JP4655886B2 - Positive radiation sensitive resin composition - Google Patents

Description

  The present invention relates to a positive radiation sensitive resin composition. More specifically, the present invention relates to a positive radiation sensitive resin composition suitable as a chemically amplified resist sensitive to (ultra) deep ultraviolet rays represented by active radiation (for example, KrF excimer laser, ArF excimer laser, EUV or electron beam).

In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, recently, a lithography technique capable of microfabrication at a level of 0.10 μm or less is required. However, in the conventional lithography process, near ultraviolet rays such as i rays are generally used as radiation, and it is said that fine processing at the subquarter micron level is extremely difficult with this near ultraviolet rays. Therefore, in order to enable microfabrication at a level of 0.10 μm or less, use of radiation having a shorter wavelength is being studied.
Examples of such short-wavelength radiation include an emission line spectrum of a mercury lamp, far-ultraviolet rays typified by an excimer laser, an X-ray, an electron beam, and the like. ) Or ArF excimer laser (wavelength 193 nm) has been attracting attention. As a resist suitable for irradiation with such an excimer laser, a component having an acid-dissociable functional group and a component that generates acid upon irradiation with radiation (hereinafter referred to as “exposure”) (hereinafter referred to as “acid generator”). Many resists using the chemical amplification effect (hereinafter referred to as “chemically amplified resist”) have been proposed. As the chemically amplified resist, for example, a resist containing a polymer in which a carboxylic acid is protected with a t-butoxycarbonyl group or a polymer in which a phenolic hydroxyl group is protected with a t-butoxycarbonyl group, and an acid generator is proposed. (See Patent Document 1). In the resist, the t-butoxycarbonyl group in the polymer is dissociated by the action of an acid generated by exposure. As a result, the polymer has an acidic group composed of a carboxyl group or a phenolic hydroxyl group, and utilizes the phenomenon that the exposed region of the resist film becomes readily soluble in an alkaline developer. Many conventional chemically amplified resists are based on phenolic resins.
However, the resolution of the resist film using these compositions is not always sufficient, and further improvement of the resolution has been desired.

  In recent years, the design rules of semiconductor devices have been further miniaturized, and particularly in the case of a pattern of 100 nm or less, the yield reduction due to pattern collapse has become remarkable due to the high aspect ratio. Therefore, a composition that hardly causes such pattern collapse, that is, a composition having a wide “pattern collapse margin” is desired.

  Under such circumstances, development of a chemically amplified resist having high resolution and excellent pattern collapse margin has been strongly demanded from the viewpoint of technological development that can cope with the progress of miniaturization in integrated circuit elements.

JP 59-45439 A

  An object of the present invention is to provide a positive radiation sensitive resin composition useful as a chemically amplified resist having high resolution and excellent pattern collapse margin.

〔一般式（１）において、Ｒ^１はメチル基又は水素原子を示し、ｋは０又は１である。〕

〔一般式（２）において、Ｒ^２はメチル基、フッ素原子又は水素原子を示し、Ｒ^３は炭素数１〜５の直鎖状又は分岐状のアルキル基を示し、Ｒ^４は一価の有機基を示し、ｍは０〜５の整数であり、ｎは１又は２である。〕

As means for achieving the above object, the invention of claim 1 includes (A) a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). Including an alkali-insoluble or hardly-alkali-soluble resin, (B) a radiation-sensitive acid generator, and (C) a phenolic compound [excluding a polymer having a structural unit represented by the following formula (i)] Is a positive-type radiation-sensitive resin composition.

[In General Formula (1), R ¹ represents a methyl group or a hydrogen atom, and k is 0 or 1. ]

[In General Formula (2), R ² represents a methyl group, a fluorine atom or a hydrogen atom, R ³ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and R ⁴ represents a monovalent organic group. Represents a group, m is an integer of 0 to 5, and n is 1 or 2. ]

  Invention of Claim 2 is a positive radiation sensitive resin composition of Claim 1 whose benzene ring number of the said (C) phenolic compound is 2-4.

  Invention of Claim 3 is a positive radiation sensitive resin composition of Claim 2 whose total number of the hydroxyl group which the benzene ring in said (C) phenolic compound has is 2-8.

  Invention of Claim 4 is content of said (C) phenolic compound, and is 0.5-5 mass parts with respect to 100 mass parts of said (A) resin, The invention in any one of Claim 1 thru | or 3 It is a positive type radiation sensitive resin composition.

  The radiation-sensitive resin composition of the present invention has the above-described structure, and thus a chemically amplified resist that is sensitive to actinic rays, for example, far ultraviolet rays represented by KrF excimer laser (wavelength 248 nm) or ArF excimer laser (wavelength 193 nm). In particular, since it has a high resolution and an excellent pattern collapse margin, it can be used extremely favorably in the manufacture of integrated circuit elements that are expected to be further miniaturized in the future.

Hereinafter, the present invention will be described in detail.
<Resin>
<1> Resin (A)
The resin (A) in the present invention comprises a repeating unit represented by the general formula (1) (hereinafter referred to as “repeating unit (1)”) and a repeating unit represented by the general formula (2) (hereinafter, "Repeating unit (2)") as an essential unit, and is an alkali-insoluble or alkali-insoluble resin that becomes alkali-soluble by the action of an acid. The term “alkali-insoluble or alkali-insoluble” as used herein refers to alkali development conditions employed when forming a resist pattern from a resist film formed from a positive radiation-sensitive resin composition containing the resin (A). Thus, when a film using only the resin (A) is developed instead of the resist film, it means that 50% or more of the initial film thickness of the film remains after development.

In the general formula (1), R ¹ is a methyl group or a hydrogen atom. In the general formula (1), k is 0 or 1.

In the general formula (2), R ² is a methyl group, a fluorine atom or a hydrogen atom. N is 1 or 2.

Further, in the general formula (2), R ³ represents a linear or branched alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, n- propyl group, i- propyl radical, n -Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like can be mentioned. Of these alkyl groups, a methyl group and an ethyl group are preferable.

Further, in the general formula (2), R ⁴ represents a monovalent organic group, and examples thereof include a linear or branched methyl group, ethyl group, propyl group, butyl group, methoxy group, and ethoxy group. be able to. Of these, a methyl group and an ethyl group are preferable.
Moreover, m is an integer of 0-5. In particular, m is preferably 0 to 3 and more preferably 0 from the viewpoint of improving the pattern collapse margin.

  Further, in the (meth) acrylic acid ester structure in the general formula (2), the bond between the carbonyloxy group in the formula and the heterocyclic ring or hydrocarbon ring is dissociated by the action of an acid to form a carboxyl group. (In the specification, “(meth) acrylic acid ester” means both acrylic acid ester and methacrylic acid ester).

  The proportion of the repeating units represented by the general formulas (1) and (2) in the resin (A) is not particularly limited, and various proportions may be used as necessary. Usually, in 100 mol% of the resin (A), the proportion of the repeating unit (1) is 10 to 60 mol%, preferably 10 to 50 mol%, more preferably 20 to 50 mol%. When the ratio of the repeating unit (1) is 10 mol% or more, it is preferable because the developability and adhesion to the substrate can be improved, and when it is 60 mol% or less, the resolution as a resist is improved. Can be improved. Moreover, in 100 mol% of the resin (A), the proportion of the repeating unit (2) is 5 to 70 mol%, preferably 7 to 60 mol%, and more preferably 10 to 50 mol%. When the ratio of the repeating unit (2) is 5 mol% or more, the resolution can be improved. On the other hand, when the ratio is 70 mol% or less, the adhesion of the resist pattern to the substrate can be improved. .

  The repeating unit having an acid dissociable group other than the general formula (2) includes a repeating unit represented by the following formula and a structure in which a part of the alicyclic structure of these repeating units is substituted with a hydroxyl group or a cyano group. The repeating unit which has. In the following formulae, R is a hydrogen atom or a methyl group, and R ′ is a methyl group or an ethyl group.

  Further, the resin (A) may have one or more repeating units other than the repeating unit having an acid dissociable group (hereinafter referred to as “other repeating unit”). Examples of the polymerizable unsaturated monomer that gives the other repeating unit include, for example, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and tetracyclo (meth) acrylate. (Meth) acrylic having a bridged hydrocarbon skeleton such as decanyl, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, 3-hydroxyadamantyl (meth) acrylate, and adamantylmethyl (meth) acrylate Acid esters; having a bridged hydrocarbon skeleton of unsaturated carboxylic acids such as carboxynorbornyl (meth) acrylate, carboxytricyclodecanyl (meth) acrylate, and carboxytetracyclodecanyl (meth) acrylate Carboxyl group-containing esters; methyl (meth) acrylate, (meta Ethyl acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Propyl, 3-hydroxypropyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, (meth) acrylic acid 2 -(Meth) acrylic acid not having a bridged hydrocarbon skeleton such as cyclopentyloxycarbonylethyl, 2- (cyclohexyloxycarbonylethyl) (meth) acrylate, 2- (4-methoxycyclohexyl) oxycarbonylethyl (meth) acrylate Esters: α-hydroxymethyl Α-hydroxymethyl acrylate esters such as methyl acrylate, α-hydroxymethyl ethyl acrylate, α-hydroxymethyl acrylate n-propyl, α-hydroxymethyl acrylate n-butyl; (meth) acrylonitrile, α-chloro Unsaturated nitrile compounds such as acrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itaconnitrile; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, fumaramide, mesaconamide , Citraconic amide, itaconic amide, etc .; N- (meth) acryloylmorpholine, N-vinyl-ε-caprolactam, N-vinyl pyrrolidone, vinyl pyridine, vinyl imi Other nitrogen-containing vinyl compounds such as sol; unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid Acids (anhydrides); 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, (meth) Carboxyl group-containing esters having no bridged hydrocarbon skeleton of unsaturated carboxylic acid such as 4-carboxycyclohexyl acrylate; α- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-β- Fluoro-γ-butyrolactone, α- (meth) acryloyloxy-β-hydroxy-γ-bu Lolactone, α- (meth) acryloyloxy-β-methyl-γ-butyrolactone, α- (meth) acryloyloxy-β-ethyl-γ-butyrolactone, α- (meth) acryloyloxy- 竅 Cβ-dimethyl-γ-butyrolactone , Α- (meth) acryloyloxy-β-methoxy-γ-butyrolactone, β- (meth) acryloyloxy-γ-butyrolactone, α-fluoro-β- (meth) acryloyloxy-γ-butyrolactone, α-hydroxy-β -(Meth) acryloyloxy-γ-butyrolactone, α-methyl-β- (meth) acryloyloxy-γ-butyrolactone, α-ethyl-β- (meth) acryloyloxy-γ-butyrolactone, α, α-dimethyl-β -(Meth) acryloyloxy-γ-butyrolactone, α-methoxy-β- (meth) a Monofunctional monomers such as (meth) acryloyloxylactone compounds having no acid dissociable groups such as acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-δ-mevalonolactone, and 1,2-adamantane Bridged hydrocarbon skeletons such as diol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate Multifunctional monomer having: methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,5-dimethyl -2,5-hexanediol di (meth) acrylate 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzenedi (meth) acrylate, 1,3-bis (2- A polyfunctional monomer such as a polyfunctional monomer having no bridged hydrocarbon skeleton such as hydroxypropyl) benzenedi (meth) acrylate can be mentioned.

  Although there is no limitation in particular about the molecular weight of the said resin (A), Usually, 3000-30000 in the polystyrene conversion weight average molecular weight (henceforth "Mw") by gel permeation chromatography (henceforth "GPC"). , Preferably 4000-30000, more preferably 4000-25000, particularly preferably 5000-25000, most preferably 5000-20000. When the Mw of the resin (A) is 3000 or more, the heat resistance when used as a resist can be further improved, and when it is 30000 or less, the developability when used as a resist can be further improved. Further, the ratio (Mw / Mn) between the Mw of the resin (A) and the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) by GPC can be set to various values as necessary. . Usually, this ratio is 1-5, preferably 1-4, more preferably 1-3.

  The production method of the resin (A) is not particularly limited. Usually, a radical polymerization initiator is used together with hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, transition metal catalysts, etc. Accordingly, it can be obtained by polymerizing a polymerizable unsaturated monomer corresponding to each repeating unit in an appropriate solvent in the presence of a chain transfer agent. As the reaction conditions in the above polymerization, for example, the reaction temperature is usually 0 to 120 ° C., preferably 0 to 90 ° C., and the reaction time is usually 1 to 48 hours, preferably 1 to 24 hours. can do.

  Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; alkyls such as methyl ethyl ketone and methyl isobutyl ketone. Ketones; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; chlorobutanes, bromohexanes, dichloroethanes, hexamethylenedi Halogenated hydrocarbons such as bromide and chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; aels such as tetrahydrofuran, dimethoxyethanes and diethoxyethanes It can be mentioned. These solvents can be used alone or in admixture of two or more.

  Furthermore, the resin (A) is more preferable as the impurities such as halogen and metal are less because the sensitivity, resolution, process stability, pattern shape and the like can be further improved when a resist is used. Therefore, it is preferable to carry out purification for removing impurities after producing the resin (A). Examples of the purification method of the resin (A) include chemical purification methods such as reprecipitation, water washing and liquid-liquid extraction, and these chemical purification methods and physical purification methods such as ultrafiltration and centrifugation. Combinations can be mentioned.

<2> Acid generator (B)
The acid generator (B) of the present invention has an action of generating an acid upon exposure. Then, by the action of the acid, the acid dissociable group in the resin (A) is dissociated to make the exposed portion of the resist film easily soluble in an alkali developer, and a positive resist pattern can be formed. The acid generator (B) is preferably a compound capable of generating an acid upon irradiation with an actinic ray or radiation having a wavelength of 220 nm or less. Specific examples of the acid generator (B) include onium salts, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds. Specific examples of the onium salt, the halogen-containing compound, the diazoketone compound, the sulfone compound, and the sulfonic acid compound include the following compounds. In addition, the said acid generator (B) may be used individually by 1 type, or can also use 2 or more types together.

(1) Onium salt Examples of the onium salt include iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n- Butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, cyclohexyl 2-oxocyclohexyl Methylsulfonium trifluoromethanesulfonate, cyclohexyl, 2-oxocyclohexyl, methylsulfonium nonafluoro-n-butanesulfonate, cyclohexyl, 2-oxocyclohexyl, methylsulfonium perfluoro-n-octanesulfonate, dicyclohexyl, 2-oxocyclohexylsulfonium trifluoro L-methanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium nonafluoro-n-butanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium perfluoro-n-octanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium nona Fluoro-n-bu Sulfonate, 2-oxocyclohexyldimethylsulfonium perfluoro-n-octanesulfonate, 4-hydroxyphenyl phenyl methylsulfonium p-toluenesulfonate, 4-hydroxyphenyl benzyl methylsulfonium p-toluenesulfonate, 1-naphthyldimethylsulfonium Trifluoromethanesulfonate, 1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 1-naphthyldimethylsulfonium perfluoro-n-octanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium nonafluoro-n-butane Sulfonate, 1-naphthyldiethylsulfonium perfluoro-n-octane sulphonate 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-cyano-1-naphthyldimethylsulfonium perfluoro-n-octanesulfonate, 4- Cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-cyano-1-naphthyldiethylsulfonium perfluoro-n-octanesulfonate, 4-nitro-1 -Naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-nitro-1-naphth Didimethylsulfonium perfluoro-n-octanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-nitro-1-naphthyldiethylsulfonium Perfluoro-n-octanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldimethylsulfonium perfluoro- n-octanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfonium Nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldiethylsulfonium perfluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium nonafluoro-n -Butanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium perfluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate 4-hydroxy-1-naphthyldiethylsulfonium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxy Phenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) Tetrahydrothiophenium perfluoro-n-octanesulfonate 1- (4-methoxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- ( 4-methoxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate 1- (2,4-dimethoxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (2, -Dimethoxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (2,4-dimethoxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-hydroxynaphthalen-1-yl) Tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-propoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-i-propoxynaphthalen-1-yl) tetrahydrothiophenium trifluor Olomethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-t-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4 -Ethoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-propoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4 -I- Lopoxinaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4 -T-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4 -Methoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n -Propoxynaphthalene 1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-i-propoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxy) Naphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4-t-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4-methoxy Methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-methoxymethoxynaphthalene-1 -Yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydro Thiophenium nonafluoro-n-butanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- [4- (1-methoxyethoxy) naphthalene-1 -Yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (1-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- [4- (1-methoxye Xyl) naphthalen-1-yl] tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- [4- (2-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- [4- (2-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium perfluoro-n- Octane sulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n- Tansulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n- Octanesulfonate, 1- (4-n-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-propoxycarbonyloxynaphthalene) -1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4- i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- ( 4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium Fluoromethanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothio Phenium perfluoro-n-octanesulfonate, 1- (4-t-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-t-butoxycarbonyloxynaphthalen-1-yl) Tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-t-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- [4- (2-te Lahydrofuranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-tetrahydrofuranyloxy) naphthalen-1-yl] tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- [4- (2-tetrahydrofuranyloxy) naphthalen-1-yl] tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- [4- (2-tetrahydropyranyloxy) naphthalen-1-yl] tetrahydro Thiophenium trifluoromethanesulfonate, 1- [4- (2-tetrahydropyranyloxy) naphthalen-1-yl] tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- [4- (2-tetrahydropyranyloxy) ) Phthalen-1-yl] tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-benzyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-benzyloxynaphthalene-1- Yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-benzyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (1-naphthalen-1-ylacetate) Talen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (1-naphthalen-1-ylacetomethalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (1-naphthyla) Tomechiru) can be exemplified tetrahydrothiophenium perfluoro -n- octanesulfonate like.

(2) Halogen-containing compound Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include (trichloro, phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine, 1-naphthylbis (trichloromethyl) -s-triazine, etc. And methyl) -s-triazine derivatives and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.

(3) Diazoketone compound Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like. Specific examples of preferred diazo ketones include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphtho of 2,3,4,4′-tetrahydroxybenzophenone. Quinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-naphthoquinonediazide-4-sulfonic acid ester of 1,1,1-tris (4-hydroxyphenyl) ethane or 1 , 2-naphthoquinonediazide-5-sulfonic acid ester and the like.

(4) Sulfone Compound Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds. Specific examples of preferred sulfone compounds include 4-tolylphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like.

(5) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, alkyl sulfonic acid imides, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept. -5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2. 2.1] Hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide nonafluoro-n-butanesulfonate, N-hydroxysuccinimide perfluoro- n-Octanesulfone 1,8-naphthalenedicarboxylic imide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic imide nonafluoro-n-butane sulfonate, 1,8-naphthalenedicarboxylic imide perfluoro-n-octane sulfonate, etc. it can.

  Among the above compounds, in particular, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro- n-butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, cyclohexyl, 2-oxocyclohexyl, methylsulfonium trifluoromethanesulfonate, cyclohexyl, 2-oxocyclohexyl, methylsulfonium nonafluoro-n- Butanesulfonate, dicyclohexyl, 2-oxocyclohexylsulfonium trifluoro Tansulfonate, dicyclohexyl 2-oxocyclohexylsulfonium nonafluoro-n-butanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1- (3,5-dimethyl- 4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium Trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 1 (1-naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide nonafluoro-n-butanesulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate 1,8-naphthalenedicarboxylic acid imidononafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-hydroxy-1-naphthyl Tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium nonafluoro- n-butanesulfonate and the like are preferable.

  The content of the acid generator (B) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 0.5 to 100 parts by mass of the resin (A). -10 parts by mass. When the total content is 0.1 parts by mass or more, it is preferable because it is possible to prevent a decrease in sensitivity and developability. On the other hand, when the content is 20 parts by mass or less, a decrease in transparency to radiation is prevented, This is preferable because a rectangular resist pattern can be easily obtained.

<3> Phenolic compounds (C)
The phenolic compound (C) of the present invention has the effect of increasing the solubility of the exposed portion and the acid generation efficiency from the acid generator (B), and the positive radiation-sensitive resin composition of the present invention. It is effective for increasing the sensitivity of Moreover, since phenolic compounds generally have absorption at 193 nm, the phenolic compound (C) of the present invention is also useful for controlling the resist shape after patterning.

この中で、溶解性及び１９３ｎｍでの吸収強度の観点から、ベンゼン環数が２〜４の化合物が好ましく挙げることができる。特に、フェノール性化合物（Ｃ）のベンゼン環が有する水酸基（フェノール性水酸基）の合計数は、２〜８であることが好ましく、より好ましくは２〜６、更に好ましくは２〜４である。
これらのフェノール性化合物（Ｃ）の具体例としては、下記に列挙されているものを例示することができる。 The phenolic compound (C) is a compound having a structure having a hydroxyl group in the benzene ring, and the number and structure of the benzene ring and the hydroxyl group are not particularly limited as long as it has the basic structure. A compound having the following structure can be used [except for a polymer having a structural unit represented by the following formula (i)] .

Among these, from the viewpoints of solubility and absorption intensity at 193 nm, compounds having 2 to 4 benzene rings can be preferably mentioned. In particular, the total number of hydroxyl groups (phenolic hydroxyl groups) contained in the benzene ring of the phenolic compound (C) is preferably 2 to 8, more preferably 2 to 6, and further preferably 2 to 4.
Specific examples of these phenolic compounds (C) include those listed below.

［上記一般式（３）中、ａ及びｂは独立に０〜３の整数であり（但し、ａとｂは同時に０ではない）、ｘ及びｙは独立に０〜３の整数であり、そしてａ＋ｘ≦５で、ｂ＋ｙ≦５である。］

[In the above general formula (3), a and b are independently integers of 0 to 3 (provided that a and b are not 0 at the same time), x and y are independently integers of 0 to 3, and a + x ≦ 5 and b + y ≦ 5. ]

［上記一般式（４）中、ａ、ｂ及びｃは独立に０〜３の整数であり（但し、ａ、ｂ及びｃは同時に０ではない）、ｘ、ｙ及びｚは独立に０〜３の整数であり、そしてａ＋ｘ≦５、ｂ＋ｙ≦４、ｃ＋ｚ≦５である。］

[In the general formula (4), a, b and c are each independently an integer of 0 to 3 (provided that a, b and c are not 0 at the same time), and x, y and z are independently 0 to 3 And a + x ≦ 5, b + y ≦ 4, and c + z ≦ 5. ]

［上記一般式（５）中、Ｘ_１は独立に水素原子又はアルキル基であり、ｐは独立に１又は２である。］

[In the above general formula (5), X ₁ is independently a hydrogen atom or an alkyl group, and p is independently 1 or 2. ]

［上記一般式（６）中、ａ_１〜ａ_１５は、独立に水素原子、Ｃ_１〜Ｃ_４のアルキル基、Ｃ_１〜Ｃ_４のアルコキシ基又は水酸基である。但し、ａ_１〜ａ_５、ａ_６〜ａ_１０及びａ_１１〜ａ_１５の各群において、少なくとも１つは水酸基である。］

[In General Formula (6), a _{1 to} a ₁₅ are each independently a hydrogen atom, a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group, or a hydroxyl group. However, in each group of a _{1 to} a ₅ , a _{6 to} a ₁₀ and a _{11 to} a ₁₅ , at least one is a hydroxyl group. ]

［上記一般式（７）中、ａ_２９〜ａ_４２は、独立に水素原子、Ｃ_１〜Ｃ_４のアルキル基又は水酸基である。但し、ａ_２９〜ａ_３２、ａ_３３〜ａ_３７及びａ_３８〜ａ_４２の各群において、少なくとも１つは水酸基である。］

[In the general formula (7), a _{29 to} a ₄₂ are independently a hydrogen atom, a C _{1 to} C ₄ alkyl group or a hydroxyl group. _However, in each group of _{a 29 ~a 32, a 33 ~a} 37 and _a 38 _{~a 42,} at least one is a hydroxyl group. ]

  As said phenolic compound (C), Preferably the following compounds are mentioned.

  The content of the phenolic compound (C) is preferably 0.5 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the resin (A). When the content of the phenolic compound (C) is 0.5 parts by mass or more, a resist pattern collapse margin which is an effect of the invention of the present application is sufficiently obtained, which is preferable. On the other hand, the content of 5 parts by mass or less is preferable because the transparency of the resist film can be prevented from being lowered and sufficient resolution can be obtained.

<4> Other components The radiation sensitive resin composition of the present invention may contain an acid diffusion controller. The acid diffusion controller controls the diffusion phenomenon in the resist film of the acid generated from the acid generator (B) by exposure, and has an action of suppressing an undesirable chemical reaction in a non-exposed region. Therefore, the storage stability of the obtained radiation sensitive resin composition can be further improved by blending the acid diffusion controller. In addition, by adding the acid diffusion control agent, the resolution as a resist can be further improved, and a change in the line width of the resist pattern due to a change in the holding time (PED) from exposure to development processing can be suppressed. As a result, a radiation sensitive resin composition having extremely excellent process stability is obtained, which is preferable.

  The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment during the resist pattern formation step. Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (8) (hereinafter referred to as “nitrogen-containing compound (i)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (i)”). "Nitrogen-containing compound (b)"), polyamino compounds and polymers having 3 or more nitrogen atoms (hereinafter collectively referred to as "nitrogen-containing compound (c)"), amide group-containing compounds, urea compounds And nitrogen-containing heterocyclic compounds. Of these nitrogen-containing organic compounds, nitrogen-containing compounds (a), nitrogen-containing compounds (b) and nitrogen-containing heterocyclic compounds are preferred. Moreover, the said acid diffusion control agent may be used individually by 1 type, and may use 2 or more types together.

In the general formula (8), each R ⁵ , R ⁶ and R ⁷ is independently a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or A substituted or unsubstituted aralkyl group is shown. Here, examples of the substituted or unsubstituted linear, branched, or cyclic alkyl group include those having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. Group, cyclopentyl group, cyclohexyl group and the like.

  Specific examples of the nitrogen-containing compound (a) include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine and the like. Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine Di (cyclo) alkylamines such as dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri -N-octylamine, tri-n-nonylamine, tri-n-decylamine, Tri (cyclo) alkylamines such as cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline , Aromatic amines such as 4-nitroaniline, diphenylamine, triphenylamine and naphthylamine.

  Specific examples of the nitrogen-containing compound (b) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4, 4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-amino Phenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-Aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-me Tilethyl] benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether and the like.

  Examples of the nitrogen-containing compound (c) include polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, and the like.

  Specific examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, and Nt-butoxycarbonyldi-n-decylamine. Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, 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-butoxycarbonyl Hexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonyl hex Methylenediamine, 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-phenylbenz Nt-butoxycarbonyl group-containing amino compounds such as imidazole, formamide, N-methylformamide N, N- dimethylformamide, acetamide, N- methylacetamide, N, N- dimethylacetamide, propionamide, benzamide, pyrrolidone, N- methylpyrrolidone and the like.

  Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri -N-butylthiourea etc. are mentioned.

  Specific examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, and Nt-butoxycarbonyl-2-phenylbenzimidazole. Pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide , Pyridines such as quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine; piperazines such as piperazine, 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine , 3-pi Rijino-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane.

  The amount of the acid diffusion controller is usually 15 parts by mass or less, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the resin (A). Especially preferably, it is 0.001-5 mass parts, Most preferably, it is 0.2-5 mass parts. It is preferable to adjust the blending amount of the acid diffusion control agent to 15 parts by mass or less, since it is possible to suppress a decrease in sensitivity as a resist and developability of an exposed part. Moreover, it is preferable to make the compounding amount of the acid diffusion control agent 0.001 part by mass or more because a decrease in pattern shape and dimensional fidelity as a resist due to process conditions can be suppressed.

  Moreover, the radiation sensitive resin composition of this invention can mix | blend 1 type (s) or 2 or more types together with the alicyclic additive which has an acid dissociable group. The alicyclic additive has an effect of further improving dry etching resistance, pattern shape, adhesion to the substrate, and the like. Here, the “acid-dissociable group” refers to a group from which a protecting group is dissociated by the action of an acid, such as a group that dissociates by the action of an acid to form a carboxyl group, a hydroxyl group, a sulfonic acid group, or the like. It is done. When mix | blending the said alicyclic additive, the compounding quantity is 50 mass parts or less normally with respect to 100 mass parts of said resin (A), Preferably it is 40 mass parts or less, More preferably, it is 30 mass parts or less. . It is preferable to adjust the blending amount of the alicyclic additive to 50 parts by mass or less because a decrease in heat resistance as a resist can be prevented.

  Examples of the alicyclic additives include 1-adamantane carboxylate t-butyl, 1-adamantane carboxylate t-butoxycarbonylmethyl, 1,3-adamantane dicarboxylate di-t-butyl, 1-adamantane acetate t- Adamantane derivatives such as butyl, 1-adamantane acetate t-butoxycarbonylmethyl, 1,3-adamantanediacetate di-t-butyl, 2,5-dimethyl-2,5-di (adamantylcarbonyloxy) -n-hexane Deoxycholate t-butyl, deoxycholate t-butoxycarbonylmethyl, deoxycholate 2-ethoxyethyl, deoxycholate 2-cyclohexyloxyethyl, deoxycholate 3-oxocyclohexyl, deoxycholate tetrahydropyranyl, deoxy Mevalonolac cholate Deoxycholic acid esters such as phosphonic acid ester; t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid, 2-cyclohexyloxyethyl lithocholic acid, 3-oxocyclohexyl lithocholic acid, tetrahydropyranyl lithocholic acid And lithocholic acid esters such as lithocholic acid mevalonolactone ester.

  Moreover, surfactant can be mix | blended with the radiation sensitive resin composition of this invention. The surfactant exhibits an effect of improving coatability, developability and the like. When blending the surfactant, the blending amount is usually 2 parts by mass or less, preferably 1.5 parts by mass or less, with respect to 100 parts by mass in total of the resin (A) and the acid generator (B). More preferably, it is 1 mass part or less. Moreover, the said surfactant may be used individually by 1 type, and may use 2 or more types together.

  Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene In addition to nonionic surfactants such as glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F173 (manufactured by Dainippon Ink and Chemicals), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( Asahi Glass Co., Ltd.).

  Furthermore, additives other than those described above can be appropriately blended as necessary within a range not impairing the object of the present invention. As additives other than the above, for example, an antihalation agent, an adhesion assistant, a storage stabilizer, an antifoaming agent, and the like can be blended.

<5> Preparation of Radiation Sensitive Resin Composition Solution The radiation sensitive resin composition of the present invention is usually dissolved in a solvent when used, and then filtered with a filter having a pore size of 0.2 μm as necessary. Thus, it is prepared as a radiation sensitive resin composition solution. The concentration of the radiation-sensitive resin composition of the present invention in the radiation-sensitive resin composition solution is generally 5 to 50% by mass, preferably 5 to 40% by mass, more preferably 5 to 30%, based on the total solid content concentration. % By mass, particularly preferably 5 to 25% by mass.

  Examples of the solvent include 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, and 3,3-dimethyl-2. -Linear or branched ketones such as butanone, 2-heptanone, 2-octanone; cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, isophorone, etc. Cyclic ketones; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol monoalkyl ether acetates such as tate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, 2-hydroxypropionic acid Ethyl, 2-hydroxypropionate n-propyl, 2-hydroxypropionate i-propyl, 2-hydroxypropionate n-butyl, 2-hydroxypropionate i-butyl, 2-hydroxypropionate sec-butyl, 2-hydroxy Alkyl 2-hydroxypropionates such as t-butyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropio In addition to alkyl 3-alkoxypropionates such as methyl 3-ethyl, ethyl 3-ethoxypropionate, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether Teracetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-acetate -Propyl, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzylethyl ester Ter, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and the like can be mentioned.

  In particular, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionate and alkyl 3-alkoxypropionate are coatable and the composition dissolves in a solvent. From the viewpoint of sex. Moreover, the said solvent may be used individually by 1 type, and may use 2 or more types together.

<6> Method for Forming Resist Pattern The radiation-sensitive resin composition of the present invention is particularly useful as a chemically amplified resist. In the chemically amplified resist, the protecting group of the acid dissociable group in the resin (A) is dissociated by the action of the acid generated from the acid generator (B) by exposure. Thereby, the solubility with respect to the alkali developing solution of the exposed part of a resist becomes high. As a result, the exposed portion is dissolved and removed by the alkali developer, and a positive resist pattern can be obtained.

  When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution was coated with, for example, a silicon wafer or aluminum by an appropriate application means such as spin coating, cast coating, or roll coating. A resist film is formed by coating on a substrate such as a wafer. In some cases, after heat treatment (hereinafter referred to as “PB”) in advance, the resist film is exposed to form a predetermined resist pattern. Depending on the type of acid generator used, etc., the actinic ray or radiation used in the exposure can be appropriately selected, for example, having a wavelength of 220 nm or less, particularly ArF excimer laser (wavelength 193 nm). Is preferred.

  When forming a resist pattern from the radiation-sensitive resin composition of the present invention, if a heat treatment (hereinafter referred to as “PEB”) is performed after exposure, the dissociation reaction of the acid-dissociable group in the resin (A) is performed. Is preferable because it proceeds smoothly. The heating condition of the PEB varies depending on the composition of the radiation sensitive resin composition, but is usually 30 to 200 ° C, preferably 50 to 170 ° C.

  In forming a resist pattern from the radiation sensitive resin composition of the present invention, for example, in order to maximize the potential of the radiation sensitive resin composition, it is disclosed in, for example, Japanese Patent Publication No. 6-12452. Thus, an organic or inorganic antireflection film can be formed on the substrate to be used. 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. Furthermore, 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- [4.3.0] An alkaline aqueous solution in which at least one of alkaline compounds such as 5-nonene is dissolved is preferable.

  Moreover, an organic solvent can also be added to the developing solution which consists of said 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. The said organic solvent may be used individually by 1 type, and may use 2 or more types together.

  The concentration of the alkaline aqueous solution is usually 10% by mass or less, preferably 8% by mass or less, and more preferably 5% by mass or less. If the concentration of the alkaline aqueous solution exceeds 10% by mass, the unexposed area may be dissolved in the developer, which is not preferable. Moreover, when adding the said organic solvent to the developing solution which consists of the said alkaline aqueous solution, the usage-amount of the said organic solvent becomes like this. Preferably it is 100 volume% or less with respect to the said alkaline aqueous solution, More preferably, it is 80 volume% or less. If the amount of the organic solvent used exceeds 100% by volume, the developability is lowered, and there is a possibility that the remaining development in the exposed area may increase, such being undesirable.

  An appropriate amount of a surfactant or the like can be added to the developer composed of the alkaline aqueous solution. In addition, after developing with the developing solution which consists of alkaline aqueous solution, generally it wash | cleans with water and dries.

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, the part is based on mass unless otherwise specified.
Each measurement and evaluation in the synthesis example was performed as follows.
(1) Mw and Mn
Gel permeation based on monodisperse polystyrene using GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation under the analysis conditions of a flow rate of 1.0 ml / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C. It was measured by chromatography (GPC). Further, the degree of dispersion Mw / Mn was calculated from the measurement results.
^{(2) 13} C-NMR analysis of ¹³ C-NMR analysis the polymer, using JEOL Ltd. "JNM-EX270", was performed using CDCl ₃ as solvent for measurement.

  Hereinafter, Synthesis Example 1 and Synthesis Example 2 will be described. In the following synthesis examples, the mol% in the description of each compound [for example, 42.40 g (40 mol%) of “compound (M-1)” in the following synthesis example 1] means the monomer solution in each synthesis example. The mol% is shown when the total monomer content is 100 mol%. Moreover, the detail of each compound is shown below.

<Synthesis Example 1>
42.40 g (40 mol%) of the above compound (M-1), 45.24 g (45 mol%) of the compound (M-2-1), 12.37 g (15 mol%) of the compound (M-3-1) A monomer solution was prepared by dissolving in 200 g of 2-butanone and further adding 8.33 g of dimethyl 2,2′-azobis (2-methylpropionate).
On the other hand, a 1000 ml three-necked flask charged with 100 g of 2-butanone was prepared and purged with nitrogen for 30 minutes. After the nitrogen purge, the contents in the three-necked flask were heated to 80 ° C. while stirring, and the monomer solution prepared in advance was added dropwise over 3 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water to 30 ° C. or lower, poured into 2000 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 400 g of methanol as a slurry, then filtered and dried at 50 ° C. for 17 hours to obtain a white powder polymer (73 g, yield 73%). . This polymer has Mw of 7200, Mw / Mn of 1.8, and as a result of ¹³ C-NMR analysis, the polymer is derived from compound (M-1), compound (M-2-1), and compound (M-3-1). The content of each repeating unit was 37.6: 49.0: 13.4 (mol%). This polymer is referred to as “resin (A-1)”.

Moreover, the following resins (A-2) to (A-7) and (a-1) were respectively prepared in the same manner as in Synthesis Example 1 by using the respective compounds.
Resin (A-2);
(M-1) / (M-2-1) / (M-3-1) = 53.3 / 14.2 / 32.5 (mol%), molecular weight: 7200, Mw / Mn: 1.7
Resin (A-3);
(M-1) / (M-2-1) / (M-3-2) = 54.7 / 35.5 / 9.8 (mol%), molecular weight: 8100, Mw / Mn: 1.7
Resin (A-4);
(M-1) / (M-2-1) / (M-3-3) = 59.7 / 25.2 / 15.1 (mol%), molecular weight: 7700, Mw / Mn: 1.8
Resin (A-5);
(M-1) / (M-2-2) / (M-3-1) = 51.2 / 17.5 / 30.7 (mol%), molecular weight: 7500, Mw / Mn: 1.7
Resin (A-6);
(M-1) / (M-2-3) / (M-3-1) = 42.5 / 22.3 / 35.2 (mol%), molecular weight: 7100, Mw / Mn: 1.6
Resin (A-7);
(M-1) / (M-2-4) / (M-3-1) = 53.3 / 14.2 / 32.5 (mol%), molecular weight: 7800, Mw / Mn: 1.7
Resin (a-1);
(M-1) / (M-3-1) = 51.2 / 48.8 (mol%), molecular weight: 8000, Mw / Mn: 1.7

<Synthesis Example 2>
Compound (M-1) 53.92 g (50 mol%), Compound (M-2-1) 35.38 g (40 mol%), Compound (M-3-2) 10.69 g (10 mol%), A solution A in which 3.37 g of dimethyl 2,2′-azobis (2-methylpropionate) was dissolved in 251 g of 2-butanone was prepared.
Next, a 1000 ml three-necked flask charged with 2.81 g of CTA3 (chain transfer agent) and 15 g of 2-butanone was prepared and purged with nitrogen by a vacuum replacement method. After the nitrogen purge, the contents in the three-necked flask were heated to 80 ° C. with stirring, and after 15 minutes, Solution A was added dropwise over 3 hours using a liquid feed pump. After completion of dropping, the mixture was further stirred for 4 hours. After completion of the polymerization, the polymerization solution was allowed to cool and then cooled to 30 ° C. or lower. Thereafter, 11.17 g of dimethyl 2,2′-azobis (2-methylpropionate) was added to the polymerization solution, heated to 80 ° C. and stirred for 3 hours. After completion of the reaction, the solution was allowed to cool, cooled to 30 ° C. or lower, poured into 4000 g of isopropyl alcohol, and the precipitated white powder was filtered off. The filtered white powder was washed twice in a slurry with 2000 g of isopropyl alcohol, filtered, and dried at 60 ° C. for 17 hours to obtain a white powder polymer (85 g, 85% yield). ). This polymer has Mw of 7600 and Mw / Mn of 1.32. As a result of 13C-NMR analysis, the polymer was compound (M-1), compound (M-2-1), and compound (M-3-2). It was a copolymer having a content of each repeating unit represented by 53.1: 38.4: 8.5 (mol%). This polymer is referred to as “resin (A-8)”.
As the chain transfer agent, the following compounds were used.

<酸拡散抑制剤（Ｄ）>
Ｄ−１：Ｎ−ｔ−ブトキシカルボニル−２−フェニルベンズイミダゾール
Ｄ−２：３−ピペリジノ−１，２−プロパンジオール
Ｄ−３：Ｎ−ｔ−ブトキシカルボニル−４−ヒドロキシピペリジン
Ｄ−４：２，６−ジイソプロピルアニリン
<溶剤（Ｅ）>
Ｅ−１：プロピレングリコールモノメチルエーテルアセテート
Ｅ−２：２−ヘプタノン
Ｅ−３：シクロヘキサノン
Ｅ−４：γ−ブチロラクトン << Evaluation of radiation sensitive resin composition >>
Various evaluations are performed on each composition composed of the components shown in Table 1, and the evaluation results are shown in Table 2. The components other than the resin shown in Table 1 are as follows. In the table, “parts” are based on mass unless otherwise specified.
<Acid generator (B)>
B-1: 1- (4-n-butoxynaphthyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate B-2: triphenylsulfonium nonafluoro-n-butanesulfonate B-3: 4-cyclohexylphenyldiphenylsulfonium nona Fluoro-n-butanesulfonate
<Phenol compound (C)>
C-1, C-2 and C-3: Each compound having the structure shown below

<Acid diffusion inhibitor (D)>
D-1: Nt-butoxycarbonyl-2-phenylbenzimidazole D-2: 3-piperidino-1,2-propanediol D-3: Nt-butoxycarbonyl-4-hydroxypiperidine D-4: 2 , 6-Diisopropylaniline
<Solvent (E)>
E-1: Propylene glycol monomethyl ether acetate E-2: 2-heptanone E-3: Cyclohexanone E-4: γ-Butyrolactone

<Evaluation method>
As a substrate, a silicon wafer having a 77 nm-thick antireflection film (Nissan Chemical Co., “ARC29A”) formed on the surface was used. Each composition solution was applied onto a substrate by spin coating, and PB was performed on a hot plate at 100 ° C. for 60 seconds to form a resist film having a thickness of 0.20 μm. The following (1) to (3) were evaluated using the formed resist film.

(1) Sensitivity:
The resist film formed by the above method was exposed through a mask pattern by a full-field reduction projection exposure apparatus S306C (numerical aperture 0.75) manufactured by Nikon. Thereafter, PEB is performed at 110 ° C. for 60 seconds, and then developed with a 2.38 mass% aqueous TMAH (tetramethylammonium hydroxide) solution at 25 ° C. for 60 seconds, washed with water, and dried to form a positive resist pattern. Formed. At this time, an exposure amount formed in a one-to-one line-and-space with a line width of 100 nm is defined as an optimum exposure amount, and the optimum exposure amount is set as a line width formed through a one-to-one line-and-space mask having a dimension of 100 nm. Sensitivity was used.
(2) Resolution:
The minimum dimension (nm) of the line and space pattern (1L1S) resolved when exposed at the optimum exposure amount was defined as the resolution.
(3) Pattern collapse margin:
In the seven-line 100 nm 1L1S pattern, the difference between the exposure amount at which three or more lines collapse for the first time and the optimum exposure amount was defined as a pattern collapse margin (hereinafter referred to as “fall margin”). That is, the fall margin is defined as follows.
As the exposure amount is gradually increased from the optimum exposure amount (P1) of each resist film, the line width of the pattern gradually becomes thinner due to the exposure, and the pattern falls sideways from a state perpendicular to the silicon wafer. End up. At this time, the exposure amount at which three or more patterns collapsed was defined as the exposure amount (P2), and the difference from the optimum exposure amount (P1) was defined as the collapse margin as shown in the following equation. Whether the pattern was perpendicular to the silicon wafer or tilted sideways was observed with a scanning electron microscope (Hitachi High-Technologies Corporation “S-9220”). In addition, the larger this value is, the more difficult the pattern is to fall, which means that the resist is excellent.
Fall margin (J / m ² ) = exposure amount (P2) −optimal exposure amount (P1)

  As is apparent from Table 2, it was found that when the positive radiation sensitive resin composition of the present invention was used, the resolution was high and the pattern collapse margin was improved.

Claims (4)

(A) Alkali-insoluble or alkali-soluble resin containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) Generation of radiation-sensitive acid A positive radiation sensitive resin composition comprising an agent and (C) a phenolic compound [excluding a polymer having a structural unit represented by the following formula (i)] .

[In General Formula (1), R ¹ represents a methyl group or a hydrogen atom, and k is 0 or 1. ]

[In General Formula (2), R ² represents a methyl group, a fluorine atom or a hydrogen atom, R ³ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and R ⁴ represents a monovalent organic group. Represents a group, m is an integer of 0 to 5, and n is 1 or 2. ]

The positive radiation sensitive resin composition according to claim 1, wherein the phenolic compound (C) has 2 to 4 benzene rings. The positive radiation-sensitive resin composition according to claim 2, wherein the total number of hydroxyl groups of the benzene ring in the (C) phenolic compound is 2 to 8. The positive radiation sensitive resin composition according to any one of claims 1 to 3, wherein a content of the (C) phenolic compound is 0.5 to 5 parts by mass with respect to 100 parts by mass of the (A) resin. object.