JP5092986B2 - Polymer, radiation-sensitive composition and monomer - Google Patents

Description

The present invention relates to a polymer, a radiation-sensitive composition and a monomer using the polymer as an acid-dissociable group-containing polymer. More specifically, the present invention relates to various kinds of radiation such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV (extreme) far ultraviolet rays, synchrotron radiation, etc., X-rays, electron beam, etc. The present invention relates to a radiation-sensitive composition, a polymer, and a monomer that are used as a chemically amplified resist suitable for microfabrication.

  Conventionally, in a manufacturing process of a semiconductor device such as an IC or LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line, KrF excimer laser light, and further ArF excimer laser light. Further, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light is also being developed.

  Lithography using an electron beam or EUV light is positioned as a next-generation or next-generation pattern forming technique, and a positive resist with high sensitivity and high resolution is desired. In particular, high sensitivity is a very important issue for shortening the wafer processing time. However, in positive resists for electron beams and EUV, if high sensitivity is sought, not only the resolution will be lowered but also the nano edge roughness will be deteriorated. It is strongly desired. Nano edge roughness is designed when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. This refers to the deviation that occurs between the dimensions and the actual pattern dimensions. Since the deviation from the design dimension is transferred by an etching process using a resist as a mask and the electrical characteristics are deteriorated, the yield is lowered. In particular, in the ultrafine region of 0.25 μm or less, nano edge roughness is an extremely important improvement issue. High sensitivity, high resolution, good pattern shape and good nanoedge roughness are in a trade-off relationship, and it is very important how to satisfy this simultaneously.

Furthermore, in lithography using KrF excimer laser light, it is also important to satisfy high sensitivity, high resolution, good pattern shape, and good nano edge roughness at the same time. is necessary.
As a resist suitable for a lithography process using KrF excimer laser light, electron beam, or EUV light, a chemically amplified resist using an acid-catalyzed reaction is mainly used from the viewpoint of high sensitivity. , A phenolic polymer (hereinafter referred to as “phenolic acid-decomposable polymer”), which is insoluble or hardly soluble in an aqueous alkali solution and becomes soluble in an aqueous alkaline solution by the action of an acid, and an acid A chemically amplified resist composition comprising a generator is effectively used.

  For these positive resists, compounds that generate sulfonic acid upon irradiation with actinic rays or radiation using a phenolic acid-decomposable polymer copolymerized with an acid-decomposable acrylate monomer (hereinafter referred to as “sulfonic acid generator”) There are some known resist compositions containing For example, positive resist compositions disclosed in Patent Documents 1 to 5 can be exemplified.

US Pat. No. 5,561,194 JP 2001-166474 A JP 2001-166478 A JP 2003-107708 A JP 2001-194792 A

  However, in any combination of the positive resist composition etc., high sensitivity, high resolution, good pattern shape, and good nano edge roughness (low roughness) are not satisfied at the same time in the ultrafine region. Is the current situation.

  The present invention has been made in view of the above circumstances, and is effectively sensitive to X-rays such as KrF excimer lasers, ArF excimer lasers, EUV (extreme) deep ultraviolet rays, synchrotron radiation, and electron beams, and nanoedges. To provide a radiation-sensitive composition, a polymer, and a monomer capable of forming a chemically amplified positive resist film having excellent roughness and resolution and capable of forming a fine pattern with high accuracy and stability. Objective.

〔一般式（１）において、Ｒは、それぞれ、置換若しくは非置換の炭素数１〜２０の直鎖状若しくは分岐状の１価のアルキル基、Ｒ^１は水素原子又はメチル基、Ｒ^２は置換若しくは非置換の炭素数１〜２０の直鎖状若しくは分岐状の１価のアルキル基、炭素数３〜２５の脂環式基、又は炭素数６〜２２のアリール基、Ｘは置換若しくは非置換のメチレン基、炭素数２〜２５の置換若しくは非置換の直鎖状若しくは分岐状のアルキレン基、又は炭素数３〜２５の脂環式炭化水素基を表す。〕
［２］前記一般式（１）で表される繰り返し単位が、下記一般式（１−１）で表される繰り返し単位である前記［１］に記載の重合体。

〔一般式（１−１）において、Ｒ^１は水素原子又はメチル基、Ｒ^３は置換若しくは非置換の炭素数１〜８の直鎖状若しくは分岐状の１価のアルキル基、炭素数３〜２５の脂環式基、又は炭素数６〜２２のアリール基を表す。〕
［３］下記一般式（２）で表される繰り返し単位、下記一般式（３）で表される繰り返し単位、及び下記一般式（４）で表される繰り返し単位のうちの少なくとも１種を更に含む前記［１］又は［２］に記載の重合体。

〔一般式（２）において、Ｒ^４は水素原子又はメチル基、Ｒ^５は水素原子又は１価の有機基、ｉは１〜３の整数、ｊは０〜３の整数を表す。〕

〔一般式（３）において、Ｒ^６は水素原子又はメチル基、Ｒ^７は水素原子又は１価の有機基、ｋは１〜３の整数、ｌは０〜３の整数を表す。〕

〔一般式（４）において、Ｒ^８は水素原子又はメチル基、Ｒ^９は水素原子又は１価の有機基、ｍは１〜３の整数、ｎは０〜３の整数を表す。〕
［４］酸解離性基含有重合体（Ａ）と、感放射線性酸発生剤（Ｂ）と、を含有する感放射線性組成物であって、
前記酸解離性基含有重合体（Ａ）が、前記［１］乃至［３］のいずれかに記載の重合体であることを特徴とする感放射線性組成物。
［５］下記一般式（Ｍ−１）で表されることを特徴とする単量体。

〔一般式（Ｍ−１）において、Ｒ^１０は水素原子又はメチル基、Ｒ^１１は置換若しくは非置換の炭素数１〜２０の直鎖状若しくは分岐状の１価のアルキル基、炭素数３〜２５の脂環式基、又は炭素数６〜２２のアリール基、Ｚは置換若しくは非置換のメチレン基、炭素数２〜２５の置換若しくは非置換の直鎖状若しくは分岐状のアルキレン基、又は炭素数３〜２５の脂環式炭化水素基を表す。〕 [1] It includes a repeating unit represented by the following general formula (1) and has a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 3000 to 100,000. To polymer.

[In General Formula (1), R is a substituted or unsubstituted linear or branched monovalent alkyl group having 1 to 20 carbon atoms, R ¹ is a hydrogen atom or a methyl group, and R ² is a substituted group. Or an unsubstituted linear or branched monovalent alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, or an aryl group having 6 to 22 carbon atoms, X is substituted or unsubstituted A methylene group, a substituted or unsubstituted linear or branched alkylene group having 2 to 25 carbon atoms, or an alicyclic hydrocarbon group having 3 to 25 carbon atoms. ]
[2] The polymer according to [1], wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (1-1).

[In General Formula (1-1), R ¹ is a hydrogen atom or a methyl group, R ³ is a substituted or unsubstituted linear or branched monovalent alkyl group having 1 to 8 carbon atoms, 3 to 3 carbon atoms, 25 represents an alicyclic group or an aryl group having 6 to 22 carbon atoms. ]
[3] At least one of a repeating unit represented by the following general formula (2), a repeating unit represented by the following general formula (3), and a repeating unit represented by the following general formula (4) is further added. The polymer according to [1] or [2].

[In General Formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a monovalent organic group, i represents an integer of 1 to 3, and j represents an integer of 0 to 3. ]

[In General Formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a monovalent organic group, k represents an integer of 1 to 3, and l represents an integer of 0 to 3. ]

[In General Formula (4), R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents a hydrogen atom or a monovalent organic group, m represents an integer of 1 to 3, and n represents an integer of 0 to 3. ]
[4] A radiation sensitive composition comprising an acid dissociable group-containing polymer (A) and a radiation sensitive acid generator (B),
The radiation-sensitive composition, wherein the acid dissociable group-containing polymer (A) is the polymer according to any one of [1] to [3].
[5] A monomer represented by the following general formula (M-1).

[In General Formula (M-1), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a substituted or unsubstituted linear or branched monovalent alkyl group having 1 to 20 carbon atoms, and 3 to 3 carbon atoms. 25 alicyclic group, or aryl group having 6 to 22 carbon atoms, Z is a substituted or unsubstituted methylene group, substituted or unsubstituted linear or branched alkylene group having 2 to 25 carbon atoms, or carbon The alicyclic hydrocarbon group of several 3-25 is represented. ]

According to the radiation-sensitive composition of the present invention, KrF excimer laser, ArF excimer laser, EUV and other (ultra) far ultraviolet rays, synchrotron radiation and other X-rays and electron beams are effectively sensitive to nanoedge roughness, and A chemically amplified positive resist film that is excellent in resolution and can form a fine pattern with high accuracy and stability can be formed.
Moreover, the said radiation sensitive composition can be easily obtained by using the polymer of this invention as an acid dissociable group containing polymer.

Hereinafter, the present invention will be described in detail.
[1] Polymer The polymer in the present invention [hereinafter referred to as “polymer (I)”] includes a repeating unit represented by the following general formula (1) [hereinafter referred to as “repeating unit (1)”]. It is characterized by that.
This polymer (I) is a polymer that is insoluble in alkali or hardly soluble in alkali, and becomes easily soluble in alkali by the action of an acid, and is suitably used as an acid-dissociable group-containing polymer in a radiation-sensitive composition. can do.

〔一般式（１）において、Ｒは、それぞれ、置換若しくは非置換の炭素数１〜２０の直鎖状若しくは分岐状の１価のアルキル基、Ｒ^１は水素原子又はメチル基、Ｒ^２は置換若しくは非置換の炭素数１〜２０の直鎖状若しくは分岐状の１価のアルキル基、炭素数３〜２５の脂環式基、又は炭素数６〜２２のアリール基、Ｘは置換若しくは非置換のメチレン基、炭素数２〜２５の置換若しくは非置換の直鎖状若しくは分岐状のアルキレン基、又は炭素数３〜２５の脂環式炭化水素基を表す。〕

[In General Formula (1), R is a substituted or unsubstituted linear or branched monovalent alkyl group having 1 to 20 carbon atoms, R ¹ is a hydrogen atom or a methyl group, and R ² is a substituted group. Or an unsubstituted linear or branched monovalent alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, or an aryl group having 6 to 22 carbon atoms, X is substituted or unsubstituted A methylene group, a substituted or unsubstituted linear or branched alkylene group having 2 to 25 carbon atoms, or an alicyclic hydrocarbon group having 3 to 25 carbon atoms. ]

  Carbon number of the alkyl group in R of the said General formula (1) is 1-20, Preferably it is 1-16, More preferably, it is 1-12, More preferably, it is 1-8. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. In addition, this alkyl group may be linear or branched. Moreover, this alkyl group may be substituted. Specific examples of the substituent include, for example, hydroxyl group, carboxyl group, halogen atom (fluorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group, etc. Can be mentioned. The two Rs may be the same alkyl group or different alkyl groups.

Carbon number of the alkyl group in R < ² > of the said General formula (1) is 1-20, Preferably it is 1-16, More preferably, it is 1-12, More preferably, it is 1-8. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. In addition, this alkyl group may be linear or branched. Moreover, this alkyl group may be substituted. Specific examples of the substituent include, for example, hydroxyl group, carboxyl group, halogen atom (fluorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group, etc. Can be mentioned.

Further, the alicyclic portion in the alicyclic group having 5 to 25 carbon atoms of R ² may be monocyclic or polycyclic. Furthermore, a bridge type may be used. Specific examples of the alicyclic structure include the following structures (a-1) to (a-50).

Moreover, carbon number of the said alicyclic group is 5-25, Preferably it is 6-20, More preferably, it is 7-15.
Among these alicyclic groups, adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group. In particular, a cycloalkyl group having 7 to 15 carbon atoms is preferable.
The alicyclic group may be substituted. Specific examples of the substituent include, for example, hydroxy group, carboxyl group, halogen atom (fluorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group, etc. Can be mentioned.

Specific examples of the R ² aryl group having 6 to 22 carbon atoms include the following structures (x-1) to (x-3). This aryl group may be substituted. Specific examples of the substituent include, for example, methyl group, ethyl group, hydroxy group, carboxyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group) Etc.), alkyloxycarbonyl groups and the like.

As the linear or branched alkylene group having 2 to 25 carbon atoms of X in the general formula (1), for example, a methylene group, an ethylene group, a propylene group and the like are preferable.
Moreover, as an alicyclic structure of a C3-C25 alicyclic hydrocarbon group in said X, the structure of said (a-1)-(a-50) etc. are preferable, for example. Among these, the structure (a-48) is particularly preferable.
Among the X, a methylene group, an ethylene group, a propylene group, and the structure (a-48) are particularly preferable.
The methylene group and alkylene group of X may be substituted. Specific examples of the substituent include, for example, hydroxyl group, carboxyl group, halogen atom (fluorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group, etc. Can be mentioned.

  In the polymer (I) of the present invention, the repeating unit (1) is a repeating unit represented by the following general formula (1-1) [hereinafter referred to as “repeating unit (1-1)”. ].

〔一般式（１−１）において、Ｒ^１は水素原子又はメチル基、Ｒ^３は置換若しくは非置換の炭素数１〜８の直鎖状若しくは分岐状の１価のアルキル基、炭素数３〜２５の脂環式基、又は炭素数６〜２２のアリール基を表す。〕

[In General Formula (1-1), R ¹ is a hydrogen atom or a methyl group, R ³ is a substituted or unsubstituted linear or branched monovalent alkyl group having 1 to 8 carbon atoms, 3 to 3 carbon atoms, 25 represents an alicyclic group or an aryl group having 6 to 22 carbon atoms. ]

Specific examples of the alkyl group in R ³ of the general formula (1-1) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. In addition, this alkyl group may be linear or branched. Moreover, this alkyl group may be substituted. Specific examples of the substituent include, for example, hydroxyl group, carboxyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl Groups and the like.
In addition, the for the alicyclic group having a carbon number of 3-25 in R ^3, it can be directly applied to the description of alicyclic group R ² in the general formula (1).
Furthermore, for the aryl group having 6 to 22 carbon atoms of R ³ , the description of the aryl group of R ² in the general formula (1) can be applied as it is.

  Moreover, the said repeating unit (1) can be obtained by using the compound represented by the following general formula (M-1) as a monomer, for example.

〔一般式（Ｍ−１）において、Ｒ^１０は水素原子又はメチル基、Ｒ^１１は置換若しくは非置換の炭素数１〜２０の直鎖状若しくは分岐状の１価のアルキル基、炭素数３〜２５の脂環式基、又は炭素数６〜２２のアリール基、Ｚは置換若しくは非置換のメチレン基、炭素数２〜２５の置換若しくは非置換の直鎖状若しくは分岐状のアルキレン基、又は炭素数３〜２５の脂環式炭化水素基を表す。〕

[In General Formula (M-1), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a substituted or unsubstituted linear or branched monovalent alkyl group having 1 to 20 carbon atoms, and 3 to 3 carbon atoms. 25 alicyclic group, or aryl group having 6 to 22 carbon atoms, Z is a substituted or unsubstituted methylene group, substituted or unsubstituted linear or branched alkylene group having 2 to 25 carbon atoms, or carbon The alicyclic hydrocarbon group of several 3-25 is represented. ]

For R ¹¹ and Z in the general formula (M-1), the descriptions of R ² and X in the general formula (1) can be applied as they are.

  The monomer represented by the general formula (M-1) is, for example, by synthesizing a tertiary alcohol compound having a urethane bond by a reaction of 3-methyl-1,3-butanediol and cyclohexyl isocyanate, It can manufacture by reaction with the tertiary alcohol compound which has the obtained urethane bond, and methacrylic acid chloride.

  The polymer (I) of the present invention may be composed of only the repeating unit (1). In addition to the repeating unit (1), the repeating unit represented by the following general formula (2) [ Hereinafter, it is referred to as “repeating unit (2)”. ], A repeating unit represented by the following general formula (3) [hereinafter referred to as “repeating unit (3)”. And a repeating unit represented by the following general formula (4) [hereinafter referred to as “repeating unit (4)”. ] May be further included.

〔一般式（２）において、Ｒ^４は水素原子又はメチル基、Ｒ^５は水素原子又は１価の有機基、ｉは１〜３の整数、ｊは０〜３の整数を表す。〕

[In General Formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a monovalent organic group, i represents an integer of 1 to 3, and j represents an integer of 0 to 3. ]

〔一般式（３）において、Ｒ^６は水素原子又はメチル基、Ｒ^７は水素原子又は１価の有機基、ｋは１〜３の整数、ｌは０〜３の整数を表す。〕

[In General Formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a monovalent organic group, k represents an integer of 1 to 3, and l represents an integer of 0 to 3. ]

〔一般式（４）において、Ｒ^８は水素原子又はメチル基、Ｒ^９は水素原子又は１価の有機基、ｍは１〜３の整数、ｎは０〜３の整数を表す。〕

[In General Formula (4), R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents a hydrogen atom or a monovalent organic group, m represents an integer of 1 to 3, and n represents an integer of 0 to 3. ]

Examples of the monovalent organic group represented by R ⁵ in the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, and a 1-methyl group. A linear or branched alkyl group having 1 to 12 carbon atoms such as propyl group and t-butyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methyl Examples thereof include a linear or branched alkoxyl group having 1 to 12 carbon atoms such as a propoxy group, a 1-methylpropoxy group and a t-butoxy group. Among these, a methyl group, an ethyl group, an n-butyl group, and a t-butyl group are preferable.
Moreover, i in General formula (2) is an integer of 1-3, and it is more preferable that it is 1 or 2.
Furthermore, j in General formula (2) is an integer of 0-3, and it is more preferable that it is 0-2.

Specific examples of the repeating unit (2) represented by the general formula (2) include repeating units represented by the following formulas (2-1) to (2-4).
In addition, when repeating unit (2) is contained in polymer (I), this repeating unit (2) may be contained only 1 type and may be contained 2 or more types.

With respect to the monovalent organic group of R ⁷ in the general formula (3), the description regarding the monovalent organic group of R ⁵ can be applied as it is.
Moreover, k in General formula (3) is an integer of 1-3, and it is more preferable that it is 1 or 2.
Furthermore, l in the general formula (3) is an integer of 0 to 3, and is more preferably 0 or 1.

Specific examples of the repeating unit (3) represented by the general formula (3) include repeating units represented by the following formulas (3-1) and (3-2).
In addition, when repeating unit (3) is contained in polymer (I), this repeating unit (3) may be contained only 1 type and may be contained 2 or more types.

Regarding the monovalent organic group of R ⁹ in the general formula (4), the description regarding the monovalent organic group of R ⁵ can be applied as it is.
Moreover, m in General formula (4) is an integer of 1-3, and it is more preferable that it is 1 or 2.
Furthermore, n in the general formula (4) is an integer of 0 to 3, and is more preferably 0 or 1.

Specific examples of the repeating unit (4) represented by the general formula (4) include repeating units represented by the following formulas (4-1) and (4-2).
In addition, when repeating unit (4) is contained in polymer (I), this repeating unit (4) may be contained only 1 type and may be contained 2 or more types.

Each repeating unit represented by the formulas (2-1) to (2-3) can be obtained by using a corresponding hydroxystyrene derivative as a monomer. Furthermore, it can also obtain by using as a monomer the compound from which a hydroxy styrene derivative is obtained by hydrolyzing.
As the monomer used for generating each repeating unit represented by the formulas (2-1) to (2-3), p-acetoxystyrene, p- (1-ethoxyethoxy) styrene, and the like are preferable. . When these monomers are used, each repeating unit represented by the formulas (2-1) to (2-3) can be generated by a side chain hydrolysis reaction after forming a polymer. it can.

Each repeating unit represented by the formulas (2-4), (3-1), (3-2), (4-1) and (4-2) uses a corresponding monomer. Can be obtained.
As a monomer used to generate each repeating unit represented by the formulas (2-4), (3-1), (3-2), (4-1) and (4-2), , P-isopropenylphenol, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like are preferable.

  In addition to the repeating units (1) to (4), the polymer (I) of the present invention is a repeating unit derived from a non-acid dissociable compound (hereinafter also referred to as “repeating unit (5)”), It may further contain a repeating unit derived from an acid dissociable compound (hereinafter also referred to as “repeating unit (6)”).

Examples of the non-acid-dissociable compound include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, isobornyl acrylate, tricyclodecanyl (meth) acrylate, and tetracyclodone. Examples include decenyl (meth) acrylate and a compound represented by the following formula (b-1). Among these, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, tricyclodecanyl acrylate, and a compound represented by the following formula (b-1) are preferable.
In addition, when the said repeating unit (5) is contained in polymer (I), this repeating unit (5) may be contained only 1 type and may be contained 2 or more types.

  Examples of the acid dissociable compound include compounds represented by the following general formulas (c-1) and (c-2).

In the general formulas (c-1) and (c-2), each R ¹² independently represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and each R ¹³ independently represents a carbon number. 4-20 monovalent alicyclic hydrocarbon group or its derivative (s), or a C1-C4 linear or branched alkyl group is represented.

Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms in R ¹³ of the general formulas (c-1) and (c-2) include norbornane, tricyclodecane, tetracyclododecane, adamantane, A group consisting of an alicyclic ring derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane; a group consisting of these alicyclic rings such as a methyl group, an ethyl group, n Of linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as -propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group One or more groups or groups substituted with one or more may be mentioned. Moreover, any two R < ¹³ > may couple | bond together and may form a bivalent alicyclic hydrocarbon group or its derivative with the carbon atom which each has couple | bonded.
Among these alicyclic hydrocarbon groups, a group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane, or a group consisting of these alicyclic rings is described above. A group substituted with an alkyl group is preferred.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in R ¹³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, 2- A methylpropyl group, a 1-methylpropyl group, a t-butyl group, etc. can be mentioned.

  Specific examples of the repeating unit (6) include repeating units represented by the following general formulas (6-1) to (6-8).

〔一般式（６−１）〜（６−８）において、Ｒ^１４は互いに独立に水素原子、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を表し、Ｒ^１５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を表す。〕

In [Formula ^{(6-1) ~ (6-8),} R 14 are independently hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl ^{group, R 15} is 1 to carbon atoms independently of one another 4 linear or branched alkyl groups are represented. ]

  In addition, when the said repeating unit (6) is contained in polymer (I), this repeating unit (6) may be contained only 1 type and may be contained 2 or more types.

The content of the repeating unit (1) in the polymer (I) of the present invention is preferably 1 mol% or more when the total of all repeating units in the polymer (I) is 100 mol%, More preferably, it is 1-90 mol%, More preferably, it is 1-50 mol%. When this content exceeds 90 mol%, when the polymer (I) is used as an acid-dissociable group-containing polymer in the radiation-sensitive composition, there is a possibility that nano edge roughness may be deteriorated.
The total content of the repeating units (2) to (4) is preferably 1 mol% or more when the total of all repeating units in the polymer (I) is 100 mol%. Preferably it is 10-95 mol%, More preferably, it is 30-95 mol%. When the total content exceeds 95 mol%, nano edge roughness may be deteriorated when the polymer (I) is used as an acid-dissociable group-containing polymer in the radiation-sensitive composition.
Furthermore, the total content of the repeating units (1) to (4) is preferably 10 mol% or more when the total of all repeating units in the polymer (I) is 100 mol%. Preferably it is 40-100 mol%, More preferably, it is 50-100 mol%. When the total content is 10 mol% or more, when the polymer (I) is used as an acid-dissociable group-containing polymer in the radiation-sensitive composition, it should have excellent nano edge roughness. Can do.

Moreover, content of the said repeating unit (5) is 60 mol% or less normally, when the sum total of all the repeating units in a polymer (I) is 100 mol%, Preferably it is 0-50 mol%. . When this content is 60 mol% or less, when this polymer (I) is used as an acid-dissociable group-containing polymer in the radiation-sensitive composition, the resolution performance and the performance of nanoedge roughness It can be excellent in balance.
Furthermore, content of the said repeating unit (6) is 70 mol% or less normally, when the sum total of all the repeating units in a polymer (I) is 100 mol%, Preferably it is 0-50 mol%. . When this content is 70 mol% or less, when this polymer (I) is used as an acid-dissociable group-containing polymer in a radiation-sensitive composition, the resolution performance and the performance of nanoedge roughness It can be excellent in balance.
Further, the total content of the repeating units (5) and (6) is 80 mol% or less, preferably 0 to 0 when the total of all repeating units in the polymer (I) is 100 mol%. 60 mol%. When this content is 80 mol% or less, when this polymer (I) is used as an acid-dissociable group-containing polymer in a radiation-sensitive composition, the resolution performance and the performance of nanoedge roughness It can be excellent in balance.

  Although the synthesis method of the polymer (I) in this invention is not specifically limited, For example, it can obtain by well-known radical polymerization or anionic polymerization. Further, the side chain hydroxystyrene unit in the repeating units (2) to (4) is obtained by subjecting the obtained polymer (I) to hydrolysis of an acetoxy group or the like in the presence of a base or acid in an organic solvent. Can be obtained.

  The radical polymerization is carried out, for example, by stirring and heating necessary monomers such as the compound (M-1) in a suitable organic solvent in a nitrogen atmosphere in the presence of a radical polymerization initiator. can do.

Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), and 2,2′-azobis- (4-methoxy). -2,4-dimethylvaleronitrile) 2,2'-azobismethylbutyronitrile, 2,2'-azobiscyclohexanecarbonitrile, cyanomethylethylazoformamide, 2,2'-azobis (2,4-dimethyl) Azo compounds such as methyl propionate) and 2,2'-azobiscyanovaleric acid; benzoyl peroxide, lauroyl peroxide, 1,1'-bis- (t-butylperoxy) cyclohexane, 3,5,5-trimethyl Examples thereof include organic peroxides such as hexanoyl peroxide and t-butylperoxy-2-ethylhexanoate, and hydrogen peroxide.
In this polymerization, a polymerization aid such as 2,2,6,6-tetramethyl-1-piperidinyloxy, iodine, mercaptan, styrene dimer may be added as necessary.

The reaction temperature in the radical polymerization is not particularly limited, and is appropriately selected depending on the type of initiator and the like (for example, 50 to 200 ° C.). In particular, when an azo initiator or a peroxide initiator is used, a temperature at which the half life of the initiator is about 10 minutes to about 30 hours is preferable, and more preferably, the half life of the initiator is about 30 minutes to about 10 hours. Temperature.
The reaction time varies depending on the type of initiator and the reaction temperature, but the reaction time during which 50% or more of the initiator is consumed is desirable, and in many cases is about 0.5 to 24 hours.

  The anionic polymerization is performed, for example, by stirring necessary monomers such as the compound (M-1) in a suitable organic solvent in a nitrogen atmosphere in the presence of an anionic polymerization initiator at a predetermined temperature. It can be carried out by maintaining the above.

  Examples of the anionic polymerization initiator include n-butyl lithium, s-butyl lithium, t-butyl lithium, ethyl lithium, ethyl sodium, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium. Organic alkali metals such as

The reaction temperature in the anionic polymerization is not particularly limited and is appropriately selected depending on the kind of the initiator. In particular, when alkyl lithium is used as an initiator, the temperature is preferably −100 to 50 ° C., more preferably −78 to 30 ° C.
The reaction time varies depending on the type of initiator and the reaction temperature, but the reaction time during which 50% or more of the initiator is consumed is desirable, and in many cases is about 0.5 to 24 hours.

  In the synthesis of the polymer (I), it is possible to carry out a polymerization reaction by heating and cationic polymerization without using a polymerization initiator.

In addition, when a hydroxystyrene unit is introduced by hydrolyzing the side chain of the polymer (I), examples of the acid used for the hydrolysis reaction include p-toluenesulfonic acid and its hydrate, methane Organic acids such as sulfonic acid, trifluoromethanesulfonic acid, malonic acid, oxalic acid, 1,1,1-fluoroacetic acid; inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid; or pyridinium p-toluenesulfonate, ammonium Examples thereof include salts such as p-toluenesulfonate and 4-methylpyridinium p-toluenesulfonate.
Furthermore, examples of the base include inorganic bases such as potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate; organic bases such as triethylamine, N-methyl-2-pyrrolidone, piperidine, and tetramethylammonium hydroxide.

Examples of the organic solvent used for the polymerization or hydrolysis include ketones such as acetone, methyl ethyl ketone, and methyl amyl ketone; ethers such as diethyl ether and tetrahydrofuran (THF); methanol, ethanol, propanol, and the like. Alcohols; aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated alkyls such as chloroform, bromoform, methylene chloride, methylene bromide, and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cellosolves; dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, etc. Protic polar solvents, and the like.
Among these, acetone, methyl amyl ketone, methyl ethyl ketone, tetrahydrofuran, methanol, ethanol, propanol, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.

The polymer (I) has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC) of 3000 to 100,000, more preferably 3000 to 60000, and still more preferably. Is 4000-40000.
Further, the ratio (Mw / Mn) of Mw of the polymer (I) and polystyrene-reduced number average molecular weight (hereinafter also referred to as “Mn”) measured by GPC is usually 1 to 5, more preferably 1 To 3, more preferably 1 to 2.5.

[2] Radiation sensitive composition The radiation sensitive composition of the present invention is characterized by containing an acid dissociable group-containing polymer (A) and a radiation sensitive acid generator (B).

[2-1] Acid-dissociable group-containing polymer The acid-dissociable group-containing polymer is a polymer that is insoluble in alkali or hardly soluble in alkali and easily soluble in alkali by the action of an acid (hereinafter referred to as “polymer”). (A) "). The term “alkali insoluble or alkali insoluble” as used herein refers to the alkali development conditions employed when a resist pattern is formed from a resist film formed from a radiation-sensitive composition containing the polymer (A). Thus, when a 100 nm-thick film using only the polymer (A) is developed instead of the resist film, 50% or more of the initial film thickness of the film remains after development.
Moreover, about this polymer (A), description of the above-mentioned polymer (I) is applicable as it is.

  Since the radiation-sensitive composition of the present invention contains a compound having the acid dissociable group [the polymer (A)], it has excellent sensitivity. From this point of view, this radiation-sensitive composition is sensitive to an electron beam or extreme ultraviolet rays in a lithography process, has low roughness, excellent resolution, and forms a fine pattern with high accuracy and stability. It is possible to form a chemically amplified positive resist film that can be formed.

[2-2] Radiation-sensitive acid generator The acid generator (B) is contained in the radiation-sensitive composition when the radiation-sensitive composition of the present invention is irradiated with an electron beam or radiation in a lithography process. It is a substance that generates acid. And the acid dissociable group in the polymer already mentioned above will dissociate by the action of the acid generated from the acid generator (B).

  The acid generator (B) is, for example, at least one selected from the group consisting of an onium salt, a diazomethane compound, and a sulfonimide compound from the viewpoint of good acid generation efficiency, heat resistance, and the like. preferable. In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.

Examples of the onium salt include iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, pyridinium salt, and the like. Here, specific examples of the onium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium 10-camphorsulfonate, and triphenylsulfonium n-octanesulfonate. , Triphenylsulfonium 4-trifluoromethylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluorobenzenesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0 .1 ^2,5 .1 ^7,10] dodecane-8-yl) ethanesulfonate, triphenylsulfonium 1,1-diphenyl Luolo-2- (bicyclo [2.2.1] heptan-2-yl) ethanesulfonate;

  (4-t-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium perfluoro-n-octanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium 10-camphorsulfonate, (4-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-hydroxyphenyl) diphenyl Sulfonium perfluoro-n-octanesulfonate, (4-hydroxyphenyl) diphenylsulfonium 10-camphorsulfonate DOO, (4-hydroxyphenyl) diphenyl sulfonium n- octane sulfonate,

  Tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, tris (4-methoxyphenyl) sulfonium perfluoro-n-octanesulfonate, tris (4-methoxyphenyl) ) Sulfonium 10-camphorsulfonate, (4-fluorophenyl) diphenylsulfonium trifluoromethanesulfonate, (4-fluorophenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) diphenylsulfonium 10-camphorsulfonate; 4-fluorophenyl) sulfonium trifluoromethanesulfonate, tris (4-fluorophenyl) sulfonium nona Ruoro -n- butane sulfonate, tris (4-fluorophenyl) sulfonium 10-camphorsulfonic full phosphonate, tris (4-fluorophenyl) sulfonium p- toluenesulfonate, tris (4-trifluoromethylphenyl) sulfonium trifluoromethanesulfonate;

  2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 2,4-difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 4-trifluoromethylbenzenesulfonate; Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium n-octanesulfonate,

  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 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium n-octanesulfonate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, (4-methoxyphenyl) phenyliodonium Nonafluoro-n-butanesulfonate, (4-methoxyphenyl) phenyliodonium perfluoro-n-octanesulfonate,

  (4-fluorophenyl) phenyliodonium trifluoromethanesulfonate, (4-fluorophenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) phenyliodonium 10-camphorsulfonate; bis (4-fluorophenyl) iodonium trifluoro Lomethanesulfonate, bis (4-fluorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-fluorophenyl) iodonium 10-camphorsulfonate;

  Bis (4-chlorophenyl) iodonium trifluoromethanesulfonate, bis (4-chlorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-chlorophenyl) iodonium perfluoro-n-octanesulfonate, bis (4-chlorophenyl) iodonium n- Dodecylbenzenesulfonate, bis (4-chlorophenyl) iodonium 10-camphorsulfonate, bis (4-chlorophenyl) iodonium n-octanesulfonate, bis (4-chlorophenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-chlorophenyl) iodonium Perfluorobenzenesulfonate;

  Bis (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, bis (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-trifluoromethylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-trifluoromethylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, bis (4-trifluoromethylphenyl) iodoniumbenzenesulfonate, bis (4-trifluoro Methylphenyl) iodonium 10-camphorsulfonate, bis (4-trifluoromethylphenyl) iodonium n-octanesulfonate, bis (4-trifluoro) B methylphenyl) iodonium 4-trifluoromethyl benzenesulfonate, bis (4-trifluoromethylphenyl) iodonium perfluoro sulfonate;

  Examples include compounds represented by the following formulas (2x-1) to (2x-27).

  Among these onium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 10-camphorsulfonate, (4-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-hydroxy) Phenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) diphenylsulfonium trifluoromethane Sulfonate, (4-fluorophenyl) diphenylsulfonium nonafluoro-n-butyl 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 2,4-difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 4-trifluoromethyl Benzene sulfonate,

Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro- n-butanesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, (4-fluorophenyl) phenyliodonium trifluoromethanesulfonate, (4-fluorophenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4 -Fluorophenyl) phenyliodonium 10-camphorsulfonate, bis (4-fluorophenyl) iodonium Fluoromethanesulfonate, bis (4-fluorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-fluorophenyl) iodonium 10-camphorsulfonate, tris (4-trifluoromethylphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2- (tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecane-8-yl) ethanesulfonate, triphenylsulfonium 1,1-difluoro - 2- (bicyclo [2.2.1] heptan-2-yl) ethanesulfonate; the above formulas (2x-13), (2x-16), (2x-17), (2x-18), (2x-19) ), (2x-20) and (2x-27) are preferred. .

Examples of the diazomethane compound include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, and bis. (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane and the like can be mentioned.
Among these diazomethane compounds, bis (cyclohexylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4] .5] Decan-7-sulfonyl) diazomethane is preferred.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy)-. 7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboximide; N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bishi B [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide, N-[(5-methyl-5-carboxymethylbicyclo [ 2.2.1] heptan-2-yl) sulfonyloxy] succinimide;

  N- (n-octylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octylsulfonyloxy) bicyclo [2.2.1] heptane- 5,6-oxy-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (nonafluoro-n-butylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 Dicarboximide, N- (nonafluoro-n-butylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butylsulfonyl) Oxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide;

  N- (perfluoro-n-octylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octylsulfonyloxy) -7-oxa Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboximide and the like can be mentioned.

  Among these sulfonimide compounds, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide N-[(5-methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide is preferred.

  Moreover, it is preferable that the compounding quantity of an acid generator (B) is 0.1-50 mass parts with respect to 100 mass parts of polymers (A), More preferably, it is 0.5-50 mass parts. . There exists a possibility that a sensitivity and developability may fall that the compounding quantity of this acid generator (B) is less than 0.1 mass part. On the other hand, if the blending amount exceeds 50 parts by mass, the transparency to radiation, pattern shape, heat resistance, etc. may be reduced.

[2-3] Acid Diffusion Control Agent In addition to the polymer (A) and the acid generator (B), the radiation sensitive composition of the present invention includes an acid diffusion control agent (hereinafter referred to as “acid diffusion control agent (C)”. It is preferable to further contain.
The acid diffusion controller (C) controls the diffusion phenomenon in the resist film (resist film) of the acid generated from the acid generator (B) by exposure, and has an action of suppressing undesired chemical reactions in the non-exposed areas. It is an ingredient. By blending such an acid diffusion controller (C), the storage stability of the resulting radiation-sensitive composition is improved, and the resolution of the formed resist film is further improved, and after exposure to after exposure. Thus, a change in the line width of the resist pattern due to fluctuations in the holding time (PED) until the heat treatment can be suppressed, and a radiation-sensitive composition having extremely excellent process stability can be obtained.

As the acid diffusion controller (C), for example, a nitrogen-containing organic compound or a photosensitive basic compound is preferably used.
Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (7) (hereinafter, referred to as “nitrogen-containing compound (i)”), a compound having two nitrogen atoms in the same molecule (hereinafter, “ Nitrogen-containing compound (ii) ”), polyamino compounds and polymers having three or more nitrogen atoms (hereinafter collectively referred to as“ nitrogen-containing compound (iii) ”), amide group-containing compounds, urea compounds, nitrogen-containing compounds Examples include heterocyclic compounds.

〔一般式（７）において、各Ｒ^１６は、相互に独立に、水素原子、直鎖状、分岐状若しくは環状の置換されていてもよいアルキル基、置換されていてもよいアリール基、又は置換されていてもよいアラルキル基を表す。〕

[In General Formula (7), each R ¹⁶ is independently of each other a hydrogen atom, a linear, branched or cyclic alkyl group which may be substituted, an aryl group which may be substituted, or a substituent. Represents an aralkyl group which may be substituted. ]

  Examples of the nitrogen-containing compound (i) include mono- (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; -Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Of di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octyl Amine, tri-n-nonylamine, tri-n-decylamine, cyclohexane Tri (cyclo) alkylamines such as sildimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as triethanolamine; 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 Aromatic amines such as

  Examples of the nitrogen-containing compound (ii) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diamino. Diphenyl 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-amino Phenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methyl Ethyl] 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 are preferable.

  As the nitrogen-containing compound (iii), for example, polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer and the like are preferable.

  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-hydroxy Piperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbo Rupiperazine, 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-phenyl In addition to Nt-butoxycarbonyl group-containing amino compounds such as benzimidazole, 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 are preferable.

  Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butyl. Thiourea and the like are preferable.

  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-phenyl Pyridines such as pyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ′: 6 ′, 2 ″ -terpyridine; piperazine, 1- (2- Piperazines such as (hydroxyethyl) piperazine Pyrazine, 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 are preferable.

  The photosensitive basic compound is a component that decomposes in the exposed region and loses basicity, and remains in the unexposed portion without being decomposed. Since such a photosensitive basic compound can effectively use an acid generated in an exposed portion (that is, an exposed region), compared with a non-photosensitive basic compound, sensitivity can be further improved. .

  The kind of the said photosensitive basic compound is not specifically limited as long as it has the said property. Specifically, for example, compounds represented by the following general formulas (8-1) and (8-2) can be suitably used.

〔一般式（８−１）及び（８−２）において、Ｒ^１７〜Ｒ^２１は、それぞれ、水素原子、ハロゲン原子、置換基を有してもよい炭素数１〜１０のアルキル基、又は置換基を有してもよい脂環式炭化水素基であり、Ｚ⁻は、ＯＨ⁻、Ｒ^２２Ｏ⁻、又はＲ^２２ＣＯＯ⁻であり、Ｒ^２２は１価の有機基である。〕

[In General Formulas (8-1) and (8-2), R ^{17 to} R ²¹ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent. An alicyclic hydrocarbon group which may have a group, Z ⁻ is OH ⁻ , R ²² O ⁻ , or R ²² COO ^— , and R ²² is a monovalent organic group. ]

Examples of the alkyl group having 1 to 10 carbon atoms that may have a substituent of R ^{17 to} R ²¹ in the general formulas (8-1) and (8-2) include a methyl group, an ethyl group, and n- Examples thereof include a butyl group, a tert-butyl group, and a trifluoromethyl group. The alkyl group includes a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), alkyloxycarbonyl group. It may be substituted with a substituent such as (t-butoxycarbonylmethyloxy group and the like).
Moreover, as an alicyclic hydrocarbon group which may have a substituent in said R < ¹⁷ > -R < ²¹ >, the structure of previous general formula (a-1)-(a-50), etc. are mentioned. The alicyclic hydrocarbon group includes a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), It may be substituted with a substituent such as an alkyloxycarbonyl group (such as t-butoxycarbonylmethyloxy group).
Furthermore, as a halogen atom in said R < ¹⁷ > -R < ²¹ >, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

Among these, it is preferable that said R < ¹⁷ > -R < ²¹ > is a hydrogen atom, a tert- butyl group, and a cyclohexyl group. In the formula (8-1), R ^{17 to} R ¹⁹ may all be the same, or part or all may be different. In the formula (8-2), R ²⁰ and R ²¹ may be the same or different.

Each Z ⁻ in the general formulas (8-1) and (8-2) is OH ⁻ , R ²² O ⁻ , or R ²² COO ^— .
Examples of the monovalent organic group for R ²² include an alkyl group which may have a substituent and an aryl group which may have a substituent.
In particular, Z ⁻ is preferably OH ⁻ , CH ₃ COO ⁻ , and compounds (Z-1) to (Z-3) represented by the following formulae.

Further, the specific examples of the photosensitive basic compound is a triphenyl sulfonium compound [compound represented by the general formula (8-1)], the anion (Z ^-) is OH ^-, CH ₃ The thing which is COO < ^- >, the said compound (Z-2) or (Z-3) etc. are mentioned.

  In addition, the said acid diffusion control agent (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, it is preferable that the compounding quantity of an acid diffusion control agent (C) is 15 mass parts or less with respect to 100 mass parts of polymers (A), More preferably, it is 0.001-10 mass parts, More preferably, it is. 0.005 to 5 parts by mass. When the compounding amount of the acid diffusion controller (C) exceeds 15 parts by mass, the sensitivity of the formed resist film and the developability of the exposed part may be deteriorated. On the other hand, if the blending amount is less than 0.001 part by mass, the pattern shape and dimensional fidelity of the formed resist film may be lowered depending on the process conditions.

[2-4] Other components The radiation-sensitive composition of the present invention is obtained by dissolving the polymer (A), the acid generator (B), and the acid diffusion controller (C) in a solvent. Is preferred. That is, it is preferable to further contain a solvent as another component.
Moreover, various additives, such as surfactant, a sensitizer, and an aliphatic additive, can further be mix | blended with the radiation sensitive composition of this invention as other components as needed.

  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. At least one selected from the group consisting of

  The amount of the solvent in the radiation-sensitive composition of the present invention is preferably such that the total solid concentration in the composition is 1 to 70% by mass, more preferably 1 to 25% by mass. More preferably, the amount is 1 to 20% by mass.

Moreover, when using the radiation sensitive composition of this invention, it is preferable that the total solid content concentration is 1-50 mass%, and it is still more preferable that it is 1-25 mass%.
The radiation-sensitive composition of the present invention comprises a polymer (A), an acid generator (B), an acid diffusion controller (C), and other components (excluding the solvent) as required, with a total solid content concentration. Can be prepared by uniformly dissolving in a solvent so that is in the above range. In addition, after preparing in this way, it is preferable to filter with a filter with a pore diameter of about 0.2 μm, for example.

The surfactant is a component having an action of improving coating properties, striations, developability and the like.
Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, and polyethylene glycol dilaurate. In addition to nonionic surfactants such as polyethylene glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck 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 (made by Asahi Glass Co., Ltd.), etc. Can do. These surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.
Moreover, it is preferable that the compounding quantity of surfactant is 0.001-2 mass parts with respect to 100 mass parts of polymers (A).

The sensitizer absorbs radiation energy and transmits the energy to the acid generator (B), thereby increasing the amount of acid produced. The apparent sensitivity of the radiation-sensitive composition It has the effect of improving sensitivity.
Examples of such sensitizers include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like. In addition, these sensitizers may be used individually by 1 type, and may be used in combination of 2 or more type.
Moreover, it is preferable that the compounding quantity of a sensitizer is 0.1-10 mass parts with respect to 100 mass parts of polymers (A).

  Further, by blending a dye or a pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be reduced. Moreover, the adhesiveness of a resist film and a board | substrate can be improved by mix | blending an adhesion aid.

The alicyclic additive is a component having a function of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like.
Examples of such alicyclic additives include 1-adamantanecarboxylic acid, 2-adamantanone, 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-adamantane diacetate di-t-butyl, 2, Adamantane derivatives such as 5-dimethyl-2,5-di (adamantylcarbonyloxy) hexane; t-butyl deoxycholic acid, t-butoxycarbonylmethyl deoxycholic acid, 2-ethoxyethyl deoxycholic acid, 2-deoxycholic acid 2- Cyclohexyloxyethyl, deoxy Deoxycholic acid esters such as 3-oxocyclohexyl cholic acid, tetrahydropyranyl deoxycholic acid, mevalonolactone ester of deoxycholic acid; t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid, Lithocholic acid esters such as 2-cyclohexyloxyethyl lithocholic acid, 3-oxocyclohexyl lithocholic acid, tetrahydropyranyl lithocholic acid, mevalonolactone ester of lithocholic acid; dimethyl adipate, diethyl adipate, dipropyl adipate, din adipate - butyl, alkyl carboxylic acid esters such as adipate t- butyl or 3- [2-hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.1 ^{2, 5} 1 ^7,10 ] dodecane and the like. These alicyclic additives may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, it is preferable that the compounding quantity of an alicyclic additive is 0.5-20 mass parts with respect to 100 mass parts of polymers (A). When the blending amount of the alicyclic additive exceeds 20 parts by mass, the heat resistance of the formed resist film may be lowered.

  Furthermore, examples of additives other than the above include alkali-soluble polymers, low-molecular alkali solubility control agents having an acid-dissociable protective group, antihalation agents, storage stabilizers, antifoaming agents, and the like. .

[3] Method for Forming Resist Pattern The radiation-sensitive composition of the present invention is useful as a material capable of forming a chemically amplified positive resist film.
In the chemical amplification type positive resist film, the acid dissociable group in the polymer is eliminated by the action of the acid generated from the acid generator by exposure, and the polymer becomes alkali-soluble. That is, an alkali-soluble site is generated in the resist film. This alkali-soluble portion is an exposed portion of the resist, and this exposed portion can be dissolved and removed by an alkali developer. In this way, a positive resist pattern having a desired shape can be formed. This will be specifically described below.

  In order to form a resist pattern using the radiation-sensitive composition of the present invention, first, a resist film is formed using the radiation-sensitive composition of the present invention. As the radiation-sensitive composition, for example, as described above, after adjusting the total solid content concentration, a composition filtered with a filter having a pore diameter of about 0.2 μm can be used. A resist film is formed by applying this radiation-sensitive composition onto a substrate such as a silicon wafer or a wafer coated with aluminum by an appropriate application means such as spin coating, cast coating, or roll coating. To do. Thereafter, in some cases, heat treatment (hereinafter referred to as “PB”) may be performed at a temperature of about 70 to 160 ° C. in advance. Next, the resist film is exposed so that a predetermined resist pattern is formed. Examples of radiation that can be used for this exposure include (extreme) far ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), EUV (extreme ultraviolet light, wavelength 13.5 nm, etc.), and synchro Examples include X-rays such as tron radiation, and charged particle beams such as electron beams. Moreover, exposure conditions, such as exposure amount, can be suitably selected according to the compounding composition of a radiation sensitive composition, the kind of additive, etc. This exposure can also be immersion exposure.

  In addition, it is preferable to perform heat processing (henceforth "PEB") after exposure. By this PEB, it is possible to smoothly proceed with elimination of the acid dissociable group of the polymer. Although the heating conditions for PEB can be appropriately selected depending on the composition of the radiation-sensitive composition, it is preferably 30 to 200 ° C, more preferably 50 to 170 ° C.

  In the present invention, in order to maximize the potential of the radiation-sensitive composition, it is used, for example, as disclosed in Japanese Patent Publication No. 6-12452 (Japanese Patent Laid-Open No. 59-93448). An organic or inorganic antireflection film can also be formed on the substrate. Further, in order to prevent the influence of basic impurities contained in the environmental atmosphere, a protective film can be provided on the resist film as disclosed in, for example, JP-A-5-188598. These techniques can be used in combination.

  Next, the exposed resist film is developed to form a predetermined resist pattern. Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine. , Triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- An alkaline aqueous solution in which at least one of alkaline compounds such as [4.3.0] -5-nonene is dissolved is preferable.

  The concentration of the alkaline aqueous solution is preferably 10% by mass or less. When the concentration of the alkaline aqueous solution exceeds 10% by mass, the unexposed area may be dissolved in the developer. Moreover, it is preferable that a developing solution is pH 8-14, More preferably, it is pH 9-14.

  Moreover, an organic solvent can also be added to the developing solution consisting of the alkaline aqueous solution, for example. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, and n-propyl. Alcohols such as alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane Esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone and dimethylformamide. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

The blending amount of the organic solvent is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. When the blending amount of the organic solvent exceeds 100 parts by volume, the developability is lowered, and there is a possibility that the remaining development in the exposed part increases. In addition, an appropriate amount of a surfactant or the like can be added to the developer composed of an alkaline aqueous solution.
In addition, after developing with the developing solution which consists of alkaline aqueous solution, it can also wash with water and can be dried.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, “part” is based on mass unless otherwise specified.

[1] Monomer synthesis
<Example 1>
3-methyl-1,3-butanediol 41.7 g, cyclohexyl isocyanate 25.3 g, and 4-dimethylaminopyridine 1.1 g were dissolved in 100 g of tetrahydrofuran (THF) and reacted at 50 ° C. for 6 hours. After completion of the reaction, ethyl acetate was added to the reaction mother liquor, the organic layer was washed with water, and the organic layer was distilled off under reduced pressure to recover a white solid. The resulting solid was recrystallized using a mixed solvent of ethyl acetate / n-hexane = 1/1 (volume ratio) to obtain a tertiary alcohol compound having a urethane bond (yield: 60% ).
Next, 36.4 g of the resulting tertiary alcohol compound having a urethane bond, 20.0 g of methacrylic acid chloride, and 21.4 g of 1,4-diazabicyclo [2.2.2] octane were dissolved in THF. The reaction was performed at 4 ° C. for 4 hours. After completion of the reaction, ethyl acetate was added to the reaction mother liquor, and the organic layer was washed with water. Then, the target compound was obtained by performing silica gel column chromatography using a mixed solvent of ethyl acetate / n-hexane = 1/1 (volume ratio) as a developing solvent (yield 70%).

The structure of the obtained compound was confirmed by ¹ H-NMR (manufactured by JEOL Ltd., model number “JNM-ECA-400 type”). The results are shown below.
¹ H-NMR (400 MHz, solvent DMSO-d ₆ , internal standard TMS): δ (ppm) = 0.80 to 2.10 (m, 18.0 H), 3.00 to 3.20 (1.0 H) 3.80 to 4.10 (t, 2.0H), 5.60 to 6.00 (2.0H), 6.50 to 7.00 (1.0H)

From the result of the ¹ H-NMR, it was found that the structure of the obtained compound was represented by the following formula. Hereinafter, this compound is referred to as “compound (M-1-1)”.

[2] Polymer synthesis
<Example 2>
112 g of p-acetoxystyrene, 88 g of the compound (M-1-1) obtained in Example 1, 6 g of azobisisobutyronitrile (hereinafter referred to as “AIBN”), and 2 g of t-dodecyl mercaptan were mixed with propylene glycol monomethyl. After dissolving in 200 g of ether, polymerization was carried out for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution was dropped into 10000 g of n-hexane to coagulate and purify the resulting copolymer. Next, 150 g of propylene glycol monomethyl ether was added to the copolymer again, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the obtained copolymer was dissolved in 220 g of acetone, then dropped into 2000 g of water to solidify, and the resulting white powder was filtered and filtered at 50 ° C. under reduced pressure. Dried overnight.
As for the obtained copolymer, Mw is 15000, Mw / Mn is 2.3, and as a result of ¹³ C-NMR analysis, the content ratio of each repeating unit derived from p-hydroxystyrene and the compound (M-1-1) It was a copolymer having a (molar ratio) of 70:30. Hereinafter, this copolymer is referred to as “polymer (A-1)”.

  In this example, Mw and Mn were measured using GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column temperature. : Measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analysis conditions of 40 ° C. Further, the degree of dispersion Mw / Mn was calculated from the measurement results.

[3] Preparation of radiation-sensitive composition
<Examples 3 to 5>
(A) A polymer, (B) an acid generator, (C) an acid diffusion controller, and (D) a solvent were mixed in the amounts shown in Table 1, and the resulting mixture was mixed with a membrane filter having a pore size of 200 nm. By filtering, each composition solution (radiation sensitive composition) of Examples 3-5 was prepared.
Details of the (A) polymer, (B) acid generator, (C) acid diffusion controller and (D) solvent are shown below.
(A) Polymer (A-1): The polymer (A-1) obtained in Example 2
(B) Acid generator (B-1): Triphenylsulfonium trifluoromethanesulfonate (B-2): Triphenylsulfonium 1,1-difluoro-2- (bicyclo [2.2.1] heptan-2-yl) Ethanesulfonate (B-3): Compound represented by the following formula (2x-16)

(C) Acid diffusion controller (C-1): Tri-n-octylamine (C-2): Triphenylsulfonium salicylate (C-3): Nt-butoxycarbonyl-2-phenylbenzimidazole D) Solvent (D-1): Ethyl lactate (D-2): Propylene glycol monomethyl ether acetate

<Comparative Examples 1-3>
(1) Synthesis of polymer (A-2) 124 g of p-acetoxystyrene, 76 g of a compound (monomer) represented by the following formula (M-2), 7 g of AIBN and 2 g of t-dodecyl mercaptan were mixed with propylene glycol monomethyl ether. After dissolving in 200 g, polymerization was performed for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution was dropped into 10000 g of n-hexane to coagulate and purify the resulting copolymer. Next, 150 g of propylene glycol monomethyl ether was added to the copolymer again, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting copolymer was dissolved in 200 g of acetone, then dropped into 2000 g of water to solidify, and the resulting white powder was filtered and filtered at 50 ° C. under reduced pressure. Dried overnight.
As for the obtained copolymer, Mw is 15000, Mw / Mn is 2.1, and as a result of ¹³ C-NMR analysis, the content ratio (moles) of each repeating unit derived from p-hydroxystyrene and the compound (M-2) The ratio was a copolymer of 70:30. Hereinafter, this copolymer is referred to as “polymer (A-2)”.

(2) Preparation of radiation-sensitive composition In the amounts shown in Table 1, (A) polymer [the polymer (A-2)], (B) acid generator, (C) acid diffusion controller, (D) Solvents were mixed, and the resulting mixed solution was filtered through a membrane filter having a pore size of 200 nm to prepare composition solutions (radiation sensitive compositions) of Comparative Examples 1 to 3.
The details of (B) acid generator, (C) acid diffusion controller and (D) solvent are the above-mentioned (B-1) to (B-3), (C-1) to (C-3). , (D-1) and (D-2).

[4] Evaluation of radiation-sensitive composition Each composition solution (Examples 3 to 5 and Comparative Examples 1 to 3) on a silicon wafer in a clean track ACT-8 manufactured by Tokyo Electron Ltd. After spin coating, PB (heat treatment) was performed under the conditions shown in Table 2 to form a resist (radiation sensitive composition) film having a film thickness of 60 nm. Thereafter, the resist film was irradiated with an electron beam using a simple electron beam drawing apparatus (manufactured by Hitachi, Ltd., model “HL800D”, output: 50 KeV, current density: 5.0 amperes / cm ² ). After the electron beam irradiation, PEB was performed under the conditions shown in Table 2. Thereafter, using a 2.38% tetramethylammonium hydroxide aqueous solution, development was carried out at 23 ° C. for 1 minute by the paddle method, followed by washing with pure water and drying to form a resist pattern. The resist thus formed was evaluated in the following manner. Table 2 shows the evaluation results of the radiation-sensitive compositions of Examples 3 to 5 and Comparative Examples 1 to 3.

(1) Sensitivity (L / S)
A pattern [a so-called line-and-space pattern (1L1S)] composed of a line portion having a line width of 150 nm and a space portion (that is, a groove) having an interval of 150 nm formed by adjacent line portions is 1: 1. The exposure amount formed in the line width was set as the optimum exposure amount, and the sensitivity was evaluated based on the optimum exposure amount.
FIG. 1 is a plan view schematically showing the shape of a line and space pattern. FIG. 2 is a cross-sectional view schematically showing the shape of the line and space pattern. However, the unevenness shown in FIGS. 1 and 2 is exaggerated from the actual.

(2) Nano-edge roughness A line-and-space pattern (1L1S) with a designed line width of 150 nm is scanned with a scanning electron microscope for semiconductors (high resolution FEB measuring device, trade name “S-9220”, manufactured by Hitachi, Ltd.) ). With respect to the observed shape, as shown in FIG. 1 and FIG. 2, the line width and the design line at the most conspicuous portion of the unevenness generated along the lateral surface 2a of the line part 2 of the resist film formed on the silicon wafer 1 are shown. The difference “ΔCD” from the width of 150 nm was measured by CD-SEM (manufactured by Hitachi High-Technologies Corporation, “S-9220”) to evaluate nanoedge roughness.

(3) Resolution (L / S)
For the line-and-space pattern (1L1S), the minimum line width (nm) of the line pattern resolved with the optimum exposure dose was taken as the resolution.

  According to Table 2, each radiation sensitive composition of Examples 3-5 containing the polymer (A-1) obtained in Example 2 is Comparative Example 1 containing the polymer (A-2). Compared with each of the radiation sensitive compositions of 3 to 3, it is more sensitive to electron beams or extreme ultraviolet rays, has low roughness and excellent resolution, and can form a fine pattern with high accuracy and stability. It was confirmed that a possible chemically amplified positive resist film could be formed.

  The radiation-sensitive composition of the present invention is not only excellent in the resolution of the line and space pattern at the time of pattern formation, but also excellent in nano edge roughness, and thus is useful for fine pattern formation by EB, EUV or X-ray. . Therefore, the radiation-sensitive composition of the present invention is extremely useful as a material capable of forming a chemically amplified resist for manufacturing semiconductor devices, which is expected to be further miniaturized in the future.

It is a typical top view at the time of seeing a line pattern from the upper part. It is typical sectional drawing of a line pattern shape.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1; Base material, 2; Resist pattern, 2a;

Claims (5)

A polymer comprising a repeating unit represented by the following general formula (1) and having a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 3000 to 100,000. .

[In General Formula (1), R is a substituted or unsubstituted linear or branched monovalent alkyl group having 1 to 20 carbon atoms, R ¹ is a hydrogen atom or a methyl group, and R ² is a substituted group. Or an unsubstituted linear or branched monovalent alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, or an aryl group having 6 to 22 carbon atoms, X is substituted or unsubstituted A methylene group, a substituted or unsubstituted linear or branched alkylene group having 2 to 25 carbon atoms, or an alicyclic hydrocarbon group having 3 to 25 carbon atoms. ] The polymer according to claim 1, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (1-1).

[In General Formula (1-1), R ¹ is a hydrogen atom or a methyl group, R ³ is a substituted or unsubstituted linear or branched monovalent alkyl group having 1 to 8 carbon atoms, 3 to 3 carbon atoms, 25 represents an alicyclic group or an aryl group having 6 to 22 carbon atoms. ] Claims further comprising at least one of a repeating unit represented by the following general formula (2), a repeating unit represented by the following general formula (3), and a repeating unit represented by the following general formula (4). The polymer according to 1 or 2.

[In General Formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a monovalent organic group, i represents an integer of 1 to 3, and j represents an integer of 0 to 3. ]

[In General Formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a monovalent organic group, k represents an integer of 1 to 3, and l represents an integer of 0 to 3. ]

[In General Formula (4), R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents a hydrogen atom or a monovalent organic group, m represents an integer of 1 to 3, and n represents an integer of 0 to 3. ] A radiation-sensitive composition containing an acid-dissociable group-containing polymer (A) and a radiation-sensitive acid generator (B),
The radiation-sensitive composition, wherein the acid-dissociable group-containing polymer (A) is the polymer according to any one of claims 1 to 3. The monomer represented by the following general formula (M-1).

[In General Formula (M-1), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a substituted or unsubstituted linear or branched monovalent alkyl group having 1 to 20 carbon atoms, and 3 to 3 carbon atoms. 25 alicyclic group, or aryl group having 6 to 22 carbon atoms, Z is a substituted or unsubstituted methylene group, substituted or unsubstituted linear or branched alkylene group having 2 to 25 carbon atoms, or carbon The alicyclic hydrocarbon group of several 3-25 is represented. ]

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