydrogen atom or a methyl group, and among these, a methyl group is preferable.

The linear or branched alkyl group having 1 to 4 carbon atoms and the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms of R ¹¹ are each a straight chain having 1 to 4 carbon atoms of R ⁸ described above. The same as the chain or branched alkyl group and the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms are preferable.

  The content ratio of the repeating unit (2) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, more preferably 40 to 60 mol%, based on all repeating units in the resin (B). % Is particularly preferred. If the content is less than 20 mol%, poor resolution may occur. On the other hand, if it exceeds 80 mol%, a resist pattern may not be formed.

[1-2-2] Repeating unit (3):
A in the general formula (3) is a single bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. Examples of the divalent hydrocarbon group having 1 to 4 carbon atoms include a methylene group and an ethylene group. Is preferred. R ⁹ is a monovalent organic group having a lactone ring structure, preferably having a lactone ring structure, preferably a monovalent organic group having 4 to 15 carbon atoms, having a lactone ring structure, and having a carbon number More preferably, it is a 4-12 monovalent organic group.

Examples of the monovalent organic group include (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl ester group, (meth) acrylic group. Acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl ester group, (meth) acrylic acid-5-oxo-4-oxa- Tricyclo [5.2.1.0 ^3,8 ] dec-2-yl ester group, (meth) acrylic acid-10-methoxycarbonyl-5-oxo-4-oxa-tricyclo [5.2.1.0 ^{3 , 8} ] Nona-2-yl ester group, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl ester group, (meth) acrylic acid-4-methoxy Carbonyl-6-oxo-7-oxa Bicyclo [3.2.1] oct-2-yl ester group, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl ester group, (meth) acrylic Acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl ester group,

  (Meth) acrylic acid-2-oxotetrahydropyran-4-yl ester group, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl ester group, (meth) acrylic acid-4-ethyl- 2-oxotetrahydropyran-4-yl ester group, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl ester group, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl ester group (Meth) acrylic acid-2,2-dimethyl-5-oxotetrahydrofuran-3-yl ester group, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-3-yl ester group, (meth) Acrylic acid-2-oxotetrahydrofuran-3-yl ester group, (meth) acrylic acid-4,4-dimethyl Ru-2-oxotetrahydrofuran-3-yl ester group, (meth) acrylic acid-5,5-dimethyl-2-oxotetrahydrofuran-3-yl ester group, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl Ester group, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl ester group, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl ester group, (meth) acrylic acid Examples include -4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl ester group.

  The repeating unit represented by the general formula (3) is at least one of a repeating unit represented by the following general formula (3-1) and a repeating unit represented by the following general formula (3-2). preferable.

（但し、前記一般式（３−１）および（３−２）中、Ｒ^１２は、相互に独立に、水素原子またはメチル基である）

(In the general formulas (3-1) and (3-2), R ¹² is independently a hydrogen atom or a methyl group)

  It is preferable that the content rate of a repeating unit (3) is 20-80 mol% with respect to all the repeating units in resin (B), and it is still more preferable that it is 40-60 mol%. There exists a possibility that the board | substrate adhesiveness of resin (B) may fall that the said content rate is less than 20 mol%. On the other hand, if it exceeds 80 mol%, the resolution may deteriorate (decrease).

[1-2-3] Other repeating units:
The resin (B) can further contain other repeating units in addition to the repeating unit (2) and the repeating unit (3). Examples of other repeating units include a repeating unit having an acidic group.

  Here, the acidic group of the repeating unit having an acidic group means a polar functional group having affinity with an alkaline aqueous solution, for example, a hydroxyethyl group, a 2-methyl-2-hydroxyethyl group, a phenolic hydroxyl group, a carboxyl group. Groups, sulfonic acid groups and the like. Among these, a phenolic hydroxyl group and a carboxyl group are preferable because the effect of improving the solubility in an alkaline aqueous solution is high.

  Resin (B) uses, for example, a monomer component, a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, and the presence of a chain transfer agent if necessary. Then, it can be produced by polymerization in an appropriate solvent.

  Examples of the solvent used for polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, norbornane. Cycloalkanes such as benzene, toluene, xylene, ethylbenzene, cumene and other aromatic hydrocarbons; chlorobutanes, bromohexanes, dichloroethanes, halogenated hydrocarbons such as hexamethylene dibromide, chlorobenzene; ethyl acetate, Saturated carboxylic acid esters such as n-butyl acetate, i-butyl acetate, methyl propionate, and propylene glycol monomethyl ether acetate; alkyl lactones such as γ-butyrolactone; and amines such as tetrahydrofuran, dimethoxyethanes, diethoxyethanes, etc. Alkyls such as 2-butanone, 2-heptanone and methyl isobutyl ketone; cycloalkyl ketones such as cyclohexanone; 2-propanol, 1-butanol, 4-methyl-2-pentanol, propylene glycol monomethyl ether, etc. And the like. These solvents can be used singly or in combination of two or more.

  The reaction temperature in the polymerization is preferably 40 to 120 ° C, and more preferably 50 to 100 ° C. The reaction time is preferably 1 to 48 hours, and more preferably 1 to 24 hours.

  Resin (B) has few impurities such as halogen and metal, and residual monomer and oligomer components are not more than predetermined values, for example, the content analyzed by liquid chromatography (HPLC) is 0.1% by mass. preferable. By reducing impurities, etc., in addition to further improving the sensitivity, resolution, process stability, pattern shape (pattern formability), etc. as a resist, a resist with less change over time in liquid foreign matter, sensitivity, etc. is formed. be able to.

  Examples of the method for purifying the resin (B) include the following methods. First, as a method for removing impurities such as the metal described above, there is a method of adsorbing a metal in a resin solution using a zeta potential filter. There is also a method of removing the metal in a chelated state by washing the resin solution with an acidic aqueous solution such as oxalic acid or sulfonic acid.

  As a method for removing the residual monomer or oligomer component below the specified value, a liquid-liquid extraction method that removes the residual monomer or oligomer component by combining water washing or an appropriate solvent, a specific molecular weight or less. Refining method that removes residual monomers by coagulating resin in poor solvent by dripping resin solution into poor solvent by dripping resin solution into poor solvent There are purification methods in a solid state such as washing the filtered resin slurry with a poor solvent. These methods can also be combined. Moreover, the poor solvent used for the reprecipitation method can be appropriately selected depending on the physical properties of the resin to be purified.

  The resin (B) has a polystyrene-reduced weight average molecular weight (hereinafter sometimes referred to as “Mw”) by gel permeation chromatography (GPC), preferably 1,000 to 300,000, and 2,000. Is more preferably from 100,000 to 100,000, and particularly preferably from 3,000 to 50,000. If the Mw of the resin (B) is less than 1,000, the heat resistance as a resist may be reduced. On the other hand, if it exceeds 300,000, developability as a resist may be lowered.

  Further, the ratio (Mw / Mn) between the Mw of the resin (B) and the polystyrene-equivalent number average molecular weight (hereinafter sometimes referred to as “Mn”) by gel permeation chromatography (GPC) is 1 to 5. It is preferable that it is 1-3. In addition, resin (B) can be used individually by 1 type or 2 types or more.

[1-3] (C) Radiation sensitive acid generator:
The (C) radiation-sensitive acid generator (acid generator (C)) used in the present invention has an action of decomposing upon exposure to radiation to generate an acid. When this acid generator (C) is contained, an acid is generated by exposure, the acid dissociable group is dissociated, the exposed portion of the resist becomes alkali-soluble, and a resist pattern can be formed.

  The acid generator (C) is not particularly limited as long as it has the above action, but is preferably a compound having a structure represented by the following general formula (4).

However, the above general formula (4), R ¹³ is a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight or branched Or a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms. R ¹⁴ is a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxyl group, or a linear, branched or cyclic alkanesulfonyl group having 1 to 10 carbon atoms.

R ¹⁵ is independently a linear or branched alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted naphthyl group, or Two R ¹⁵ may be bonded to each other to form a divalent group having 2 to 10 carbon atoms. In addition, the formed bivalent group may be substituted. k is an integer of 0 to 2, Y ⁻ represents a general formula: R ¹⁶ C _n F _2n SO ₃ ^— (in the above general formula, R ¹⁶ is a fluorine atom or an optionally substituted carbon atom having 1 to 12 carbon atoms. And n is an integer of 1 to 10). Moreover, q is an integer of 0-10.

In the general formula (4), “a divalent group having 2 to 10 carbon atoms formed by bonding two R ¹⁵ to each other” means a 5-membered ring or a 6-membered ring together with the sulfur atom in the general formula (4). A group that forms a ring is preferable, and a group that forms a 5-membered ring (that is, a tetrahydrothiophene ring) is more preferable.

Examples of the substituent for the divalent group include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxyl group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. As the R ¹⁵ in the formula (4), a methyl group, an ethyl group, a phenyl group, a 4-methoxyphenyl group, a 1-naphthyl group, with two R ¹⁵ bond to a sulfur atom together tetrahydrothiophene ring structure A divalent group that forms is preferred.

  Examples of the cation moiety in the general formula (4) include triphenylsulfonium cation, tri-1-naphthylsulfonium cation, tri-tert-butylphenylsulfonium cation, 4-fluorophenyl-diphenylsulfonium cation, and di-4-fluorophenyl. -Phenylsulfonium cation, tri-4-fluorophenylsulfonium cation, 4-cyclohexylphenyl-diphenylsulfonium cation, 4-methanesulfonylphenyl-diphenylsulfonium cation, 4-cyclohexanesulfonyl-diphenylsulfonium cation, 1-naphthyldimethylsulfonium cation, 1 -Naphthyl diethylsulfonium cation, 1- (4-hydroxynaphthyl) dimethylsulfonium cation, 1- 4-methylnaphthyl) dimethylsulfonium cation, 1- (4-methylnaphthyl) diethylsulfonium cation, 1- (4-cyanonaphthyl) dimethylsulfonium cation, 1- (4-cyanonaphthyl) diethylsulfonium cation, 1- (3 5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium cation, 1- (4-methoxynaphthyl) tetrahydrothiophenium cation, 1- (4-ethoxynaphthyl) tetrahydrothiophenium cation, 1- (4-n- Propoxynaphthyl) tetrahydrothiophenium cation, 1- (4-n-butoxynaphthyl) tetrahydrothiophenium cation, 2- (7-methoxynaphthyl) tetrahydrothiophenium cation, 2- (7-ethoxynaphthyl) teto Hydro thiophenium cation, 2- (7-n- propoxy-naphthyl) tetrahydrothiophenium cation, 2- (7-n- butoxynaphthyl) can be exemplified tetrahydrothiophenium cation, or the like.

The “C _n F _2n ⁻ ” group in the anion represented by Y ⁻ in the general formula (4) (general formula: R ¹⁶ C _n F _2n SO ₃ ⁻ ) is a perfluoroalkylene group having n carbon atoms. However, the perfluoroalkylene group may be linear or branched. Note that n is preferably 1, 2, 4, or 8. Examples of the hydrocarbon group substituted carbon atoms and optionally 1 to 12 represented by R ^16, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a bridged alicyclic hydrocarbon group.

  Examples of the anion moiety in the general formula (4) include trifluoromethanesulfonate anion, nonafluoro-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 like. In addition, the compound which has a structure represented by General formula (4) can be used individually by 1 type or 2 types or more.

  In addition to the compound having the structure represented by the general formula (4) as the acid generator (C), the radiation sensitive resin composition of the present invention can also use other acid generators. Examples of other acid generators include onium salt compounds (excluding compound (A)), halogen-containing compounds (excluding compound (A)), diazoketone compounds, sulfone compounds, and sulfonic acid compounds.

  Examples of other acid generators include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, and diphenyliodonium 2-bicyclo [2.2.1] hepta. 2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2 -Te La tetrafluoroethane sulfonate, cyclohexyl 2-oxo-cyclohexyl methyl trifluoromethanesulfonate, dicyclohexyl-2-oxo-cyclohexyl trifluoromethanesulfonate,

  2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept- 5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, 2-bicyclo [2.2.1] hepta 2-yl-1,1,2,2-tetrafluoroethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N- (trifluoromethanesulfonyloxy) succinimide, N- (Nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro -N-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, 1,8-naphthalenedicarbon Examples thereof include acid imide trifluoromethanesulfonate. These other acid generators can be used alone or in combination of two or more.

  In addition, as an acid generator (C), it is also preferable to use together the compound which has a structure represented by the said General formula (4), and another acid generator. When other acid generators are used in combination, the use ratio of the other acid generators is 80% by mass with respect to the total amount of the compound having the structure represented by the general formula (4) and the other acid generators. Or less, more preferably 60% by mass or less.

  The compounding amount of the acid generator (C) is 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin (B) from the viewpoint of ensuring the sensitivity and developability as a resist. Preferably, it is 0.1-20 mass parts. There exists a possibility that a sensitivity and developability may fall that the said compounding quantity is less than 0.1 mass part. On the other hand, if it exceeds 30 parts by mass, the transparency to radiation is lowered, and it may be difficult to obtain a rectangular resist pattern.

[1-4] Other components:
The radiation-sensitive resin composition of the present invention can further contain other components in addition to the compound (A), the resin (B), and the acid generator (C) described above.

  Other components include, for example, a nitrogen-containing organic compound, an alicyclic additive having an acid dissociable group (excluding the resin (B)), an alicyclic additive having no acid dissociable group, a surfactant, Examples thereof include a sensitizer, an antihalation agent, an adhesion assistant, a storage stabilizer, and an antifoaming agent.

  The nitrogen-containing organic compound is a component having an action of controlling a diffusion phenomenon in the resist of an acid generated from the acid generator by exposure and suppressing an undesirable chemical reaction in a region other than the exposed portion. By blending such a nitrogen-containing organic compound, the storage stability of the resist agent is improved, the resolution of the resist is further improved, and due to fluctuations in the holding time (PED) from exposure to heat treatment after exposure. A change in the line width of the resist pattern can be suppressed, and a radiation-sensitive resin composition having extremely excellent process stability can be obtained.

  Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (5) (hereinafter sometimes referred to as “nitrogen-containing compound (I)”), a compound having two nitrogen atoms in the same molecule ( Hereinafter, it may be referred to as “nitrogen-containing compound (II)”), a polyamino compound having three or more nitrogen atoms in the same molecule and a polymer thereof (hereinafter collectively referred to as “nitrogen-containing compound (III)”) Amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.

（但し、一般式（５）中、Ｒ^１７は、相互に独立に、水素原子、置換されていてもよい直鎖状、分岐状若しくは環状のアルキル基、アリール基、またはアラルキル基である）

(In the general formula (5), R ¹⁷ are each independently a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group.)

  Examples of the nitrogen-containing compound (I) include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n- Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Di (cyclo) 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, cyclohexyl Tri (cyclo) alkylamines such as dimethylamine, methyldicyclohexylamine and 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 And aromatic amines such as 2,6-diisopropylaniline.

  Examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenylether. 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-methyl ester Benzene], 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 nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, and the like.

  Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt- Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)-( -)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxypiperidine Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonyl Perazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′- Diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonylhexamethylenediamine,

  N, N′-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl- 1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N′-di -T-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, N In addition to Nt-butoxycarbonyl group-containing amino compounds such as -t-butoxycarbonylpyrrolidine, formamide, N Methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, isocyanuric acid tris (2 -Hydroxyethyl) and the like.

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea. Etc.

  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- Imidazoles such as methyl-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, Gin, pyrazole, 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 can be mentioned.

  The compounding amount of the nitrogen-containing organic compound is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less with respect to 100 parts by mass of the resin (B). preferable. If the amount is more than 15 parts by mass, the sensitivity as a resist and the developability of the exposed part may be deteriorated. If the amount of the nitrogen-containing organic compound is less than 0.001 part by mass, the pattern shape and dimensional fidelity as a resist may be lowered depending on the process conditions.

  Next, an alicyclic additive having an acid dissociable group or an alicyclic additive having no acid dissociable group is a component that further improves dry etching resistance, pattern shape, adhesion to a substrate, and the like. It is.

  Examples of the alicyclic additives include 1-adamantanecarboxylic acid t-butyl, 1-adamantanecarboxylic acid t-butoxycarbonylmethyl, 1-adamantanecarboxylic acid α-butyrolactone ester, 1,3-adamantane dicarboxylic acid di-t- Butyl, 1-adamantane acetate t-butyl, 1-adamantane acetate t-butoxycarbonylmethyl, 1,3-adamantanediacetate di-t-butyl, 2,5-dimethyl-2,5-di (adamantylcarbonyloxy) hexane Adamantane derivatives such as;

  Deoxycholate t-butyl, deoxycholate t-butoxycarbonylmethyl, deoxycholate 2-ethoxyethyl, deoxycholate 2-cyclohexyloxyethyl, deoxycholate 3-oxocyclohexyl, deoxycholate tetrahydropyranyl, deoxychol Deoxycholic acid esters such as acid mevalonolactone ester; t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid, 2-cyclohexyloxyethyl lithocholic acid, 3-oxocyclohexyl lithocholic acid, lithol Lithocholic acid esters such as tetrahydropyranyl acid, lithocholic acid mevalonolactone ester; dimethyl adipate, diethyl adipate, dipropyl adipate, di-n-adipate Chill, and the like alkyl carboxylic acid esters such as adipate t- butyl. In addition, the said alicyclic additive can be used individually by 1 type or 2 or more types.

  A surfactant is a component that exhibits an effect of improving coating properties, striation, developability, and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene In addition to nonionic surfactants such as glycol distearate, the following are all trade names: KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Asahi Glass Co., Ltd.), etc. Can do. In addition, the said surfactant can be used individually by 1 type or 2 or more types. It is preferable that the compounding quantity of surfactant is 2 mass parts or less with respect to 100 mass parts of resin (B).

  The sensitizer absorbs radiation energy and transmits the energy to the photoacid generator, thereby increasing the amount of acid generated, thereby improving the apparent sensitivity of the radiation-sensitive resin composition. It has an effect. Examples of the sensitizer include carbazoles, benzophenones, rose bengals, anthracenes, phenols and the like. In addition, the said sensitizer can be used individually by 1 type or 2 or more types. It is preferable that the compounding quantity of a sensitizer is 50 mass parts or less with respect to 100 mass parts of resin (B).

[2] Method for producing radiation-sensitive resin composition:
In the radiation-sensitive resin composition of the present invention, for example, the compound (A), the resin (B), the acid generator (C) and other components have a total solid content concentration of 3 to 50% by mass (preferably 5 to 5%). It can be obtained by dissolving in a solvent so as to be 25% by mass, and then filtering with a filter having a pore size of about 200 nm.

  Examples of the solvent include linear or branched ketones such as 2-pentanone, 2-hexanone, 2-heptanone, and 2-octanone; cyclic ketones such as cyclopentanone and cyclohexanone; propylene glycol monomethyl ether Propylene such as acetate and propylene glycol monoethyl ether acetate, glycol monoalkyl ether acetates; 2-hydroxypropionates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; methyl 3-methoxypropionate, 3 In addition to alkyl 3-alkoxypropionates such as ethyl methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate,

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, n-butyl acetate, methyl pyruvate , Ethyl pyruvate, N-methylpyrrolidone, γ-butyrolactone and the like. In addition, the said solvent can be used individually by 1 type or 2 or more types.

  Among these, at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, γ-butyrolactone, ethyl 2-hydroxypropionate, and ethyl 3-ethoxypropionate is preferable. However, cyclohexanone is an effective solvent from the viewpoint of good solubility, but it is preferable to avoid using it as much as possible in terms of toxicity.

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

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]:
Gel permeation based on monodisperse polystyrene using GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation under the analysis conditions of flow rate 1.0 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. It was measured by chromatography (GPC). Further, the degree of dispersion Mw / Mn was calculated from the measurement results.

[ ¹³ C-NMR analysis]:
The ¹³ C-NMR analysis of each polymer was measured using “JNM-EX270” manufactured by JEOL.

[sensitivity]:
First, on a 12-inch silicon wafer, a lower layer (trade name “ARC66”, manufactured by Brewer Science Co., Ltd.) was spin-coated using a trade name “CLEAN TRACK ACT12” (manufactured by Tokyo Electron), and then at 205 ° C. A coating film having a film thickness of 105 nm was formed by performing PB under the condition of 60 seconds. Next, the radiation sensitive resin composition was spin-coated using the trade name “CLEAN TRACK ACT12”, PB was performed at 110 ° C. for 60 seconds, and then cooled at 23 ° C. for 30 seconds to obtain a film thickness. A 100 nm coating film was formed.

  Next, an ArF immersion exposure apparatus (trade name “NSR-S610C”, manufactured by Nikon Corporation) is used for the formed coating film, and the optical condition of NA: 1.30 is 48 nm line / 2 × 48 nm pitch. Exposure was through a mask of mask size. Then, after performing PEB under the PEB conditions shown in Table 1 on a hot plate with a trade name “CLEAN TRACK LITHIUS PROI (manufactured by Tokyo Electron)”, cooling at 23 ° C. for 30 seconds and using a GP nozzle of the developing cup 2. Paddle development (10 seconds) was performed using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer, and rinsed with ultrapure water. Thereafter, the substrate for evaluation on which a resist pattern was formed was obtained by spin-drying at 2000 rpm for 15 seconds.

When the evaluation substrate was obtained, the exposure amount formed with a resist pattern having a line width of 48 nm and a distance (space) between adjacent lines of 48 nm (line and space is 1: 1) (MJ / cm ² ) was determined as the optimum exposure amount. The optimum exposure amount was evaluated as sensitivity (resolution performance) (shown as “sensitivity” in Table 2). A scanning electron microscope (trade name “CG-4000”, manufactured by Hitachi High-Technologies Corporation) was used for the measurement of the line width and the space distance.

[LWR (Line Roughness Characteristics)]:
A 48 nm line and space pattern resolved at the optimum exposure for the sensitivity evaluation was observed from above the pattern using a scanning electron microscope (trade name “CG-4000”, manufactured by Hitachi High-Technologies Corporation). . The line width (line width) was measured at an arbitrary point, and the variation in the measurement was evaluated at 3σ (nm).

[Minimum dimensions before collapse]:
The exposure was sequentially performed with an exposure amount stepwise larger than the optimum exposure amount for the sensitivity evaluation. At this time, since the line width of the obtained pattern is gradually narrowed, the collapse of the resist pattern is finally observed at the line width corresponding to a certain exposure amount. Therefore, the line width corresponding to the maximum exposure amount at which the resist pattern is not confirmed to be collapsed is defined as the minimum dimension before collapse (nm) and used as an index for pattern collapse resistance. The measurement before the minimum collapse (nm) was performed using a scanning electron microscope (trade name “CG-4000”, manufactured by Hitachi High-Technologies Corporation). Note that the smaller the line width, the better the resist film.

[Pattern shape of pattern]:
The cross-sectional shape of the 48 nm line-and-space pattern of the resist film obtained by the sensitivity evaluation was observed with a scanning electron microscope (trade name “S-4800”) manufactured by Hitachi High-Technologies Corporation. The line width Lb and the line width La at the top of the film were measured. As a result of the measurement, when the value calculated by La / Lb was within the range of 0.9 ≦ La / Lb ≦ 1.1, it was judged as “good”, and when it was outside the range, it was judged as “bad”. In Table 2, it is described as “pattern shape”.

(Synthesis Example 1)
First, 45.22 g (50 mol%) of a compound represented by the following formula (M-1) (compound (M-1)), a compound represented by the following formula (M-2) (compound (M-2)) 7.00 g (10 mol%) and 47.79 g (40 mol%) of a compound represented by the following formula (M-3) (compound (M-3)) were dissolved in 200 g of 2-butanone to obtain a solution. Thereafter, 4.41 g of azobisisobutyronitrile was added to this solution to prepare a monomer solution.

  Next, a 500 mL three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. After purging with nitrogen, the reactor was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped into the three-necked flask over 3 hours using a dropping funnel. A polymerization solution was obtained by carrying out the polymerization reaction 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 and cooled to 30 ° C. or lower, and poured into 2000 g of hexane to precipitate a white substance. The precipitated white substance was filtered off, and the filtered white substance was washed twice with 400 g of hexane. Thereafter, the white substance was again filtered off and dried at 50 ° C. for 17 hours to obtain a white powder (copolymer) (89 g, yield 89%).

This copolymer had a weight average molecular weight (Mw) of 6400, Mw / Mn of 1.47, and as a result of ¹³ C-NMR analysis, the compound (M-1), the compound (M-2) and the compound (M-3) ), The content (mol%) of each repeating unit was 40.3, 10.3, and 39.4 with respect to these totals. Let the copolymer obtained by this synthesis example be resin (B-1) (resin (B)).

(Synthesis Example 2)
First, 34.675 g (40 mol%) of a compound represented by the following formula (M-1) (compound (M-1)), a compound represented by the following formula (M-2) (compound (M-2)) 6.700 g (10 mol%) and 45.83 g (40 mol%) of a compound represented by the following formula (M-3) (compound (M-3)) were dissolved in 200 g of 2-butanone to obtain a dissolved solution. . To the obtained solution, 4.23 g of azobisisobutyronitrile was added to obtain a monomer solution.

  Next, a 1000 mL three-necked flask charged with 12.80 g (10 mol%) of the compound represented by the above formula (M-4) (compound (M-4)) and 100 g of 2-butanone is purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped into the three-necked flask using a dropping funnel over 3 hours. A polymerization solution was obtained by carrying out the polymerization reaction 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 and cooled to 30 ° C. or lower, and poured into 2000 g of methanol to precipitate a white substance. The precipitated white substance was filtered off, and the filtered white substance was washed with 800 g of methanol. Thereafter, the white substance was again filtered off and dried at 50 ° C. for 17 hours to obtain a white powder (copolymer) (66.0 g, yield 66%).

This copolymer has a weight average molecular weight (Mw) of 6800, Mw / Mn of 1.35, and as a result of ¹³ C-NMR analysis, the compound (M-1), the compound (M-2), and the compound (M-3). ) And the content (mol%) of each repeating unit derived from the compound (M-4) was 39.5, 10.0, 9.2, 41.3 with respect to these totals. Let the copolymer obtained by this synthesis example be resin (B-2) (resin (B)).

(Synthesis Example 3)
First, 71.67 g (70 mol%) of a compound represented by the following formula (compound (M-5)) and 28.33 g (30 mol%) of a compound represented by the following formula (compound (M-6)) were converted into 2-butanone. Dissolved in 100 g to obtain a dissolved solution. To the obtained solution, 4.61 g of dimethyl-2,2′-azobisisobutyrate was added to prepare a monomer solution.

  Next, a 500 mL three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. After purging with nitrogen, the reactor was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped into the three-necked flask over 3 hours using a dropping funnel. A polymerization solution was obtained by carrying out the polymerization reaction 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 and cooled to 30 ° C. or lower, and poured into 1000 g of methanol to precipitate a white substance. The precipitated white substance was filtered off, and the filtered white substance was washed twice with 400 g of methanol. Thereafter, the white substance was again filtered off and dried at 50 ° C. for 17 hours to obtain a white powder (copolymer) (68.0 g, yield 68%).

This copolymer has a molecular weight (Mw) of 6000, Mw / Mn of 1.35, and as a result of ¹³ C-NMR analysis, it contains compound (M-5) and each repeating unit derived from compound (M-6). The rate (mol%) was 70.2 and 29.8 based on these totals. Let the copolymer obtained by this synthesis example be resin additive (F-1).

(Synthesis Example 4)
First, 50.4 g (50 mol%) of a compound represented by the following formula (M-3) (compound (M-3)), a compound represented by the following formula (M-5) (compound (M-5)). 12.4 g (15 mol%) and 37.2 g (35 mol%) of a compound represented by the following formula (M-7) (compound (M-7)) were dissolved in 200 g of 2-butanone to obtain a solution. . A monomer solution was obtained by adding 3.72 g of azobisisobutyronitrile to the resulting solution.

  Next, a 1000 mL three-necked flask charged with 100 g of 2-butanone is purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped into the three-necked flask using a dropping funnel over 3 hours. A polymerization solution was obtained by carrying out the polymerization reaction 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 and cooled to 30 ° C. or lower, and poured into 2000 g of methanol to precipitate a white substance. The precipitated white substance was filtered off, and the filtered white substance was washed with 400 g of methanol. Thereafter, the white substance was again filtered off and dried at 50 ° C. for 17 hours to obtain a white powder (copolymer) (70.2 g, yield 70%).

This copolymer has a weight average molecular weight (Mw) of 6400, Mw / Mn of 1.36, and as a result of ¹³ C-NMR analysis, the compound (M-3), the compound (M-5), and the compound (M-7). ), The content (mol%) of each repeating unit was 51.0, 14.8, and 34.2, respectively, with respect to these totals. Let the copolymer obtained by this synthesis example be resin (B-3) (resin (B)).

(Synthesis Example 5)
First, 54.94 g (50 mol%) of a compound represented by the following formula (M-3) (compound (M-3)), a compound represented by the following formula (M-5) (compound (M-5)). 45.06 g (50 mol%) was dissolved in 200 g of 2-butanone to obtain a dissolved solution. 4.06 g of azobisisobutyronitrile was added to the resulting solution to obtain a monomer solution.

  Next, a 1000 mL three-necked flask charged with 100 g of 2-butanone is purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped into the three-necked flask using a dropping funnel over 3 hours. A polymerization solution was obtained by carrying out the polymerization reaction 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 and cooled to 30 ° C. or lower, and poured into 2000 g of methanol to precipitate a white substance. The precipitated white substance was filtered off, and the filtered white substance was washed with 400 g of methanol. Thereafter, the white substance was again filtered off and dried at 50 ° C. for 17 hours to obtain a white powder (copolymer) (72.1 g, yield 72%).

This copolymer has a weight average molecular weight (Mw) of 6600, Mw / Mn of 1.38, and as a result of ¹³ C-NMR analysis, each repeating unit derived from the compound (M-3) and the compound (M-5). The content ratios (mol%) were 50.5 and 49.5, respectively, with respect to these totals. Let the copolymer obtained by this synthesis example be resin (B-4) (resin (B)).

(Synthesis Example 6):
First, 53.0 g (51 mol%) of a compound represented by the following formula (M-3) (compound (M-3)), a compound represented by the following formula (M-5) (compound (M-5)) 39.2 g (46 mol%) and 7.81 g (3 mol%) of a compound represented by the following formula (M-8) (compound (M-8)) were dissolved in 300 g of 2-butanone to obtain a dissolved solution. It was. A monomer solution was obtained by adding 3.84 g of azobisisobutyronitrile to the resulting solution.

  Next, a 1000 mL three-necked flask charged with 100 g of 2-butanone is purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped into the three-necked flask using a dropping funnel over 3 hours. A polymerization solution was obtained by carrying out the polymerization reaction 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 and cooled to 30 ° C. or lower, and poured into 2000 g of methanol to precipitate a white substance. The precipitated white substance was filtered off, and the filtered white substance was washed with 400 g of methanol. Thereafter, the white substance was again filtered off and dried at 50 ° C. for 17 hours to obtain a white powder (copolymer) (68.3 g, yield 68%).

This copolymer has a weight average molecular weight (Mw) of 6100, an Mw / Mn of 1.28, and as a result of ¹³ C-NMR analysis, the compound (M-3), the compound (M-5), and the compound (M-8). ), The content (mol%) of each repeating unit was 50.2, 45.8, and 3.0, respectively. Let the copolymer obtained by this synthesis example be resin (B-5) (resin (B)).

(Synthesis Example 7):
First, a compound represented by the following formula (M-3) (compound (M-3) 20.0 g (20 mol%), a compound represented by the following formula (M-7) (compound (M-7)) 63. .2 g (60 mol%) and 16.8 g (20 mol%) of a compound represented by the following formula (M-9) (compound (M-9)) were dissolved in 200 g of 2-butanone to obtain a dissolved solution. 3.7 g of azobisisobutyronitrile was added to the resulting solution to obtain a monomer solution.

  Next, a 1000 mL three-necked flask charged with 100 g of 2-butanone is purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped into the three-necked flask using a dropping funnel over 3 hours. A polymerization solution was obtained by carrying out the polymerization reaction 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 and cooled to 30 ° C. or lower, and poured into 2000 g of methanol to precipitate a white substance. The precipitated white substance was filtered off, and the filtered white substance was washed with 400 g of methanol. Thereafter, the white substance was again filtered off and dried at 50 ° C. for 17 hours to obtain a white powder (copolymer) (71.2 g, yield 71%).

This copolymer had a weight average molecular weight (Mw) of 6300, an Mw / Mn of 1.31, and as a result of ¹³ C-NMR analysis, the compound (M-3), the compound (M-7), and the compound (M-9). The content (mol%) of each repeating unit derived from (2) was 20.2, 59.8, and 20.0, respectively, with respect to these totals. Let the copolymer obtained by this synthesis example be resin (B-6) (resin (B)).

(Synthesis Example 8):
First, 74.6 g (70 mol%) of a compound represented by the following formula (M-7) (compound (M-7)), a compound represented by the following formula (M-9) (compound (M-9)). 25.4 g (30 mol%) was dissolved in 200 g of 2-butanone to obtain a dissolved solution. 3.7 g of azobisisobutyronitrile was added to the resulting solution to obtain a monomer solution.

  Next, a 1000 mL three-necked flask charged with 100 g of 2-butanone is purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped into the three-necked flask using a dropping funnel over 3 hours. A polymerization solution was obtained by carrying out the polymerization reaction 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 and cooled to 30 ° C. or lower, and poured into 2000 g of methanol to precipitate a white substance. The precipitated white substance was filtered off, and the filtered white substance was washed with 400 g of methanol. Thereafter, the white substance was again filtered off and dried at 50 ° C. for 17 hours to obtain a white powder (copolymer) (68.3 g, yield 68%).

This copolymer has a weight average molecular weight (Mw) of 6200, Mw / Mn of 1.30, and as a result of ¹³ C-NMR analysis, each repeating unit derived from the compound (M-7) and the compound (M-9). The content ratios (mol%) were 70.2 and 29.8, respectively, with respect to these totals. Let the copolymer obtained by this synthesis example be resin (B-7) (resin (B)).

(Synthesis Example 9):
First, 58.3 g (60 mol%) of a compound represented by the following formula (M-4) (compound (M-4)), a compound represented by the following formula (M-10) (compound (M-10)). 41.7 g (40 mol%) was dissolved in 200 g of 2-butanone to obtain a dissolved solution. To the obtained solution, 3.2 g of azobisisobutyronitrile was added to obtain a monomer solution.

  Next, a 1000 mL three-necked flask charged with 100 g of 2-butanone is purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped into the three-necked flask using a dropping funnel over 3 hours. A polymerization solution was obtained by carrying out the polymerization reaction 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 and cooled to 30 ° C. or lower, and poured into 2000 g of methanol to precipitate a white substance. The precipitated white substance was filtered off, and the filtered white substance was washed with 400 g of methanol. Thereafter, the white substance was again filtered off and dried at 50 ° C. for 17 hours to obtain a white powder (copolymer) (68.3 g, yield 68%).

This copolymer has a weight average molecular weight (Mw) of 6500, Mw / Mn of 1.35, and as a result of ¹³ C-NMR analysis, each repeating unit derived from the compound (M-4) and the compound (M-10). The content ratios (mol%) were 60.5 and 39.5, respectively, with respect to these totals. Let the copolymer obtained by this synthesis example be resin (B-8) (resin (B)).

(Synthesis Example 10):
First, 54.2 g (60 mol%) of a compound represented by the following formula (M-11) (compound (M-11)), a compound represented by the following formula (M-12) (compound (M-12)) 28.0 g (25 mol%) and 17.8 g (15 mol%) of a compound represented by the following formula (M-13) (compound (M-13)) were dissolved in 200 g of 2-butanone to obtain a solution. . To the obtained solution, 4.6 g of dimethyl-2,2′-azobisisobutyrate was added to obtain a monomer solution.

  Next, a 1000 mL three-necked flask charged with 100 g of 2-butanone is purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped into the three-necked flask using a dropping funnel over 3 hours. The start of dropping was set as the polymerization start time, and the polymerization reaction was performed for 6 hours to obtain a polymerization solution. After completion of the polymerization, the polymerization solution was cooled with water and cooled to 30 ° C. or less, and poured into a 2000 g methanol / water = 9/1 solution to precipitate a white substance. The precipitated white substance was filtered off, and the filtered white substance was washed with 400 g of methanol. Then, it dried at 50 degreeC for 17 hours, and obtained white powder (copolymer) (72.3g, yield 72%).

This copolymer has a weight average molecular weight (Mw) of 6200, an Mw / Mn of 1.32, and as a result of ¹³ C-NMR analysis, the compound (M-11), the compound (M-12), and the compound (M-13). ), The content (mol%) of each repeating unit was 60.5, 23.3, and 16.2, respectively. Let the copolymer obtained by this synthesis example be a resin additive (F-2).

Example 1
1.78 parts of triphenylsulfonium salicylate (shown as “D-1” in Table 1) as the photodegradable base (compound (A)), 100 parts of resin (B-1) as the resin (B), (C) 5 parts triphenylsulfonium nonafluoro-n-butanesulfonate (shown as “C-1” in Table 1), 3 parts resin additive (F-1), solvent as radiation sensitive acid generator After mixing 1460 parts of propylene glycol monomethyl ether acetate (shown as “G-1” in Table 1) and 626 parts of cyclohexanone (shown as “G-2” in Table 1), the pore size was 0. The mixture was filtered through a 0.05 μm filter to obtain a radiation sensitive resin composition (A-1). Each of the above evaluations was performed on the obtained radiation-sensitive resin composition (A-1) (denoted as “A-1)” in the “Composition” column of Tables 1 and 2).

The radiation sensitive resin composition (A-1) of this example has a sensitivity evaluation (optimum exposure amount) of 22.5 mJ / cm ² and an LWR (line roughness characteristic) evaluation result of 3.6 nm. The evaluation result of the dimension before the minimum collapse was 35 nm, and the evaluation of the cross-sectional shape of the pattern was “good”.

(Examples 2-14, Comparative Examples 1-4)
Except having used the compound shown in Table 1 with the compounding quantity shown in Table 1, it was the same method as Example 1, and the radiation sensitive resin composition (Table 1 of Examples 2-14 and Comparative Examples 1-4) was used. And in Table 2, "A-2" to "A-18" are obtained). And various evaluation was performed about the obtained radiation sensitive resin composition. The evaluation results are shown in Table 2. In Comparative Examples 1 to 4, the trade name “tert-butyl-4-pyrrolidine-1-piperidinecarboxylate” (referred to as “E-1” in Table 1) manufactured by ALDRICH is 0 as the acid diffusion control agent. .472 parts were used.

  In addition, the kind of the radiation sensitive acid generator and photodegradable base which are abbreviated in Table 1 is described below. “C-2” in Table 1 is a compound represented by the following formula (C-2), “C-3” is a compound represented by the following formula (C-3), and “C-4” "Is a compound represented by the following formula (C-4)," C-5 "is a compound represented by the following formula (C-5), and" D-2 "is represented by the following formula (D-2). ).

  As is apparent from Table 2, the radiation sensitive resin compositions of Examples 1 to 14 are superior in resolution performance to the radiation sensitive resin compositions of Comparative Examples 1 to 4, and have a low LWR. It was confirmed that it can be used as a material for a chemically amplified resist having excellent pattern formability and resistance to pattern collapse.

  The radiation sensitive resin composition of the present invention is suitable as a material for forming a resist film used in a photolithography process using, for example, an ArF excimer laser or an electron beam as a light source.

Claims (4)

(A) a compound represented by the following general formula (1);
(B) a resin having a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3);
(C) A radiation sensitive resin composition containing a radiation sensitive acid generator.
X ⁺ Z ^- ··· (1)
(However, in the general formula (1), X ⁺ is a cation represented by the following general formula (1-1) or (1-2). Z ⁻ is OH ^{− or} a general formula (1-3). ) An anion represented by R ¹ —COO ^— or an anion represented by general formula (1-4) R ¹ —SO ₃ ^— (provided that the above general formulas (1-3) and (1-4) And R ¹ is an optionally substituted alkyl group, alicyclic hydrocarbon group or aryl group))

(However, in said general formula (1-1), R < ² > -R < ⁴ > is a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom mutually independently, and said general formula (1-2) R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom)

(In the general formula (2) and (3), R ⁷ are independently of each other, is a hydrogen atom or a methyl group. In formula (2), each R ⁸ is, independently of each other, A monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, wherein at least one of a plurality of R ⁸ is the above-mentioned fat. A cyclic hydrocarbon group or a derivative thereof, or any two R ⁸ 's bonded to each other, and each of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atom to which each is bonded, or The derivative is formed, and the remaining one R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof. In the general formula (3), A is a single bond or 2 having 1 to 4 carbon atoms. A hydrocarbon group, R ⁹ is a monovalent organic group having a lactone ring structure) 2. The radiation-sensitive resin composition according to claim 1, wherein Z ⁻ in the general formula (1) is an anion represented by the following formula (1a) or an anion represented by the following formula (1b).

The radiation sensitivity according to claim 1 or 2, wherein the repeating unit represented by the general formula (2) is at least one selected from the group consisting of the following general formulas (2-1) to (2-8). Resin composition.

(In the general formula ^{(2-1) ~ (2-8),} R 10 are independently of each other, ^{.R 11} is a hydrogen atom or a methyl group, independently of each other, 1 to 4 carbon atoms A linear or branched alkyl group or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof) The repeating unit represented by the general formula (3) is at least one of a repeating unit represented by the following general formula (3-1) and a repeating unit represented by the following general formula (3-2). Item 4. The radiation-sensitive resin composition according to any one of Items 1 to 3.

(In the general formulas (3-1) and (3-2), R ¹² is independently a hydrogen atom or a methyl group)