JP2010134126A - Radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition or the like for highly precisely and stably forming fine patterns and forming a chemical amplification positive type resist film by responding to active light or radiation and having excellent nano-edge roughness, sensitivity and resolution. <P>SOLUTION: The composition contains a resin, an acid generating agent expressed by formula (b1), and a low molecular compound. The low molecular compound contains a compound expressed by formula (c1), a compound having two nitrogen atoms, and one of compounds or the like having three or more nitrogen atoms. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a radiation sensitive resin composition. 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 resin composition 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.

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. An object of the present invention is to provide a radiation-sensitive resin composition that is excellent in roughness, sensitivity, and resolution and that can form a chemically amplified positive resist film capable of forming a fine pattern with high accuracy and stability.

〔一般式（ｂ１）において、Ｒｆは炭素数１〜４０の少なくとも１つのフッ素原子を有するアルキル基を示す。Ｒ^１及びＲ^２は、相互に独立して、フッ素原子、炭素数１〜８のアルキル基、炭素数１〜８のパーフルオロアルキル基、炭素数１〜８のアルコキシル基、ニトロ基、シアノ基、又はカルボキシル基を表す。ｍ及びｎは、相互に独立して、０〜４の整数である。Ｘ⁻は一価のアニオンを示す。〕

〔一般式（ｃ１）において、Ｒ^３及びＲ^４は、相互に独立して、水素原子、アルキル基、アリール基、又はアラルキル基を表す。Ｒ^５は、水素原子、アルキル基、アリール基、アラルキル基、又は下記式（ｉ）で表される基を示す。〕

〔一般式（ｉ）において、Ｒ^６は、相互に独立して、炭素数１〜５のアルキル基を示す。〕
［２］前記一般式（ｂ１）のＸ⁻で表される１価のアニオンが、炭素数１〜４０の少なくとも１つのフッ素原子を有するアルキルスルホネートアニオン、下記一般式（ｘ−１）で表されるアニオン、及び下記一般式（ｘ−２）で表されるアニオンのうちのいずれかである前記［１］に記載の感放射線性樹脂組成物。

〔一般式（ｘ−１）において、Ｒｆ^１及びＲｆ^２は、それぞれ、１個又は２個以上のフッ素原子で置換された炭素数１〜２０のアルキル基を示す。但し、Ｒｆ^１及びＲｆ^２が相互に結合して、２価の環状構造を形成していてもよい。〕

〔一般式（ｘ−２）において、Ｒｆ^３、Ｒｆ^４及びＲｆ^５は、それぞれ、１個又は２個以上のフッ素原子で置換された炭素数１〜２０のアルキル基を示す。但し、Ｒｆ^３、Ｒｆ^４及びＲｆ^５のうちのいずれか２つが相互に結合して、２価の環状構造を形成していてもよい。〕
［３］前記酸解離性基を有する繰り返し単位が、下記一般式（１−ａ）で表される繰り返し単位、及び下記一般式（１−ｂ）で表される繰り返し単位のうちの少なくとも一方である前記［１］又は［２］に記載の感放射線性樹脂組成物。

〔一般式（１−ａ）において、Ｒ^７は、水素原子、メチル基、トリフルオロメチル基、又はヒドロキシメチル基を表す。Ｒ^８は相互に独立して、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、又は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を表す。但し、いずれか２つのＲ^８が相互に結合して、それぞれが結合している炭素原子と共に２価の脂環式炭化水素基若しくはその誘導体を形成していてもよい。〕

〔一般式（１−ｂ）において、Ｒ^９は、水素原子、メチル基、トリフルオロメチル基、又はヒドロキシメチル基を表す。Ｒ^１０は相互に独立して、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、又は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を表す。但し、いずれか２つのＲ^１０が相互に結合して、それぞれが結合している炭素原子と共に２価の脂環式炭化水素基若しくはその誘導体を形成していてもよい。〕
［４］前記（Ｃ）低分子化合物が、下記一般式（ｃ１−１）で表される低分子化合物である前記［１］乃至［３］のいずれかに記載の感放射線性樹脂組成物。

〔一般式（ｃ１−１）において、Ｒ^１１及びＲ^１２は、相互に独立して、水素原子、アルキル基、アリール基又はアラルキル基を示す。〕 The present invention is as follows.
[1] (A) An alkali-insoluble or hardly alkali-soluble resin containing a repeating unit having an acid-dissociable group, which becomes alkali-soluble when the acid-dissociable group is dissociated;
(B) a radiation sensitive acid generator represented by the following general formula (b1);
(C) a low molecular weight compound,
The (C) low molecular weight compound is a compound represented by the following general formula (c1), a compound having two nitrogen atoms in the same molecule, a compound having three or more nitrogen atoms in the same molecule, an amide group-containing compound , A urea compound, and a nitrogen-containing heterocyclic compound.

[In General Formula (b1), Rf represents an alkyl group having at least one fluorine atom having 1 to 40 carbon atoms. R ¹ and R ² are each independently a fluorine atom, an alkyl group having 1 to 8 carbon atoms, a perfluoroalkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a nitro group, or a cyano group. Or a carboxyl group. m and n are integers of 0 to 4 independently of each other. X ⁻ represents a monovalent anion. ]

[In General Formula (c1), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a group represented by the following formula (i). ]

[In general formula (i), R < ⁶ > shows a C1-C5 alkyl group mutually independently. ]
[2] The monovalent anion represented by X ⁻ in the general formula (b1) is an alkyl sulfonate anion having at least one fluorine atom having 1 to 40 carbon atoms, represented by the following general formula (x-1). The radiation-sensitive resin composition according to the above [1], which is any one of an anion represented by the following general formula (x-2):

[In General Formula (x-1), Rf ¹ and Rf ² each represents an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms. However, Rf ¹ and Rf ² may be bonded to each other to form a divalent cyclic structure. ]

[In General Formula (x-2), Rf ³ , Rf ⁴ and Rf ⁵ each represent an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms. However, any two of Rf ³ , Rf ⁴ and Rf ⁵ may be bonded to each other to form a divalent cyclic structure. ]
[3] The repeating unit having the acid dissociable group is at least one of a repeating unit represented by the following general formula (1-a) and a repeating unit represented by the following general formula (1-b). The radiation sensitive resin composition according to [1] or [2].

[In General Formula (1-a), R ⁷ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R ⁸ independently represents 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. However, attached to any two R ⁸ are mutually may form a divalent alicyclic hydrocarbon group or a derivative thereof with the carbon atom to which each is attached. ]

[In General Formula (1-b), R ⁹ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R ¹⁰ independently represents 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. However, any two of R ¹⁰ may be bonded to each other to form a divalent alicyclic hydrocarbon group or a derivative thereof together with the carbon atoms to which they are bonded. ]
[4] The radiation sensitive resin composition according to any one of [1] to [3], wherein the low molecular compound (C) is a low molecular compound represented by the following general formula (c1-1).

[In General Formula (c1-1), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. ]

  According to the radiation sensitive resin composition of the present invention, KrF excimer laser, ArF excimer laser, EUV and other (extreme) deep ultraviolet rays, synchrotron radiation and other X-rays and electron beams are effectively sensitive to nano edge roughness, A chemically amplified positive resist film that is excellent in sensitivity and resolution and can form a fine pattern with high accuracy and stability can be formed.

Hereinafter, the present invention will be described in detail.
[1] Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention comprises (A) an alkali-insoluble or alkali-insoluble resin containing a repeating unit having an acid-dissociable group (hereinafter referred to as “resin (A)”). And (B) a radiation sensitive acid generator (hereinafter also referred to as “acid generator (B)”) and (C) a low molecular compound (hereinafter referred to as “low molecular compound (C)”). And).

[1-1] Resin (A)
The resin (A) in the present invention is a resin that is alkali-insoluble or hardly alkali-soluble containing a repeating unit having an acid-dissociable group, and is easily alkali-soluble by the action of an acid. The term “alkali insoluble or alkali insoluble” as used herein refers to an alkali development condition employed when a resist pattern is formed from a resist film formed from a radiation-sensitive composition containing the resin (A). When a 100 nm-thick film using only the resin (A) is developed instead of the resist film, 50% or more of the initial film thickness of the film remains after development.

  Since the radiation sensitive resin composition of this invention contains such resin (A), it is excellent in sensitivity. From this point of view, this radiation-sensitive resin composition is effectively sensitive to an electron beam or extreme ultraviolet rays in a lithography process, has low roughness, has excellent sensitivity and resolution, and stabilizes a fine pattern with high accuracy and stability. It is possible to form a chemically amplified positive resist film that can be formed in this manner.

  The repeating unit having the acid dissociable group contained in the resin (A) is a repeating unit represented by the following general formula (1-a) and a repeating unit represented by the following general formula (1-b). Preferably at least one of the units.

〔一般式（１−ａ）において、Ｒ^７は、水素原子、メチル基、トリフルオロメチル基、又はヒドロキシメチル基を表す。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、又は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を表す。但し、いずれか２つのＲ^８が相互に結合して、それぞれが結合している炭素原子と共に２価の脂環式炭化水素基若しくはその誘導体を形成していてもよい。〕

[In General Formula (1-a), R ⁷ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R ⁸ independently represents 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. However, attached to any two R ⁸ are mutually may form a divalent alicyclic hydrocarbon group or a derivative thereof with the carbon atom to which each is attached. ]

〔一般式（１−ｂ）において、Ｒ^９は、水素原子、メチル基、トリフルオロメチル基、又はヒドロキシメチル基を表す。Ｒ^１０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、又は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を表す。但し、いずれか２つのＲ^１０が相互に結合して、それぞれが結合している炭素原子と共に２価の脂環式炭化水素基若しくはその誘導体を形成していてもよい。〕

[In General Formula (1-b), R ⁹ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R ¹⁰ independently represents 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. However, any two of R ¹⁰ may be bonded to each other to form a divalent alicyclic hydrocarbon group or a derivative thereof together with the carbon atoms to which they are bonded. ]

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ^{8 in} the general formula (1-a) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n- A butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like can be mentioned.
Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms in R ⁸ include norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like. Groups composed of alicyclic rings derived from cycloalkanes of the above; groups composed of these alicyclic rings include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, Examples include groups substituted with one or more linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as 2-methylpropyl group, 1-methylpropyl group and t-butyl group. be able to.
In addition, any two R ^{8 s} bonded to each other and the divalent alicyclic hydrocarbon group or derivative thereof formed together with the carbon atom to which each is bonded include, for example, norbornane, tricyclodecane, A group composed of an alicyclic ring derived from tetracyclododecane, adamantane, cyclopentane or cyclohexane, a group obtained by substituting a group composed of these alicyclic rings with the alkyl group, and the like are preferable.

Note that ^{R 9} and ^{R 10} in the general formula (1-b), respectively, it can be directly applied to the description of ^{R 8} and ^{R 10} in the general formula (1-a).

  Among the repeating units (1) having an acid dissociable group, repeating units represented by the following general formulas (1-1) to (1-8) are preferable. Among these, the repeating units represented by the following general formulas (1-2), (1-3) and (1-4) are particularly preferable.

〔一般式（１−１）〜（１−８）において、Ｒ^１３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^１４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 General Formulas (1-1) to (1-8), R ¹³ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group independently of each other, and R ¹⁴ represents a C 1 to C 1 independently of each other. 4 linear or branched alkyl groups are represented. ]

  In addition, in the resin (A) in this invention, the said repeating unit (1) may be contained only 1 type, and may be contained 2 or more types.

  In addition, the resin (A) in the present invention may be composed only of the repeating unit (1), but in addition to the repeating unit (1), the repeating unit represented by the following general formula (2) [below , "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^１５は水素原子又はメチル基、Ｒ^１６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 ¹⁵ represents a hydrogen atom or a methyl group, R ¹⁶ 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^１７は水素原子又はメチル基、Ｒ^１８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 ¹⁷ represents a hydrogen atom or a methyl group, R ¹⁸ 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^１９は水素原子又はメチル基、Ｒ^２０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 ¹⁹ represents a hydrogen atom or a methyl group, R ²⁰ 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 ¹⁶ 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 resin (A), this repeating unit (2) may be contained only 1 type and may be contained 2 or more types.

Regarding the monovalent organic group of R ¹⁸ in the general formula (3), the description regarding the monovalent organic group of R ¹⁶ 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 resin (A), this repeating unit (3) may be contained only 1 type and may be contained 2 or more types.

Regarding the monovalent organic group represented by R ²⁰ in the general formula (4), the description relating to the monovalent organic group represented by R ¹⁶ 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 the repeating unit (4) is contained in resin (A), 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 above 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 resin (A) of the present invention further includes a repeating unit derived from a non-acid dissociable compound (hereinafter also referred to as “repeating unit (5)”). May be included.

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 (5-1) are preferable.
In addition, when the said repeating unit (5) is contained in resin (A), this repeating unit (5) may be contained only 1 type and may be contained 2 or more types.
Further, “(meth) acrylate” in the present specification means “acrylate” or “methacrylate”.

The content of the repeating unit (1) in the resin (A) of the present invention is preferably 1 mol% or more, more preferably, when the total of all repeating units in the resin (A) is 100 mol%. Is 20 to 70 mol%, more preferably 20 to 50 mol%. When this content is 51 mol% or more, the nano edge roughness can be excellent.
The total content of the repeating units (2) to (4) is preferably 1 mol% or more, more preferably, when the total of all repeating units in the resin (A) is 100 mol%. Is 10 to 95 mol%, more preferably 40 to 80 mol%. When the total content exceeds 95 mol%, the nano edge roughness may be deteriorated.
Furthermore, the total content of the repeating units (1) to (4) is preferably 10 mol% or more, more preferably, when the total of all repeating units in the resin (A) is 100 mol%. Is 40 to 100 mol%, more preferably 50 to 100 mol%. When the total content is 10 mol% or more, the nano edge roughness can be improved.
Moreover, content of the said repeating unit (5) is 60 mol% or less normally, when the sum total of all the repeating units in resin (A) is 100 mol%, Preferably it is 0-50 mol%. When this content is 60 mol% or less, it can be excellent in performance balance between resolution performance and nanoedge roughness.

  Although the synthesis | combining method of resin (A) in this invention is not specifically limited, For example, it can obtain by well-known radical polymerization or anionic polymerization. The side chain hydroxystyrene units in the repeating units (2) to (4) can be obtained by hydrolyzing the obtained resin (A) in the presence of a base or acid in an organic solvent. Obtainable.

  In the radical polymerization, for example, a necessary monomer such as a monomer giving the repeating unit (1) is stirred in a suitable organic solvent in a nitrogen atmosphere in the presence of a radical polymerization initiator and heated. Can be implemented.

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 repeating unit (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 implemented by maintaining.

  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 addition, in the synthesis | combination of the said resin (A), it is also possible to perform a polymerization reaction by heating and to perform cationic polymerization, without using a polymerization initiator.

In addition, when the hydroxystyrene unit is introduced by hydrolyzing the side chain of the resin (A), examples of the acid used for the hydrolysis reaction include p-toluenesulfonic acid and its hydrate, methanesulfone Acids, organic acids such as trifluoromethanesulfonic acid, malonic acid, succinic acid, 1,1,1-fluoroacetic acid; inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid; or pyridinium p-toluenesulfonate, ammonium p -Salts such as toluene sulfonate and 4-methylpyridinium p-toluene sulfonate.
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 resin (A) has a polystyrene-reduced weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC), preferably 3000 to 100,000, more preferably 3000 to 40000, More preferably, it is 3000-25000.
The ratio (Mw / Mn) of the Mw of the resin (A) and the polystyrene-equivalent number average molecular weight (hereinafter also referred to as “Mn”) measured by GPC is usually 1 to 5, more preferably 1 to 5. 3, more preferably 1 to 2.5.

[1-2] Acid generator (B)
The acid generator (B) is an onium salt represented by the following general formula (b1), and generates an acid when irradiated with radiation.
In the radiation sensitive resin composition of the present invention, when the acid generator (B) is blended, in the lithography process, when irradiated with an electron beam or radiation, the radiation sensitive resin composition is used. Acid is generated. Then, the acid generated from the acid generator (B) dissociates the acid dissociable group present in the resin (A) contained in the composition (releases the protecting group), and the resin ( A) is alkali-soluble. As a result, for example, the exposed portion of the resist film becomes readily soluble in an alkaline developer, and a positive resist pattern is formed.

〔一般式（ｂ１）において、Ｒｆは炭素数１〜４０の少なくとも１つのフッ素原子を有するアルキル基を示す。Ｒ^１及びＲ^２は、相互に独立して、フッ素原子、炭素数１〜８のアルキル基、炭素数１〜８のパーフルオロアルキル基、炭素数１〜８のアルコキシル基、ニトロ基、シアノ基、又はカルボキシル基を表す。ｍ及びｎは、相互に独立して、０〜４の整数である。Ｘ⁻は一価のアニオンを示す。〕

[In General Formula (b1), Rf represents an alkyl group having at least one fluorine atom having 1 to 40 carbon atoms. R ¹ and R ² are each independently a fluorine atom, an alkyl group having 1 to 8 carbon atoms, a perfluoroalkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a nitro group, or a cyano group. Or a carboxyl group. m and n are integers of 0 to 4 independently of each other. X ⁻ represents a monovalent anion. ]

The alkyl group having at least one fluorine atom having 1 to 40 carbon atoms of Rf in the general formula (b1) may be linear, branched, or cyclic.
Specifically, for example, a trifluoromethyl group (CF ₃ ), a perfluoroethyl group (—C ₂ F ₅ ), a perfluoropropyl group (—C ₃ F ₇ ), a perfluoroisopropyl group (—CF (CF _{3) 2} ), perfluorobutyl group (—C ₄ F ₉ ), perfluoroisobutyl group (—CF ₂ CF (CF ₃ ) ₂ ), perfluoro-sec-butyl group (—CF (CF ₃ ) CF ₂ CF ₃ ), Perfluoro-t-butyl group (—C (CF ₃ ) ₃ ), perfluoropentyl group (—C ₅ F ₁₁ ), perfluorohexyl group (—C ₆ F ₁₃ ), perfluoroheptyl group (—C ₇ F _15), perfluoro-5-methylhexyl group _{(- (CF 2) 4 CF} (CF 3) CF 3), perfluorooctyl group _{(-C 8 F 17),} perfluoro Noni Perfluoroalkyl, such as a sulfur group (—C ₉ F ₁₉ ), a perfluoro-7-methyloctyl group (— (CF ₂ ) ₆ CF (CF ₃ ) CF ₃ ), and a perfluorodecyl group (—C ₁₀ F ₂₁ ) Groups are preferred.

Further, examples of the Rf, in addition to the perfluoroalkyl group described _{above, -CHF 2, -C 2 HF 4} , -C 3 HF 6, -C 4 HF 8, -C 5 HF 10, -C 6 HF ₁₂ , -C ₇ HF ₁₄ , -C ₈ HF ₁₆ , -C ₉ HF ₁₈ , -C ₁₀ HF ₂₀ , -CH ₂ F ₂ , -C ₂ H ₂ F ₃ , -C ₃ H ₂ F ₅ , -C _{4 H 2 F 7, -C 5} H 2 F 9, -C 6 H 2 F 11, -C 7 H 2 F 13, -C 8 H 2 F 15, -C 9 H 2 F 17, -C 10 H _{2 F 19, -C 2 H 3} F, -C 3 H 3 F 4, -C 4 H 3 F 6, -C 5 H 3 F 8, -C 6 H 3 F 10, -C 7 H 3 F 12 _{, -C 8 H 3 F 14,} -C 9 H 3 F 17, -C 10 H 3 F18, -CClF 2, -C 2 ClF 4 , -C ₃ ClF ₆ , -C ₄ ClF ₈ , -C ₅ ClF ₁₀ , -C ₆ ClF ₁₂ , -C ₇ ClF ₁₄ , -C ₈ ClF ₁₆ , -C ₉ ClF ₁₈ , -C ₁₀ ClF ₂₀ ,- _{CBrF 2, -C 2 BrF 4,} -C 3 BrF 6, -C 4 BrF 8, -C 5 BrF 10, -C 6 BrF 12, -C 7 BrF 14, -C 8 BrF 16, -C 9 BrF 18 _{, -C 10 BrF 20, -CF 2} I, -C 2 F 4 I, -C 3 F 6 I, -C 4 F 8 I, -C 5 F 10 I, C 6 F 12 I, -C 7 F Examples include linear or branched haloalkyl groups having 1 to 10 carbon atoms (preferably fluoroalkyl groups) such as ₁₄ I, C ₈ F ₁₆ I, —C ₉ F ₁₈ I, C ₁₀ F ₂₀ I, etc. Can do.

Examples of the alkyl group having 1 to 8 carbon atoms of R ¹ and R ² in the general formula (b1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group, cyclopentyl group, cyclohexyl group and the like.
As the alkoxyl group having 1 to 8 carbon atoms of ^{R 1} and ^{R 2,} for example, a methoxy group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy group, 2-methyl-propoxy group, 1- Examples thereof include a methylpropoxy group, a t-butoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
In addition, about the perfluoroalkyl group, the example of said Rf can be mentioned.

X < ^- > in the general formula (b1) is a monovalent anion, and is preferably a monovalent sulfonic acid or carboxylic acid anion. In particular, this X ⁻ is represented by an alkyl sulfonate anion having at least one fluorine atom having 1 to 40 carbon atoms, an anion represented by the following general formula (x-1), and the following general formula (x-2). It is preferable that it is any one of the anions.

〔一般式（ｘ−１）において、Ｒｆ^１及びＲｆ^２は、それぞれ、１個又は２個以上のフッ素原子で置換された炭素数１〜２０のアルキル基を示す。但し、Ｒｆ^１及びＲｆ^２が相互に結合して、２価の環状構造を形成していてもよい。〕

[In General Formula (x-1), Rf ¹ and Rf ² each represents an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms. However, Rf ¹ and Rf ² may be bonded to each other to form a divalent cyclic structure. ]

〔一般式（ｘ−２）において、Ｒｆ^３、Ｒｆ^４及びＲｆ^５は、それぞれ、１個又は２個以上のフッ素原子で置換された炭素数１〜２０のアルキル基を示す。但し、Ｒｆ^３、Ｒｆ^４及びＲｆ^５のうちのいずれか２つが相互に結合して、２価の環状構造を形成していてもよい。〕

[In General Formula (x-2), Rf ³ , Rf ⁴ and Rf ⁵ each represent an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms. However, any two of Rf ³ , Rf ⁴ and Rf ⁵ may be bonded to each other to form a divalent cyclic structure. ]

The alkyl sulfonate anion may be linear, branched or cyclic. Specifically, for example, trifluoromethanesulfonate, difluoroethanesulfonate, nonafluoro-n-butanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10} ] dodecan-8-yl) ethanesulfonate, 1,1-difluoro-2- (bicyclo [2.2.1] heptan-2-yl) ethanesulfonate, and the like.

The alkyl group having 1 to 20 carbon atoms substituted with one or two or more fluorine atoms of Rf ^{1 to} Rf ^{5 in} the general formulas (x-1) and (x-2) is linear. Also, it may be branched or cyclic. Specific examples include a trifluoromethyl group, a difluoroethyl group, a nanofluorobutyl group, a tetrafluoroethylene group, a hexafluoropropylene group, and an octafluorobutylene group. Further, among the examples of Rf, those having 1 to 20 carbon atoms are exemplified.

Divalent cyclic structure Rf ¹ and Rf ² in the general formula (x-1) is formed by bonding to each other, and, one of ^Rf 3 ^{~Rf 5} in the general formula (x-2) Examples of the divalent cyclic structure formed by bonding two to each other include structures represented by the following general formulas (xx-1) to (xx-5).

  Specific examples of the acid generator (B) include compounds represented by the following formulas (b1-1) to (b1-24). Among these, the formulas (b1-1), (b1-2), (b1-4), (b1-6), (b1-7), (b1-8), (b1-9), (b1 The compound represented by -11) is preferred.

  In addition, the said acid generator (B) 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 the said acid generator (B) is 0.1-40 mass parts with respect to 100 mass parts of said resin (A), More preferably, it is 0.5-30 mass parts. is there. When the amount of the acid generator (B) is less than 0.1 parts by mass, the sensitivity and developability may be lowered. On the other hand, when it exceeds 40 mass parts, there exists a possibility that transparency with respect to a radiation, a pattern shape, heat resistance, etc. may fall.

[1-3] Low molecular compound (C)
The low molecular weight compound (C) controls acid diffusion in the resist film (resist film) of the acid generated from the acid generator (B) upon exposure, and suppresses undesired chemical reactions in non-exposed areas. It is a component having a control action (hereinafter also referred to as “acid diffusion controller (C)”).
In the radiation sensitive resin composition of the present invention, by adding this acid diffusion controller (C), the storage stability of the resulting composition is improved and the resolution of the resist film to be formed is sufficient. Can be improved. Furthermore, a radiation-sensitive resin composition that can suppress a change in the line width of the resist pattern due to fluctuations in the holding time (PED) from the exposure to the heat treatment after the exposure, and has extremely excellent process stability. can get.

  The acid diffusion controller (C) in the present invention is a compound represented by the following general formula (c1) (hereinafter also referred to as “nitrogen-containing compound (i)”), a compound having two nitrogen atoms in the same molecule ( Hereinafter, also referred to as “nitrogen-containing compound (ii)”, a compound having three or more nitrogen atoms in the same molecule (hereinafter also referred to as “nitrogen-containing compound (iii)”), an amide group-containing compound, a urea compound, and It is at least one of nitrogen-containing heterocyclic compounds.

〔一般式（ｃ１）において、Ｒ^３及びＲ^４は、相互に独立して、水素原子、アルキル基、アリール基、又はアラルキル基を表す。Ｒ^５は、水素原子、アルキル基、アリール基、アラルキル基、又は下記式（ｉ）で表される基を示す。〕

[In General Formula (c1), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a group represented by the following formula (i). ]

〔一般式（ｉ）において、Ｒ^６は、相互に独立して、炭素数１〜５のアルキル基を示す。〕

[In general formula (i), R < ⁶ > shows a C1-C5 alkyl group mutually independently. ]

The alkyl group of R ^{3 to} R ⁵ in the general formula (c1) may be linear, branched, or cyclic. Further, one or two or more hydrogen atoms may be substituted. Moreover, it is preferable that carbon number of an alkyl group is 1-10. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl group, and a cyclopentyl group. Cyclohexyl group, octyl group and the like.

The aryl group in R ^{3 to} R ⁵ in the general formula (c1) may be one in which one or two or more hydrogen atoms are substituted. Moreover, it is preferable that carbon number of this aryl group is 6-12. Examples of such an aryl group include a phenyl group and a naphthyl group.
The aralkyl group in R ^{3 to} R ⁵ in the general formula (c1) may be one in which one or two or more hydrogen atoms are substituted. Moreover, it is preferable that carbon number of this aralkyl group is 7-12. Examples of such an aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Moreover, the C1-C5 alkyl group in R < ⁶ > of the said general formula (i) may be linear, branched or cyclic. The three R ^{6 s} may all be the same alkyl group, or some or all of them may be different alkyl groups.
Specifically, for example, alkyl such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, and cyclopentyl group. The group can be mentioned. Among these, a methyl group is preferable. In particular, all three R ⁶ are preferably methyl groups.

  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 Furthermore, it is preferable that it is a compound represented by the following general formula (c1-1).

〔一般式（ｃ１−１）において、Ｒ^１１及びＲ^１２は、相互に独立して、水素原子、アルキル基、アリール基又はアラルキル基を示す。〕

[In General Formula (c1-1), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. ]

The description of R ³ and R ⁴ in the general formula (c1) can be applied as it is to R ¹¹ and R ¹² in the general formula (c1-1).

  Specific examples of the compound represented by the general formula (c1-1) include compounds represented by the following formulas (c1-1-1) to (c1-1-5).

  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.

  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-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, Examples include pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, and isocyanuric acid tris (2-hydroxyethyl).

  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. Examples include thiourea.

  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 and 2,4,5-triphenylimidazole; 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, 2,2 ′: 6 ′, 2 ″ -terpyridine, etc. Pyridines; piperazine, 1- (2-hydroxy In addition to piperazines such as (til) 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, 1,8-diazabicyclo [4.3.0] non-5-ene and the like.

  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.

  The molecular weight of the acid diffusion controller (C) [low molecular compound (C)] is preferably 100 to 10,000, more preferably 100 to 1,000, and still more preferably 100 to 500. In addition, when this acid diffusion controlling agent (C) is a polymer (polyethyleneimine or the like), it means a weight average molecular weight (Mw).

  Moreover, it is preferable that the compounding quantity of the said acid diffusion control agent (C) is 15 mass parts or less with respect to 100 mass parts of said resin (A), More preferably, it is 0.001-10 mass parts, More preferably. 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, when the 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.

[1-4] Other components The radiation-sensitive resin composition of the present invention is obtained by dissolving the resin (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, the radiation sensitive resin composition of this invention can further mix | blend various additives, such as surfactant, a sensitizer, and an aliphatic additive, as another component 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 resin composition of the present invention is preferably such that the total solid content in the composition is 1 to 70% by mass, more preferably 1 to 15% by mass. The amount is more preferably 1 to 10% by mass.

  The radiation-sensitive resin composition of the present invention comprises the above-mentioned resin (A), acid generator (B), acid diffusion controller (C), and other components (excluding the solvent) as necessary. It can be prepared by uniformly dissolving in a solvent so that the partial concentration 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 resin (A).

The sensitizer absorbs radiation energy and transmits the energy to the acid generator (B), thereby increasing the amount of acid produced. Has the effect of improving the 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 resin (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 lithocholic acid 2-cyclohexyloxyethyl, lithocholic acid 3-oxocyclohexyl, lithocholic acid tetrahydropyranyl, lithocholic acid mevalonolactone ester; dimethyl adipate, diethyl adipate, dipropyl adipate, di-n - 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 resin (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. .

[2] Method for Forming Resist Pattern The radiation-sensitive resin 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 resin composition of the present invention, first, a resist film is formed with the radiation sensitive resin composition of the present invention. As the radiation-sensitive resin composition, for example, as described above, after adjusting the total solid content concentration, it can be filtered with a filter having a pore diameter of about 0.2 μm. By applying this radiation-sensitive resin composition to a substrate such as a silicon wafer or a wafer coated with aluminum by an appropriate coating means such as spin coating, cast coating or roll coating, a resist film is formed. Form. 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 composition of the radiation-sensitive resin composition, the type of additive, and the like. 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. The heating condition of PEB can be appropriately selected depending on the composition of the radiation sensitive resin composition, but 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 resin composition, for example, as disclosed in Japanese Patent Publication No. 6-12252 (Japanese Patent Laid-Open No. 59-93448), etc. 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] Resin synthesis
<Synthesis Example 1>
Synthesis of Resin (A-1) 56 g of p-acetoxystyrene, 44 g of a compound (monomer) represented by the following formula (M-1), 4 g of azobisisobutyronitrile (hereinafter referred to as “AIBN”), and 1 g of t-dodecyl mercaptan was dissolved in 100 g of propylene glycol monomethyl ether, and then the 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 1000 g of n-hexane to coagulate and purify the resulting copolymer. Next, 150 g of propylene glycol monomethyl ether was added again to the copolymer, and then 150 g of methanol, 35 g of triethylamine and 7 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 150 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 11000, Mw / Mn is 2.0, and as a result of ¹³ C-NMR analysis, the content ratio (mol) of each repeating unit derived from p-hydroxystyrene and the compound (M-1). The ratio) was a 65:35 copolymer. Hereinafter, this copolymer is referred to as “resin (A-1)”.

In addition, the measurement of Mw and Mn in a present Example uses the Tosoh Co., Ltd. product GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL), 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.
In ¹³ C-NMR analysis, a model “JNM-EX270” manufactured by JEOL Ltd. was used.

<Synthesis Example 2>
Synthesis of Resin (A-2) 55 g of p-acetoxystyrene, 45 g of a compound (monomer) represented by the following formula (M-2), 4 g of AIBN and 1 g of t-dodecyl mercaptan were dissolved in 100 g of propylene glycol monomethyl ether. Thereafter, 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 1000 g of n-hexane to coagulate and purify the resulting copolymer. Next, 150 g of propylene glycol monomethyl ether was added to the copolymer, and then 150 g of methanol, 34 g of triethylamine and 6 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 150 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 10,000, 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 65:35 copolymer. Hereinafter, this copolymer is referred to as “resin (A-2)”.

<Synthesis Example 3>
Synthesis of Resin (A-3) 68 g of p-acetoxystyrene, 32 g of a compound (monomer) represented by the following formula (M-3), 4 g of AIBN and 1 g of t-dodecyl mercaptan were dissolved in 100 g of propylene glycol monomethyl ether. Thereafter, 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 1000 g of n-hexane to coagulate and purify the resulting copolymer. Next, 150 g of propylene glycol monomethyl ether was added to the copolymer, and then 150 g of methanol, 43 g of triethylamine and 8 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 150 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 11000, Mw / Mn is 2.1, and as a result of ¹³ C-NMR analysis, the content ratio (mol) of each repeating unit derived from p-hydroxystyrene and the compound (M-3) The ratio) was a 65:35 copolymer. Hereinafter, this copolymer is referred to as “resin (A-3)”.

[2] Preparation of radiation-sensitive resin composition
<Examples 1-9 and Comparative Examples 1-2>
(A) Resin, (B) Acid generator, (C) Acid diffusion controller, (D) Solvent were mixed in the amounts shown in Table 1, and the resulting mixture was filtered through a membrane filter having a pore size of 200 nm. By doing this, each composition solution (radiation sensitive resin composition) of Examples 1-9 and Comparative Examples 1-2 was prepared.

The details of the (A) resin, (B) acid generator, (C) acid diffusion controller and (D) solvent are shown below.
(A) Resin (A-1): Resin (A-1) obtained in Synthesis Example 1
(A-2): Resin (A-2) obtained in Synthesis Example 2
(A-3): Resin (A-3) obtained in Synthesis Example 3
(B) Acid generator (B-1): Compound represented by the following formula (B-1) (B-2): Compound represented by the following formula (B-2) (B-3): The following formula Compound represented by (B-3) (B-4): Compound represented by the following formula (B-4) (B-5): Compound represented by the following formula (B-5)

(C-1): Compound represented by the following formula (C-1) (C-2): Compound represented by the following formula (C-2) (C-3): In the following formula (C-3) Compound represented (C-4): Tri-n-octylamine (C-5): 1,8-diazabicyclo [4.3.0] non-5-ene (C-6): 2,4,5 -Triphenylimidazole

(D) Solvent (D-1): Ethyl lactate (D-2): Propylene glycol monomethyl ether acetate

[3] Evaluation of Radiation Sensitive Resin Composition Each of the composition solutions (Examples 1 to 9 and Comparative Examples 1 and 2 of the radiation sensitive resin) on a silicon wafer in a clean track ACT-8 manufactured by Tokyo Electron Ltd. After spin coating the composition, PB (heat treatment) was performed under the conditions shown in Table 2 to form a resist (radiation sensitive resin composition) film having a thickness of 70 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, a 2.38% tetramethylammonium hydroxide aqueous solution was used and developed by the paddle method at 23 ° C. for 1 minute, and then washed with pure water and dried 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 resin compositions of Examples 1 to 9 and Comparative Examples 1 and 2.

(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 design 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, the radiation sensitive resin compositions of Examples 1 to 9 containing acid generators (B-1) to (B-3) are acid generators (B-4) to (B-5). Compared with the radiation-sensitive resin compositions of Comparative Examples 1 and 2 containing), it is sensitive to electron beams or extreme ultraviolet rays, has low roughness and excellent sensitivity, and has a fine pattern with high accuracy. It was confirmed that a chemically amplified positive resist film that can be stably formed can be formed.
Among the radiation sensitive resin compositions of Examples 1 to 9 containing acid generators (B-1) to (B-3), acid diffusion control agents (C-1) to (C-3) In particular, the radiation-sensitive resin compositions of Examples 1 to 6 containing low-roughness and excellent sensitivity, and a chemically amplified positive electrode capable of forming a fine pattern with high accuracy and stability. It was confirmed that a type resist film can be formed.

  The radiation-sensitive resin composition of the present invention is not only excellent in line and space pattern resolution during pattern formation, but also excellent in nano edge roughness, so it is useful for fine pattern formation by EB, EUV and X-rays. is there. Therefore, the radiation-sensitive resin 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 (4)

(A) an alkali-insoluble or hardly alkali-soluble resin containing a repeating unit having an acid-dissociable group, which becomes alkali-soluble when the acid-dissociable group is dissociated;
(B) a radiation sensitive acid generator represented by the following general formula (b1);
(C) a low molecular weight compound,
The (C) low molecular weight compound is a compound represented by the following general formula (c1), a compound having two nitrogen atoms in the same molecule, a compound having three or more nitrogen atoms in the same molecule, an amide group-containing compound , A urea compound, and a nitrogen-containing heterocyclic compound.

[In General Formula (b1), Rf represents an alkyl group having at least one fluorine atom having 1 to 40 carbon atoms. R ¹ and R ² are each independently a fluorine atom, an alkyl group having 1 to 8 carbon atoms, a perfluoroalkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a nitro group, or a cyano group. Or a carboxyl group. m and n are integers of 0 to 4 independently of each other. X ⁻ represents a monovalent anion. ]

[In General Formula (c1), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a group represented by the following formula (i). ]

[In general formula (i), R < ⁶ > shows a C1-C5 alkyl group mutually independently. ] Anionic monovalent anion represented by the alkyl sulfonate anion having at least one fluorine atom having 1 to 40 carbon atoms, represented by the following general formula (x-1), ^- X in the general formula (b1) And the radiation sensitive resin composition of Claim 1 which is either an anion represented by the following general formula (x-2).

[In General Formula (x-1), Rf ¹ and Rf ² each represents an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms. However, Rf ¹ and Rf ² may be bonded to each other to form a divalent cyclic structure. ]

[In General Formula (x-2), Rf ³ , Rf ⁴ and Rf ⁵ each represent an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms. However, any two of Rf ³ , Rf ⁴ and Rf ⁵ may be bonded to each other to form a divalent cyclic structure. ] The repeating unit having an acid dissociable group is at least one of a repeating unit represented by the following general formula (1-a) and a repeating unit represented by the following general formula (1-b). 3. The radiation sensitive resin composition according to 1 or 2.

[In General Formula (1-a), R ⁷ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R ⁸ independently represents 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. However, attached to any two R ⁸ are mutually may form a divalent alicyclic hydrocarbon group or a derivative thereof with the carbon atom to which each is attached. ]

[In General Formula (1-b), R ⁹ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R ¹⁰ independently represents 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. However, any two of R ¹⁰ may be bonded to each other to form a divalent alicyclic hydrocarbon group or a derivative thereof together with the carbon atoms to which they are bonded. ] The radiation sensitive resin composition according to any one of claims 1 to 3, wherein the low molecular compound (C) is a low molecular compound represented by the following general formula (c1-1).

[In General Formula (c1-1), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. ]

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