JP2004210771A - Norbornene-based compound, silicon-containing compound, polysiloxane, and radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new polysiloxane having a fluorine-containing norbornane skeleton, having high transparency to radiations of ≤200nm wavelength, excellent in resolution and useful as a resin component of a resist easily controlled its solubility to an alkali developing solution, a new silicon-containing compound useful as a raw material and the like for synthesizing the polysiloxane, a new norbornene-based compound useful as a raw material and the like for synthesizing the silicon-containing compound, and a radiation-sensitive resin composition containing the polysiloxane. <P>SOLUTION: The norbornene-based compound is expressed by general formula (α) (wherein n expresses 0 or 1). The silicon-containing compound has a structure of the norbornene to which triethoxysilane or the like is added. The polysiloxane has a structural unit derived from the silicon-containing compound. The radiation-sensitive resin composition contains the polysiloxane and a radiation-sensitive acid generator. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a novel silicon-containing compound useful as a raw material for synthesizing a novel polysiloxane having a fluorine atom-containing norbornane skeleton, a novel norbornene-based compound useful as a raw material for synthesizing the silicon-containing compound, the polysiloxane, and the polysiloxane. The present invention relates to a radiation-sensitive resin composition contained therein.

In recent years, demands for higher density and higher integration of LSIs (highly integrated circuits) have been increasing, and accordingly, miniaturization of wiring patterns has been rapidly progressing.
As one of means that can respond to such miniaturization of wiring patterns, there is a method of shortening the wavelength of radiation used in a lithography process. In recent years, g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm) have been used. Instead of ultraviolet light, far ultraviolet light represented by KrF excimer laser (wavelength 248 nm) or ArF excimer laser (wavelength 193 nm), electron beam, X-ray, or the like is used, and F ₂ excimer laser (wavelength 157 nm) is also being considered.
By the way, novolak resins, poly (vinylphenol), and the like have been used as resin components in conventional resist compositions, but these materials contain an aromatic ring in the structure and have strong absorption at a wavelength of 193 nm. Therefore, for example, in a lithography process using an ArF excimer laser, high accuracy corresponding to high sensitivity, high resolution, and high aspect ratio cannot be obtained.
Therefore, a resin component for a resist that is transparent to a wavelength of 200 nm or less and has a dry etching resistance equal to or higher than that of an aromatic ring is required. One such example is a siloxane-based polymer. MIT RRKunz et al. Have shown that polysiloxane-based polymers have excellent transparency at wavelengths of 200 nm or less, particularly at 157 nm, and this polymer has been reported to be 193 nm or less. It is reported that it is suitable for a resist material in a lithography process using a wavelength (for example, see Non-Patent Document 1). It is also known that a polysiloxane-based polymer has excellent dry etching resistance, and that a resist containing a polyorganosilsesquioxane having a ladder structure has high plasma resistance.

On the other hand, some resist materials using a siloxane-based polymer have already been reported. That is, a radiation-sensitive resin using a polysiloxane having an acid-dissociable group in a side chain in which an acid-dissociable group such as a carboxylic acid ester group or a phenol ether group is bonded to a silicon atom via one or more carbon atoms. A positive resist using a composition (for example, see Patent Document 1) and a polymer in which a carboxyl group of poly (2-carboxyethylsiloxane) is protected by an acid-dissociable group such as a t-butyl group (for example, Patent Document 2) And a resist resin composition using a polyorganosilsesquioxane having an acid dissociable ester group (see, for example, Patent Document 3). However, resist materials using these conventional acid-dissociable group-containing siloxane-based polymers are still not at a satisfactory level in terms of basic physical properties as a resist such as transparency to radiation, resolution, and developability. .
Further, a non-aromatic monocyclic or polycyclic hydrocarbon group having a carboxyl group or a bridged cyclic hydrocarbon group is present in the side chain, and at least a part of the carboxyl group is an acid labile group. A substituted siloxane-based polymer and a resist material using the polymer have been reported (for example, see Patent Document 4), and the resist material is a KrF excimer laser (wavelength 248 nm) or an ArF excimer laser (wavelength 193 nm). It is said that it has a small absorption, a good pattern shape, and excellent sensitivity, resolution, dry etching resistance and the like.
However, even if the siloxane-based polymer of Patent Document 4 is included, there are few types of siloxane-based polymers useful as a resin component of the resist material, and the siloxane-based polymer is effectively responsive to short-wavelength radiation and has a high dry etching resistance, The development of a new siloxane-based polymer that can provide a resist material having excellent basic physical properties has become an important issue from the viewpoint of technology development that can cope with rapid progress in miniaturization of semiconductor devices.

SPIE, 3678 (1999) P.13-23 JP-A-5-323611 JP-A-8-160623 JP-A-11-60733 JP-A-11-302382

An object of the present invention is to effectively respond to radiation having a wavelength of 200 nm or less represented by an ArF excimer laser (wavelength 193 nm) or an F ₂ excimer laser (wavelength 157 nm), have high transparency to radiation, have excellent resolution, and A novel polysiloxane having a fluorine atom-containing norbornane skeleton, which is easy to control the solubility of the component in an alkali developer, and is useful as a resin component of a resist excellent in sensitivity, developability, dry etching resistance and the like. An object of the present invention is to provide a novel norbornene-based compound useful as a raw material for synthesizing a silicon-containing compound, a novel silicon-containing compound useful as a raw material for synthesizing the polysiloxane, and a radiation-sensitive resin composition containing the polysiloxane.

The present invention firstly
It is composed of a norbornene-based compound represented by the following general formula (α) (hereinafter, referred to as “norbornene-based compound (α)”).

〔一般式（α）において、ｎは０または１である。〕

[In the general formula (α), n is 0 or 1. ]

The present invention, secondly,
It is composed of a silicon-containing compound represented by the following general formula (1) or (2) (hereinafter, referred to as “silicon-containing compound (a)”).

[In the general formula (1), X ¹ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom or a primary or secondary group. Or a tertiary amino group, a plurality of X ¹ may be the same or different, and Y ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogen group having 1 to 20 carbon atoms. A plurality of Y ^{1 s} may be the same or different from each other, x is an integer of 0 to 2, and n is 0 or 1.
In the general formula (2), X ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a primary, secondary or A tertiary amino group; n is 0 or 1; ]
In the silicon-containing compound (a), the silicon atom is bonded to the 2-position or 3-position of the bicyclo [2.2.1] heptane ring at the highest position.

The present invention is, thirdly,
The structural unit represented by the following general formula (I) (hereinafter, referred to as “structural unit (I)”) and the structural unit represented by the general formula (II) (hereinafter, referred to as “structural unit (II)”). Having a polystyrene equivalent weight average molecular weight of 500 to 1,000,000 (hereinafter referred to as "polysiloxane (A)") by gel permeation chromatography (GPC) and having at least one member selected from the group consisting of Become.

〔一般式（Ｉ）において、ｎは０または１である。
一般式（II）において、Ｘは水素原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、ハロゲン原子または１級、２級もしくは３級のアミノ基を示し、ｎは０または１である。〕

[In the general formula (I), n is 0 or 1.
In the general formula (II), X is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a primary, secondary or tertiary group. And n represents 0 or 1. ]

Fourth, the present invention provides:
(A) Among the polysiloxanes (A), resins which are alkali-insoluble or hardly alkali-soluble resins having an acid-dissociable group, and which become alkali-soluble when the acid-dissociable group is dissociated (hereinafter referred to as “polysiloxane”). (A1) ”) and (b) a radiation-sensitive resin composition containing a radiation-sensitive acid generator.

Hereinafter, the present invention will be described in detail.
Norbornene compound (α)
The norbornene-based compound (α) is converted into a norbornene derivative (α-1) substituted with an ester group by a Diels-Alder reaction between a corresponding vinyl compound substituted with an ester group and cyclopentadiene as shown in the following reaction formula, for example. '), The norbornene-based compound (α-1) where n = 0 in the general formula (α) can be synthesized by hydrolyzing the ester group, and these reactions are carried out by a conventional method. Can be implemented. In the above reaction process, the produced norbornene derivative (α-1 ′) further undergoes a Diels-Alder reaction with cyclopentadiene, and the norbornene-based compound (α-2) in which n = 1 in the general formula (α) is simultaneously formed. May be generated.
Further, a norbornene-based compound (α-2) is synthesized by subjecting the norbornene derivative (α-1 ′) to a Diels-Alder reaction with cyclopentadiene and a hydrolysis reaction of an ester group in the same manner as described above. be able to.

（式中、Ｒは有機カルボン酸残基である。）

(In the formula, R is an organic carboxylic acid residue.)

  The norbornene-based compound (α) is particularly useful as a raw material for synthesizing the silicon-containing compound (a) described below, and also used as a raw material for synthesizing related norbornene derivatives and norbornane derivatives, a raw material for synthesizing related polymers, and the like. Can be.

Silicon-containing compound (a)
In the general formulas (1) and (2), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of X ¹ and X ² include a methyl group, an ethyl group, an n-propyl group, and an i-propyl. Group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, 3-methylbutyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl Linear group such as a group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. , Branched or cyclic alkyl groups; aromatics such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, benzyl group, phenethyl group, α-naphthyl group and β-naphthyl group Hydrocarbon group; norbornyl group, tricyclodecanyl group, tetra tricyclodecanyl group, and the like can be given bridged hydrocarbon groups such as adamantyl groups.
Among these monovalent hydrocarbon groups, a methyl group, an ethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and the like are preferable.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms of X ¹ and X ² include, for example, one or more halogenated monovalent hydrocarbon groups of X ¹ and X ^2. An atom, preferably a group substituted by one or more fluorine atoms, more specifically, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoro-n-propyl group , Heptafluoro-n-propyl group, 4,4,4-trifluoro-n-butyl group, 3,3,4,4,4-pentafluoro-n-butyl group, pentafluorophenyl group, 4-t- Butoxytetrafluorophenyl group and the like.

Examples of the halogen atom for X ¹ and X ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among these halogen atoms, a fluorine atom and a chlorine atom are preferred.
Examples of the secondary or tertiary amino group of X ¹ and X ² include a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, an n-butylamino group, and a cyclopentylamino group. , Cyclohexylamino group, phenylamino group, benzylamino group, dimethylamino group, diethylamino group, di-i-propylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, dibenzylamino group and the like. it can.
As the amino group for X ¹ and X ² , an amino group, a dimethylamino group, a diethylamino group, a dicyclopentylamino group, a dicyclohexylamino group, a diphenylamino group, and the like are preferable.

As X ¹ in the general formula (1) and X ² in the general formula (2), particularly, a methyl group, an ethyl group, a 3,3,3-trifluoro-n-propyl group, a 4,4,4-triol Fluoro-n-butyl group, 3,3,4,4,4-pentafluoro-n-butyl group, pentafluorophenyl group, 4-t-butoxytetrafluorophenyl group, fluorine atom, chlorine atom, dimethylamino group, etc. Is preferred.
Further, x in the general formula (1) is preferably 0 or 1, and n in the general formulas (1) and (2) is preferably both 0 and 1.

  In the present invention, specific examples of particularly preferable silicon-containing compound (a) include compounds represented by the following formulas (1-1-1) to (1-1-3) and compounds represented by the following formula (1-2-1) ) To compounds represented by the formula (1-2-3).

  The silicon-containing compound (a) is obtained, for example, by reacting a norbornene-based compound (α) with a corresponding hydrosilane compound by a conventional hydrosilylation reaction in the presence of a hydrosilylation catalyst, in the absence of a solvent or in an appropriate solvent. Can be synthesized.

  The silicon-containing compound (a) is particularly useful as a raw material for synthesizing the polysiloxane (A) described below, and can also be used as a raw material for synthesizing other polysiloxanes and other related silicon-containing compounds.

Polysiloxane (A)
The polysiloxane (A) can be produced by polycondensing at least one silicon-containing compound (a) in the presence of an acidic catalyst or a basic catalyst in the absence of a solvent or in a solvent by a conventional method. In this polycondensation, the silicon-containing compound (a) may be partially or wholly used as a partial condensate.

Hereinafter, the polycondensation method for producing the polysiloxane (A) will be described.
Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, n-propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, and terephthalic acid. Examples include acid, acetic anhydride, maleic anhydride, citric acid, boric acid, phosphoric acid, titanium tetrachloride, zinc chloride, aluminum chloride, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, and the like.
These acidic catalysts can be used alone or in combination of two or more.

  Among the basic catalysts, examples of the inorganic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like. Can be mentioned.

Further, among the basic catalysts, as the organic bases, for example,
linear, branched or cyclic monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine;
Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, Linear, branched or cyclic dialkylamines such as dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n- Linear, branched or cyclic trialkylamines such as heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine and tricyclohexylamine;

Aromatic amines such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine and naphthylamine;
Ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 4, 4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- ( 3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1, Diamines such as 3-bis [1- (4-aminophenyl) -1-methylethyl] benzene;

Imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole;
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 and acridine; piperazines such as piperazine and 1- (2'-hydroxyethyl) piperazine;
Other nitrogen-containing heterocyclic compounds such as pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane And the like.
These basic catalysts can be used alone or in combination of two or more.

Among the acidic catalyst and the basic catalyst, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, acetic anhydride, maleic anhydride, triethylamine, tri-n-propylamine, tri-n-butylamine, Pyridine and the like are preferred.
The amount of the acidic catalyst or the basic catalyst to be used is generally 0.01 to 10,000 parts by weight based on 100 parts by weight of the total amount of the silicon-containing compound.

Further, as the solvent used for the polycondensation, for example,
2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, Linear or branched ketones such as 2-octanone;
Cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, and isophorone;
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 mono-i-butyl ether acetate Propylene glycol monoalkyl ether acetates such as propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate;

Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, Alkyl 2-hydroxypropionates such as sec-butyl 2-hydroxypropionate and t-butyl 2-hydroxypropionate;
Alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate;
Ethanol, n-propanol, i-propanol, n-butanol, t-butanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene Alcohols such as glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether;

Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, and diethylene glycol di-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and ethylene glycol mono-n-propyl ether acetate;
Aromatic hydrocarbons such as toluene and xylene;
Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3 -Methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate and others. In addition to esters,

N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzylethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, -Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and the like.
These solvents can be used alone or in combination of two or more.
The amount of the solvent used is usually 2,000 parts by weight or less based on 100 parts by weight of the total amount of the silicon-containing compound.

  The polycondensation for producing the polysiloxane (A) is carried out without solvent or with 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2. -Pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone, cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, 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- It is preferably carried out in a solvent such as Ropi ether acetate.

In the case of polycondensation, water can be added to the reaction system. The amount of water added in this case is usually 10,000 parts by weight or less based on 100 parts by weight of the total amount of the silicon-containing compound.
The reaction temperature in the polycondensation is usually -50 to + 300C, preferably 20 to 100C, and the reaction time is usually about 1 minute to 100 hours.

The polysiloxane (A) can have one or more types of structural units other than the structural units (I) and (II) (hereinafter, referred to as “other structural units”).
Examples of a preferred silicon-containing compound that provides another structural unit (hereinafter, referred to as “other silicon-containing compound”) include, for example, a silicon-containing compound represented by the following general formula (3) (hereinafter, “silicon-containing compound (3 ) "), A silicon-containing compound having an acid-dissociable group, such as a silane compound represented by the following general formula (4) (hereinafter, referred to as" silicon-containing compound (4) "); ) (Hereinafter, referred to as “silicon-containing compound (5)”), and a silicon-containing compound represented by the following general formula (6) (hereinafter, referred to as “silicon-containing compound (6)”). And a silicon-containing compound represented by the following general formula (7) (hereinafter, referred to as “silicon-containing compound (7)”). Each of these silicon-containing compounds (3) to (7) may be partially or entirely used as a partial condensate.

〔一般式（３）および一般式（４）において、各Ｅは相互に独立に酸解離性基を有する１価の有機基を示し、各Ｒ¹ は相互に独立に炭素数１〜２０の１価の炭化水素基または炭素数１〜２０の１価のハロゲン化炭化水素基を示し、Ｒ² は水素原子、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数１〜２０の直鎖状もしくは分岐状のハロゲン化アルキル基、炭素数６〜２０の１価の芳香族炭化水素基または炭素数６〜２０の１価のハロゲン化芳香族炭化水素基を示す。〕

[In the general formulas (3) and (4), each E independently represents a monovalent organic group having an acid-dissociable group, and each R ¹ independently represents a 1 to 20 carbon atom. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a C 1 to C 20 monovalent halogenated hydrocarbon group or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; A linear or branched halogenated alkyl group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monovalent halogenated aromatic hydrocarbon group having 6 to 20 carbon atoms. ]

〔一般式（５）〜（７）において、各Ｒ¹ および各Ｒ² は一般式（３）および一般式（４）におけるそれぞれＲ¹ およびＲ² と同義であり、各Ｒ³ は相互に独立にヒドロキシル基、カルボキシル基、ヒドロキシル基を有する１価の有機基またはカルボキシル基を有する１価の有機基を示す。〕

In [Formula (5) to (7), each R ¹ and each R ² is Formula (3) and have the same meanings as R ¹ and R ^2, respectively, in the general formula (4), each R ³ independently of one another Shows a hydroxyl group, a carboxyl group, a monovalent organic group having a hydroxyl group or a monovalent organic group having a carboxyl group. ]

Hereinafter, the silicon-containing compounds (3) to (7) will be sequentially described.
In the general formulas (3) and (4), the monovalent organic group having an acid dissociable group of E is preferably dissociated by an acid to generate a phenolic hydroxyl group, an alcoholic hydroxyl group or a carboxyl group. Polysiloxanes such as a linear or branched alkyl group having 1 to 20 carbon atoms having an acid dissociable group, and a monovalent alicyclic hydrocarbon group having 4 to 30 carbon atoms having an acid dissociable group; Groups which are stable under the reaction conditions for preparing A) can be mentioned.
As the acid dissociable group in E, for example, a group represented by the following formula (8) or (9) (hereinafter referred to as “acid dissociable group (e)”) is preferable.

〔一般式（８）および一般式（９）において、Ｐは単結合、メチレン基、ジフルオロメチレン基、炭素数２〜２０の直鎖状、分岐状もしくは環状のアルキレン基、炭素数２〜２０の直鎖状、分岐状もしくは環状のフルオロアルキレン基、炭素数６〜２０の２価の芳香族基または炭素数３〜２０の２価の他の脂環式基を示し、Ｇは酸により解離して水素原子を生じる１価の有機基を示す。〕

[In the general formulas (8) and (9), P represents a single bond, a methylene group, a difluoromethylene group, a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms; A linear, branched or cyclic fluoroalkylene group, a divalent aromatic group having 6 to 20 carbon atoms or another divalent alicyclic group having 3 to 20 carbon atoms, wherein G is dissociated by an acid; Represents a monovalent organic group that generates a hydrogen atom. ]

  In the general formulas (8) and (9), examples of the linear, branched or cyclic alkylene group having 2 to 20 carbon atoms of P include an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, Examples thereof include a 1,3-cyclopentylene group and a 1,4-cyclohexylene group. Examples of the linear, branched, or cyclic fluoroalkylene group having 2 to 20 carbon atoms include a tetrafluoroethylene group. , 2,2-di (trifluoromethyl) ethylene group, hexafluorotrimethylene group, octafluorotetramethylene group and the like. Examples of the divalent aromatic group having 6 to 20 carbon atoms include, for example, 1 , 4-phenylene group, 1,4-naphthylene group, tetrafluoro-1,4-phenylene group, perfluoro-1,4-naphthylene group, etc. Other examples of the divalent alicyclic group having 3 to 20 carbon atoms include divalent hydrocarbon groups having a norbornene skeleton, a tricyclodecane skeleton, or an adamantane skeleton, and halides of these groups. be able to.

  P in the general formulas (8) and (9) has an ethylene group, a cyclohexylene group, a phenylene group, a tetrafluorophenylene group, a divalent hydrocarbon group having a norbornene skeleton, a halide thereof, and an adamantane skeleton. Preferred are divalent hydrocarbon groups and their halides.

Examples of the monovalent organic group that generates a hydrogen atom when dissociated by an acid of G include, for example,
Methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, n-pentyl, n-hexyl, n- Linear, branched or cyclic alkyl groups such as heptyl group, n-octyl group, n-decyl group, cyclopentyl group, cyclohexyl group, 4-t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group;
Aryloxycarbonyl group such as phenoxycarbonyl group, 4-t-butylphenoxycarbonyl group, 1-naphthyloxycarbonyl group;
Aralkyl groups such as benzyl group, 4-t-butylbenzyl group, phenethyl group, 4-t-butylphenethyl group;
t-butoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, 9-fluorenylmethylcarbonyl group, 2,2,2-trichloroethylcarbonyl group, 2- (trimethylsilyl) ethylcarbonyl group, i Organic carbonyl groups such as -butylcarbonyl group, vinylcarbonyl group, allylcarbonyl group, benzylcarbonyl group, 4-ethoxy-1-naphthylcarbonyl group, methyldithiocarbonyl group;

Methoxymethyl group, methylthiomethyl group, t-butylthiomethyl group, (phenyldimethylsilyl) methoxymethyl group, benzyloxymethyl group, t-butoxymethyl group, siloxymethyl group, 2-methoxyethoxymethyl group, 2,2 2-trichloroethoxymethyl group, bis (2-chloroethoxy) methyl group, 2- (trimethylsilyl) ethoxymethyl group, 1-methoxycyclohexyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrofuran Thiopyranyl group, tetrahydrothiofuranyl group, 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, 1-methyl-1-benzyloxyethyl group, 1- (2-chloroethoxy) ethyl group, 1 -Methyl-1-benzyloxy-2-fluoroe Organic groups that form an acetal group by bonding with an oxygen atom in the general formula (8), such as a benzyl group, a 2,2,2-trichloroethyl group, a 2-trimethylsilylethyl group, or a 2- (phenylselenyl) ethyl group. Group;
Trimethylsilyl group, triethylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, dimethylethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, Examples thereof include organic silyl groups such as a tribenzylsilyl group, a tri-p-xylylsilyl group, a triphenylsilyl group, a diphenylmethylsilyl group, and a t-butylmethoxyphenylsilyl group.

Among the monovalent organic groups that dissociate with these acids to generate a hydrogen atom, a t-butyl group, a tetrahydropyranyl group, a 1-ethoxyethyl group, a t-butyldimethylsilyl group, and the like are preferable.
In the general formulas (3) and (4), E represents a 2-t-butoxycarbonylethyl group, a 4-t-butoxycarbonylcyclohexyl group, a 4-t-butoxycarbonylphenyl group, a 4-t-butoxycarbonyl- group. 2,3,5,6-tetrafluorophenyl group, 5-t-butoxycarbonylnorbonyl group, 5-trifluoromethyl-5-t-butoxycarbonylnorbonyl group, 4-t-butoxycarbonyltetracyclo [6. 2.1.
^13-6 . 0 ^2,7 ] dodecanyl group, 4-trifluoromethyl-4-t-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . [0 ^2,7 ] dodecanyl group, 5-t-butoxycarbonyladamantyl group and the like.

Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and a 2-alkyl group. Methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group And the like, and examples of the linear, branched or cyclic halogenated alkyl group having 1 to 10 carbon atoms include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, A trifluoromethyl group and the like can be mentioned.
As R ¹ in the general formulas (3) and (4), a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and the like are preferable.

In the general formula (4), examples of the linear or branched alkyl group having 1 to 20 carbon atoms for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n- Butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. Examples of the linear or branched halogenated alkyl group having 1 to 20 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, and a heptafluoro-i group. -Propyl group and the like. Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, an α-naphthyl group, a β-naphthyl group, a benzyl group, a phenethyl group and the like. Examples of the monovalent halogenated aromatic hydrocarbon group having 6 to 20 carbon atoms include a pentafluorophenyl group, a perfluorobenzyl group, a perfluorophenethyl group, and 2- (pentafluorophenyl) hexafluoro -N-propyl group and 3- (pentafluorophenyl) hexafluoro-n-propyl group.
As R ² in the general formula (4), a methyl group, an ethyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluorophenethyl group, a 3- (pentafluorophenyl) hexafluoro-n-propyl group and the like are preferable.

Next, in the general formulas (5) to (7), R ¹ and R ² are, for example, the same as the groups exemplified for R ¹ and R ² in the general formulas (3) and (4), respectively. Things can be mentioned.

Examples of the monovalent organic group having a hydroxyl group of R ³ include a group represented by the following general formula (10). Examples of the monovalent organic group having a carboxyl group of R ³ include For example, a group represented by the following general formula (11) can be mentioned.

〔一般式（１０）および一般式（１１）において、Ｑはメチレン基、ジフルオロメチレン基、炭素数２〜２０の直鎖状、分岐状もしくは環状のアルキレン基、炭素数２〜２０の直鎖状、分岐状もしくは環状のフルオロアルキレン基、炭素数６〜２０の２価の芳香族基または炭素数３〜２０の２価の他の脂環式基を示す。〕

[In the general formulas (10) and (11), Q is a methylene group, a difluoromethylene group, a linear or branched or cyclic alkylene group having 2 to 20 carbon atoms, or a linear alkylene group having 2 to 20 carbon atoms. A branched or cyclic fluoroalkylene group, a divalent aromatic group having 6 to 20 carbon atoms, or another divalent alicyclic group having 3 to 20 carbon atoms. ]

In the general formulas (10) and (11), Q is a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, or a linear, branched or cyclic fluoroalkylene having 2 to 20 carbon atoms. Examples of the group, a divalent aromatic group having 6 to 20 carbon atoms and another divalent alicyclic group having 3 to 20 carbon atoms include, for example, P in the general formulas (8) and (9). The same groups as the corresponding groups described above can be exemplified.
Q in the general formulas (10) and (11) represents a methylene group, a difluoromethylene group, a 2,2-di (trifluoromethyl) ethylene group, a divalent hydrocarbon group having a norbornene skeleton, or a halide thereof. And a divalent hydrocarbon group having an adamantane skeleton or a halide thereof.

  In the present invention, the other silicon-containing compounds can be used alone or in admixture of two or more. By appropriately selecting or appropriately combining them, the molecular weight and the molecular weight of the polysiloxane (A) obtained can be adjusted. The glass transition temperature (Tg) can be controlled, and the transparency at a wavelength of 193 nm or less, particularly 157 nm can be further improved.

The specific content of each structural unit in the polysiloxane (A) varies depending on the type and combination thereof, the use of the polysiloxane (A), and the like. A preferable content of each structural unit in each case is as follows: A person skilled in the art can appropriately select a test according to a test or the like.
For example, in a resist material for microfabrication using radiation such as far ultraviolet rays, electron beams, and X-rays, it has an acid-dissociable group and is used as a resin component that becomes easily alkali-soluble when the acid-dissociable group is dissociated. In this case, the content of the structural unit (I) is usually from 5 to 80 mol%, preferably from 5 to 70 mol%, based on all structural units, and the content of the structural unit (II) is It is usually from 0 to 80 mol%, preferably from 0 to 60 mol%, particularly preferably from 0 to 30 mol%, based on the unit, and the total content of the structural unit (I) and the structural unit (II) The ratio is usually from 5 to 80 mol%, preferably from 5 to 70 mol%, based on all structural units.
The content of other structural units having an acid dissociable group (e) (ie, structural units derived from silicon-containing compound (3) or silicon-containing compound (4)) is usually , 1 to 60 mol%, preferably 5 to 50 mol%, particularly preferably 10 to 50 mol%, and the content of other structural units is usually 90 mol% with respect to all structural units. Or less, preferably 80 mol% or less.

  The polysiloxane (A) has a polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “Mw”) measured by gel permeation chromatography (GPC) of 500 to 1,000,000, preferably 500 to 50,000, and particularly preferably. Is from 800 to 50,000. In this case, if Mw is less than 500, the glass transition temperature (Tg) of the obtained polymer tends to decrease, while if it exceeds 1,000,000, the solubility of the obtained polymer in a solvent tends to decrease. is there.

  Polysiloxane (A) has a property of high transparency to radiation and easy control of solubility in an alkaline developer, and is a resist for fine processing using radiation such as far ultraviolet rays, electron beams, and X-rays. It is extremely useful as a resin component in a radiation-sensitive resin composition suitable as a resin. Further, the polysiloxane (A) is useful alone or as a mixture with a general polysiloxane, for example, as a molded product, a film, a laminate material, a paint component and the like.

Hereinafter, the radiation-sensitive resin composition of the present invention useful as a chemically amplified resist will be described.
Radiation-Sensitive Resin Composition The radiation-sensitive resin composition of the present invention contains (A) polysiloxane (A1) and (B) a radiation-sensitive acid generator (hereinafter, simply referred to as “acid generator”). Is what you do.
In the radiation-sensitive resin composition of the present invention, the polysiloxane (A1) can be used alone or as a mixture of two or more. In addition to the polysiloxane (A1), one or more other polysiloxanes can be used. Can be used together.
Examples of the other polysiloxane include those having at least one structural unit derived from the silicon-containing compounds (3) to (7).

-Acid generator-
The acid generator in the radiation-sensitive resin composition of the present invention is a component that generates an acid upon exposure, and the action of the acid causes the acid-dissociable group present in the polysiloxane (A1) to be dissociated. The exposed portion of the resist film becomes easily soluble in an alkali developing solution, and has an effect of forming a positive resist pattern.
The acid generator in the present invention is not particularly limited as long as it has the above-mentioned action. Preferred acid generators include, by exposure, trifluoromethanesulfonic acid or an acid represented by the following general formula (12) (hereinafter referred to as an acid generator). And a compound that generates a compound (hereinafter referred to as “acid (β)”) (hereinafter referred to as “acid generator (B1)”).

〔一般式（１２）において、各Ｒf¹は相互に独立にフッ素原子またはトリフルオロメチル基を示し、Ｒa は水素原子、フッ素原子、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数１〜２０の直鎖状もしくは分岐状のフッ素化アルキル基、炭素数３〜２０の環状の１価の炭化水素基または炭素数３〜２０の環状の１価のフッ素化炭化水素基を示し、該環状の１価の炭化水素基および該環状の１価のフッ素化炭化水素基は置換されていてもよい。〕

[In the general formula (12), each Rf ¹ independently represents a fluorine atom or a trifluoromethyl group, Ra represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 20 carbon atoms, A linear or branched fluorinated alkyl group having 1 to 20 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic monovalent fluorinated hydrocarbon group having 3 to 20 carbon atoms; As shown, the cyclic monovalent hydrocarbon group and the cyclic monovalent fluorinated hydrocarbon group may be substituted. ]

Examples of the acid generator (B1) include an onium salt compound, a sulfone compound, a sulfonic acid compound, a carboxylic acid compound, a diazoketone compound, and a halogen-containing compound.
As the acid generator in the present invention, only the acid generator (B1) can be used, but the acid generator (B1) and an acid represented by the following general formula (13) (hereinafter referred to as “acid (γ) -1) "), an acid represented by the general formula (14) (hereinafter referred to as" acid (γ-2) ") or an acid represented by the general formula (15) (hereinafter referred to as" acid (γ) -3) ") can be used in combination with a radiation-sensitive acid generator (hereinafter, referred to as" acid generator (B2) ").

[In the general formula (13), Rf ¹ represents a fluorine atom or a trifluoromethyl group, Rf ² represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Rb represents a hydrogen atom, and has 1 to 20 carbon atoms. A linear or branched alkyl group, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic monovalent fluorinated hydrocarbon group having 3 to 20 carbon atoms; And the cyclic monovalent fluorinated hydrocarbon group may be substituted.

In the general formula (14), Rs represents a linear or branched alkyl group having 1 to 20 carbon atoms or a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms; The groups may be substituted.

In the general formula (15), Rc is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. A monovalent hydrocarbon group or a cyclic monovalent fluorinated hydrocarbon group having 3 to 20 carbon atoms, wherein the cyclic monovalent hydrocarbon group and the cyclic monovalent fluorinated hydrocarbon group are substituted It may be. ]

  In the general formulas (12) to (15), specific examples of the linear or branched alkyl group having 1 to 20 carbon atoms of Ra, Rb, Rs and Rc include a methyl group, an ethyl group, an n-propyl group, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like. .

Specific examples of the linear or branched fluorinated alkyl group having 1 to 20 carbon atoms of Ra and Rc include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, and a heptafluoro- i-propyl group, nonafluoro-n-butyl group, nonafluoro-i-butyl group, nonafluoro-sec-butyl group, nonafluoro-t-butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, par Examples thereof include a fluoro-n-heptyl group and a perfluoro-n-octyl group.
Examples of the cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms or the monovalent cyclic fluorinated hydrocarbon group having 3 to 20 carbon atoms of Ra, Rb, Rs and Rc or a substituted derivative thereof include, for example, And groups represented by the following formulas (16) to (22).

[In the formulas (16) to (22), each R ⁴ is independently a hydrogen atom, a halogen atom, a hydroxyl group, an acetyl group, a carboxyl group, a nitro group, a cyano group, a primary amino group, a secondary amino group, a carbon atom. A linear or branched alkoxyl group having 1 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 10 carbon atoms. Each R ⁵ independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched fluorinated alkyl group having 1 to 10 carbon atoms; Is an integer of 0 to 10.
In the formula (19), q is an integer of 1 to 18.
In the formula (20), m is an integer of 0 to 3. ]

Preferred acids (β) in the present invention include, for example,
Trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-n-propanesulfonic acid, nonafluoro-n-butanesulfonic acid, perfluoro-n-octanesulfonic acid, 1,1,2,2, -tetrafluoro-n -Propanesulfonic acid, 1,1,2,2, -tetrafluoro-n-butanesulfonic acid, 1,1,2,2, -tetrafluoro-n-octanesulfonic acid,

A bond of a group represented by the above formulas (16) to (22) has —CF ₂ CF ₂ SO ₃ H,
_{-CF 2 CF (CF 3) SO} 3 H, -CF (CF 3) CF 2 SO 3 H,
An acid to which a group of —CF (CF ₃ ) CF (CF ₃ ) SO ₃ H, —C (CF ₃ ) ₂ CF ₂ SO ₃ H or —CF ₂ C (CF ₃ ) ₂ SO ₃ H is bonded, for example, Acids of the formulas (12-1) to (12-10) can be exemplified.

Further, preferred acids (γ-1) in the present invention include, for example,
1-fluoroethanesulfonic acid, 1-fluoro-n-propanesulfonic acid, 1-fluoro-n-butanesulfonic acid, 1-fluoro-n-octanesulfonic acid, 1,1-difluoroethanesulfonic acid, 1,1-difluoro -N-propanesulfonic acid, 1,1-difluoro-n-butanesulfonic acid, 1,1-difluoro-n-octanesulfonic acid, 1-trifluoromethyl-n-propanesulfonic acid, 1-trifluoromethyl-n -Butanesulfonic acid, 1-trifluoromethyl-n-octanesulfonic acid, 1,1-bis (trifluoromethyl) ethanesulfonic acid, 1,1-bis (trifluoromethyl) -n-propanesulfonic acid, 1-bis (trifluoromethyl) -n-butanesulfonic acid, 1,1-bis (trifluoromethyl) -n-octa Or a sulfonic acid,

A bond of a group represented by the above formulas (16) to (22) has —CF ₂ SO ₃ H,
_{-CHFSO 3 H, -CH (CF 3} ) SO 3 H or -C (CF _{3) 2} SO ₃ acid H groups attached thereto, e.g., such as an acid of formula (13-1) - (13-40) Can be mentioned.

Further, preferred acids (γ-2) in the present invention include, for example,
Methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, n-butanesulfonic acid, i-butanesulfonic acid, sec-butanesulfonic acid, t-butanesulfonic acid, n-pentanesulfonic acid, n-hexanesulfonic acid, linear, branched or cyclic alkylsulfonic acids such as n-octanesulfonic acid, cyclopentanesulfonic acid, and cyclohexanesulfonic acid;
Aromatic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, benzylsulfonic acid, α-naphthalenesulfonic acid, and β-naphthalenesulfonic acid;
10-camphorsulfonic acid,
The bond of the group represented by the formulas (16) to (22) includes an acid having a —SO ₃ H group bonded thereto.

Further, preferred acids (γ-3) in the present invention include, for example,
Acetic acid, n-propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, benzoic acid, salicylic acid, phthalic acid, terephthalic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, cyclobutanecarboxylic acid, cyclo Pentanecarboxylic acid, cyclohexanecarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-norbornanecarboxylic acid, 2,3-norbornanedicarboxylic acid, norbornyl-2 -Acetic acid, 1-adamantane Carboxylic acid, 1-adamantane acetic acid, 1,3-adamantane dicarboxylic acid, 1,3-adamantane diacetic acid, lithocholic acid, deoxycholic acid, chenodeoxycholic acid, cholic acid,
An acid having a -COOH group bonded thereto as a bond of the group represented by the above formulas (16) to (22) can be given.

Examples of the onium salt compound that generates an acid (β), an acid (γ-1), an acid (γ-2) or an acid (γ-3) include, for example,
Diphenyliodonium salt, bis (4-t-butylphenyl) iodonium salt, triphenylsulfonium salt,
4-hydroxyphenyl phenyl methyl sulfonium salt, cyclohexyl 2-oxocyclohexyl methyl sulfonium salt, dicyclohexyl 2-oxocyclohexyl sulfonium salt, 2-oxocyclohexyl dimethyl sulfonium salt, 4-hydroxyphenyl benzyl methyl sulfonium salt,
1-naphthyldimethylsulfonium salt, 1-naphthyldiethylsulfonium salt, 4-cyano-1-naphthyldimethylsulfonium salt, 4-cyano-1-naphthyldiethylsulfonium salt, 4-nitro-1-naphthyldimethylsulfonium salt, 4-nitro -1-naphthyldiethylsulfonium salt, 4-methyl-1-naphthyldimethylsulfonium salt, 4-methyl-1-naphthyldiethylsulfonium salt, 4-hydroxy-1-naphthyldimethylsulfonium salt, 4-hydroxy-1-naphthyldiethylsulfonium salt salt,

1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-ethoxynaphthalen-1-yl) tetrahydrothio Phenium salt, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-ethoxyto Methoxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- [4- (1-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium salt, 1- [4- (2-methoxyethoxy) naphthalene-1 -Yl] tetrahydrothiophenium salt, 1- (4-methoxycarbonyloxynaphthalene-1-i ) Tetrahydrothiophenium salt, 1- (4-ethoxycarbonyloxynaphnaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-n-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- (4-t -Butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium salt, 1- [4- (2-tetrahydrofuranyloxy) naphthalen-1-yl] tetrahydrothiophenium salt, 1- [4- (2-tetrahydropyrani Ruoxy) naphthalen-1-yl] tetrahydrothio Eniumu salt, 1- (4-benzyloxy-naphthalen-1-yl) tetrahydrothiophenium salt, and 1- [1- (1-naphthyl acetamide methyl)] tetrahydrothiophenium salt.

Examples of the sulfone compound generating an acid (β), an acid (γ-1) or an acid (γ-2) include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds. Can be mentioned.
Examples of the sulfonic acid compound generating an acid (β), an acid (γ-1) or an acid (γ-2) include a sulfonic acid ester, a sulfonic acid imide, an arylsulfonic acid ester, and an iminosulfonate. Can be.
Examples of the carboxylic acid compound generating an acid (γ-3) include a carboxylic acid ester, a carboxylic acid imide, and a carboxylic acid cyanate.

Examples of the diazoketone compound that generates an acid (β), an acid (γ-1), an acid (γ-2) or an acid (γ-3) include, for example, a 1,3-diketo-2-diazo compound, a diazobenzoquinone And diazonaphthoquinone compounds.
Examples of the halogen-containing compound that generates the acid (β), the acid (γ-1), the acid (γ-2) or the acid (γ-3) include, for example, a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic ring. Formula compounds and the like can be mentioned.

Further, examples of preferred acid generators other than the acid generator (B1) and the acid generator (B2) (hereinafter, simply referred to as “other acid generators”) include, for example,
Diphenyliodonium pyrene sulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate Bis (4-t-butylphenyl) iodonium naphthalene sulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium 10-camphorsulfonate, 4-hydroxyphenylphenylmethylsulfonium p-toluenesulfonate, 4-hydroxyphenyl / benzyl / methylsulfonium p-toluene Other onium salt compounds such as Honeto;
Other sulfone compounds such as 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane;
Other sulfonic acid compounds such as benzoin tosylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate;

1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonic acid ester of 2,3,4,4'-tetrahydroxybenzophenone or 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5 Other diazoketone compounds such as sulfonic esters;
(Trichloromethyl) -s-triazine derivatives such as phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine, 1-naphthylbis (trichloromethyl) -s-triazine, 1, Other halogen-containing compounds such as 1-bis (4-chlorophenyl) -2,2,2-trichloroethane can be exemplified.
In the present invention, only another acid generator may be used as the acid generator, but the other acid generator may be used in combination with the acid generator (B1) or a mixture thereof with the acid generator (B2). It is also preferred to use.

In the present invention, the acid generators can be used alone or in combination of two or more.
The amount of the acid generator to be used is generally 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight, based on 100 parts by weight of all polysiloxane components, from the viewpoint of securing the sensitivity and developability as a resist. Department. In this case, if the amount of the acid generator used is less than 0.1 part by weight, sensitivity and developability tend to decrease, while if it exceeds 10 parts by weight, the transparency to radiation decreases and the rectangular resist pattern is reduced. Tends to be difficult to obtain.

-Additive-
The radiation-sensitive resin composition of the present invention may contain various additives such as an acid diffusion controller, a dissolution controller, and a surfactant.
The acid diffusion controller is a component having a function of controlling a diffusion phenomenon of an acid generated from an acid generator upon exposure in a resist film and suppressing an undesirable chemical reaction in a non-exposed area.
By blending such an acid diffusion controller, the storage stability of the obtained radiation-sensitive resin composition is further improved, and the resolution as a resist is further improved, and the withdrawal time from exposure to development processing is increased. Variations in the line width of the resist pattern due to fluctuations in (PED) can be suppressed, and a composition having extremely excellent process stability can be obtained.
As the acid diffusion controller, a nitrogen-containing organic compound whose basicity is not changed by exposure or heat treatment during a resist pattern forming step is preferable.
Examples of such a nitrogen-containing organic compound include a compound represented by the following general formula (23) (hereinafter, referred to as “acid diffusion controller (C)”).

〔一般式（２３）において、各Ｒ⁶ は相互に独立に水素原子、直鎖状、分岐状もしくは環状のアルキル基、アリール基またはアラルキル基を示し、これらのアルキル基、アリール基およびアラルキル基は水酸基等の官能基で置換されていてもよく、Ｕ¹ は２価の有機基を示し、ｒは０〜２の整数である。〕

[In the general formula (23), each R ⁶ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group, and these alkyl groups, aryl groups and aralkyl groups are It may be substituted with a functional group such as a hydroxyl group, U ¹ represents a divalent organic group, and r is an integer of 0 to 2. ]

In the acid diffusion controller (C), the compound with r = 0 is referred to as “nitrogen-containing compound (C1)”, and the compound with r = 1 to 2 is referred to as “nitrogen-containing compound (C2)”. Further, a polyamino compound and a polymer having three or more nitrogen atoms are collectively referred to as "nitrogen-containing compound (C3)".
Examples of the nitrogen-containing organic compound other than the acid diffusion controller (C) include, for example, quaternary ammonium hydroxide compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.

  Examples of the nitrogen-containing compound (C1) include mono- (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine; di-n- Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine , Tri-n-nonylamine, tri-n-decylamine, cyclohexyl Tri (cyclo) alkylamines such as dimethylamine, dicyclohexylmethylamine and tricyclohexylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, Examples thereof include aromatic amines such as 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, diphenylamine, triphenylamine, and naphthylamine.

Examples of the nitrogen-containing compound (C2) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, tetramethylenediamine, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzenetetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether, 4,4′- Diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl ) -2- (3-Hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-h Droxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, Bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether and the like can be mentioned.
Examples of the nitrogen-containing compound (C3) include polyethyleneimine, polyallylamine, and 2-dimethylaminoethylacrylamide polymers.
Examples of the quaternary ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide 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-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-tert-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-tert-butoxycarbonylhexamethylenediamine, N, N, N ', N'-tetra-t-butoxycarbonylhexamethylene Amine, N, N'-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-t-butoxycarbonyl-1,8-diaminooctane, N, N'-di-t-butoxy Carbonyl-1,9-diaminononane, N, N′-di-tert-butoxycarbonyl-1,10-diaminodecane, N, N′-di-tert-butoxycarbonyl-1,12-diaminododecane,
N, N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2 N-t-butoxycarbonyl group-containing amino compounds such as -phenylbenzimidazole, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, Benzamide, pyrrolidone, N-methylpyrrolidone and the like can be mentioned.

  Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n-butyl Thiourea and the like can be mentioned. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole and 2-phenylbenzimidazole; pyridine , 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline Pyridines, such as piperazine, 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, and the like; Piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, and 1,4-diazabicyclo [2.2.2] octane.

These acid diffusion controllers can be used alone or in combination of two or more.
The compounding amount of the acid diffusion controller is usually 100 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less, based on the acid generator. In this case, when the compounding amount of the acid diffusion controller exceeds 100 mol%, the sensitivity as a resist and the developability of an exposed portion tend to decrease. If the amount of the acid diffusion controller is less than 0.1 mol%, the pattern shape and dimensional fidelity of the resist may be reduced depending on the process conditions.

  As the dissolution controlling agent, preferably, for example, a compound represented by the following general formula (24) (hereinafter, referred to as “dissolution controlling agent (D1)”), a compound represented by the following general formula (25) ( Hereinafter, referred to as “dissolution control agent (D2)”), a polyketone having a repeating unit represented by the following general formula (26) (hereinafter referred to as “dissolution control agent (D3)”), and the following general formula (27) And a polyspiroketal having a repeating unit represented by the following formula (hereinafter, referred to as “dissolution controlling agent (D4)”), and more preferably, a dissolution controlling agent (D1) and a dissolution controlling agent (D2). At least one member selected from the group and / or at least one member selected from the group consisting of the solubility control agent (D3) and the solubility control agent (D4). By containing such a dissolution controlling agent, the dissolution contrast and dissolution rate of a resist can be more appropriately controlled.

〔一般式（２４）および一般式（２５）において、各Ｒ⁷ は相互に独立に水素原子、フッ素原子、炭素数１〜１０の直鎖状もしくは分岐状のアルキル基、炭素数１〜１０の直鎖状もしくは分岐状のフッ素化アルキル基、または下記式（ｉ）で表される基

[In the general formula (24) and the general formula (25), each R ⁷ is independently a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, A linear or branched fluorinated alkyl group, or a group represented by the following formula (i)

（式中、各Ｒf³は相互に独立に水素原子、メチル基またはトリフルオロメチル基を示し、Ｕ² は単結合、メチレン基、シクロヘキシレン基またはフェニレン基を示し、Ｒ⁸ は水素原子または酸により解離して水素原子を生じる１価の有機基を示し、ｕは０〜３の整数であり、ｖは０または１である。）
を示し、かつＲ⁷ の少なくとも１つが式（ｉ）で表される基であり、ｓおよびｔは相互に独立に０〜２の整数である。〕

(Wherein each Rf ³ independently represents a hydrogen atom, a methyl group or a trifluoromethyl group, U ² represents a single bond, a methylene group, a cyclohexylene group or a phenylene group, and R ⁸ represents a hydrogen atom or an acid Represents a monovalent organic group which dissociates to generate a hydrogen atom, u is an integer of 0 to 3, and v is 0 or 1.)
And at least one of R ⁷ is a group represented by the formula (i), and s and t are each independently an integer of 0 to 2. ]

〔一般式（２６）および一般式（２７）において、各Ｒ⁷ は一般式（２４）および一般式（２５）におけるＲ⁷ と同義である。但し、一般式（２６）および一般式（２７）におけるＲ⁷ は、一般式（２４）および一般式（２５）におけるＲ⁷ と相互に同一でも異なってもよい。〕

In [Formula (26) and the general formula (27), each R ⁷ has the same meaning as R ⁷ in the general formula (24) and the general formula (25). However, R ⁷ in the general formula (26) and the general formula (27) may be the same or different and R ⁷ in the general formula (24) and the general formula (25). ]

In the general formulas (24) to (27), examples of the linear or branched alkyl group having 1 to 10 carbon atoms of R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. Can be mentioned.
Examples of the linear or branched fluorinated alkyl group having 1 to 10 carbon atoms for R ⁷ include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoro-n- Propyl group, heptafluoro-i-propyl group, nonafluoro-n-butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, perfluoro-n-heptyl group, perfluoro-n-octyl group, Examples thereof include a perfluoro-n-nonyl group and a perfluoro-n-decyl group.

In the group represented by the above formula (i) representing R ⁷ (hereinafter referred to as “functional group (i)”), two bonds in the cyclohexylene group and the phenylene group of U ² are each 1 , 2-position, 1,3-position or 1,4-position.

Examples of the monovalent organic group which dissociates with an acid of R ⁸ to generate a hydrogen atom include, for example,
t-butoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, 9-fluorenylmethylcarbonyl group, 2,2,2-trichloroethylcarbonyl group, 2- (trimethylsilyl) ethylcarbonyl group, i Organic carbonyl groups such as -butylcarbonyl group, vinylcarbonyl group, allylcarbonyl group, benzylcarbonyl group, 4-ethoxy-1-naphthylcarbonyl group, methyldithiocarbonyl group;

Methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, t-butoxymethyl group, t-butylthiomethyl group, (phenyldimethylsilyl) methoxymethyl group, benzyloxymethyl group, t-butoxymethyl group, Siloxymethyl group, 2-methoxyethoxymethyl group, 2,2,2-trichloroethoxymethyl group, bis (2-chloroethoxy) methyl group, 2- (trimethylsilyl) ethoxymethyl group, 1-methoxycyclohexyl group, tetrahydropyranyl Group, 4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1- (2-chloroethoxy) ethyl group, 1 -Methyl-1-methoxyethyl group, 1-methyl 1-benzyloxyethyl group, 1- (2-chloroethoxy) ethyl group, 1-methyl-1-benzyloxy-2-fluoroethyl group, 2,2,2-trichloroethyl group, 2-trimethylsilylethyl group, An organic group such as a 2- (phenylselenyl) ethyl group which forms an acetal structure by bonding to an oxygen atom in the formula (i);

Trimethylsilyl group, triethylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, dimethylethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, Alkyl silyl groups such as tribenzylsilyl group, tri-p-xylylsilyl group, triphenylsilyl group, diphenylmethylsilyl group, t-butylmethoxyphenylsilyl group;
2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 2-methyl-2-norbornyl group, 2-ethyl-2-norbornyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1- Examples thereof include an alkyl-substituted alicyclic group such as a methylcyclohexyl group and a 1-ethylcyclohexyl group.

  Among the monovalent organic groups which dissociate with these acids to generate a hydrogen atom, a t-butoxycarbonyl group, a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group and the like are preferable.

  Preferred examples of the dissolution controlling agent (D1) include compounds represented by the following formulas (D1-1) to (D1-4).

[In the general formulas (D1-1) to (D1-4), each R ⁹ is independently a hydrogen atom, a t-butoxycarbonyl group, a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group or a 1-ethoxy group. It represents an ethyl group, and each Rf ⁴ independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group. However, in the general formula (D1-3) and the general formula (D1-4), 8 two Rf ⁴ each does not take hydrogen atoms at the same time. ]

  Preferred examples of the dissolution controlling agent (D2) include compounds represented by the following formulas (D2-1) to (D2-5).

In [Formula (D2-1) ~ (D2-5), each R ⁹ and each Rf ⁴ is the same meaning as R ⁹ and Rf ^4, respectively, in the general formula (D1-1) ~ (D1-4). However, in the general formulas (D2-3) and (D2-4), each of the four Rf ⁴ does not take a hydrogen atom at the same time, and the R in the general formulas (D2-1) to (D2-5) ⁹ and Rf ⁴ are each may be the same or different and R ⁹ and Rf ⁴ in the general formula (D1-1) ~ (D1-4). ]

  Examples of the dissolution controlling agent (D1) include compounds represented by the following formulas (D1-1-1), (D1-1-2), (D1-2-1) or (D1-2-2). More preferably, as the dissolution controlling agent (D2), for example, the following formulas (D2-1-1), (D2-1-2), (D2-2-1), and (D2-2-2) Or a compound of the formula (D2-5-1).

  Further, as the dissolution controlling agent (D4), polyspiroketal having a repeating unit represented by the following formula (D4-1) is more preferable.

  Mw of the polyketone as the dissolution controlling agent (D3) and the polyspiroketal as the dissolution controlling agent (D4) is usually 300 to 100,000, preferably 800 to 3,000.

  In the present invention, the amount of the dissolution controlling agent is usually 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the total polysiloxane component. In this case, if the amount of the dissolution controlling agent exceeds 50 parts by weight, the heat resistance of the resist tends to decrease.

The surfactant is a component having an effect of improving coating properties, striation, developability, and the like.
Examples of such a surfactant 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.) and Polyflow No. No. 75, the same No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, and EF352 (manufactured by Tochem Products), Megafax F171 and F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahigard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( Manufactured by Asahi Glass Co., Ltd.).
These surfactants can be used alone or in combination of two or more.
The amount of the surfactant is usually 2 parts by weight or less based on 100 parts by weight of the total polysiloxane component.
In addition, examples of the additives other than the above include an antihalation agent, an adhesion aid, a storage stabilizer, and an antifoaming agent.

-Preparation of composition solution-
The radiation-sensitive resin composition of the present invention is usually dissolved in a solvent so that the total solid concentration is usually 1 to 25% by weight, preferably 2 to 15% by weight, when used, for example, It is prepared as a composition solution by filtering with a filter having a pore size of about 0.2 μm.
As the solvent used for preparing the composition solution, for example,
2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, Linear or branched ketones such as 2-octanone;
Cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, and isophorone;
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 mono-i-butyl ether acetate Propylene glycol monoalkyl ether acetates such as propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate;
Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, Alkyl 2-hydroxypropionates such as sec-butyl 2-hydroxypropionate and t-butyl 2-hydroxypropionate;
Alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate;

2,3-difluorobenzyl alcohol, 2,2,2-trifluoroethanol, 1,3-difluoro-2-propanol, 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro -1-propanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 3,3,4,4,5,5,5-heptafluoro-2-pentanol, 1H, 1H-perfluoro-1-octanol, 1H, 1H, 2H, 2H-perfluoro-1-octanol, 1H, 1H, 9H-perfluoro-1-nonanol, 1H, 1H, 2H, 3H, 3H-perfluorononane-1,2-diol, 1H, 1H, 2H, 2H-perfluoro-1-decanol, 1H, H, 2H, 3H, fluorine-containing alcohols such as 3H- perfluoro undecanoic 1,2-diol;

2,2,2-trifluoroethyl butyrate, ethyl heptafluorobutyrate, ethyl heptafluorobutyl acetate, ethyl hexafluoroglutarate, ethyl-3-hydroxy-4,4,4-trifluorobutyrate, ethyl-2 -Methyl-4,4,4-trifluoroacetoacetate, ethylpentafluorobenzoate, ethylpentafluoropropionate, ethyl pentafluoropropionate, ethyl perfluorooctanoate, ethyl-4,4,4-trifluoroacetate Acetate, ethyl-4,4,4-trifluorobutyrate, ethyl-4,4,4-trifluorocrotonate, ethyltrifluorosulfonate, ethyl-3- (trifluoromethyl) butyrate, ethyltrifluoropyruvate, Ethyl trifluoroa Tate, isopropyl-4,4,4-trifluoroacetoacetate, methyl perfluorodecanoate, methyl perfluoro (2-methyl-3-oxahexanoate), methyl perfluorononanoate, methyl perfluorooctanoate , Methyl-2,3,3,3-tetrafluoropropionate, methyltrifluoroacetoacetate, methyltrifluoroacetoacetate, perfluoro (2,5,8-trimethyl-3,6,9-trioxadodecanoic acid ) Methyl, propylene glycol trifluoromethyl ether acetate, propylene glycol methyl ether trifluoromethyl acetate, n-butyl trifluoromethylacetate, methyl 3-trifluoromethoxypropionate, 1,1,1-trifluoro-2-propionate Acetate, fluorine-containing esters such as n- butyl trifluoroacetate;

2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 2,3-difluoroanisole, 2,4-difluoroanisole, 2,5-difluoroanisole, 5,8-difluoro-1,4-benzodioxane, tri Fluoroacetaldehyde ethyl hemiacetal, 2H-perfluoro (5-methyl-3,6-dioxanonane), 2H-perfluoro (5,8,11,14-tetramethyl-3,6,9,12,15-pentaoxa Fluorine-containing ethers such as (octadecane), (perfluoro-n-butyl) tetrahydrofuran, perfluoro (n-butyltetrahydrofuran), propylene glycol trifluoromethyl ether;

2,4-difluoropropiophenone, fluorocyclohexane, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, 1,1,1,3, 5,5,5-heptafluoropentane-2,4-dione, 3,3,4,4,5,5,5-heptafluoro-2-pentanone, 1,1,1,2,2,6,6 Fluorine-containing ketones such as 2,6-octafluoro-2,4-hexanedione, trifluorobutanol-1,1,1-trifluoro-5-methyl-2,4-hexanedione and perfluorocyclohexanone;
Fluorine-containing amines such as trifluoroacetamide, perfluorotributylamine, perfluorotrihexylamine, perfluorotripentylamine and perfluorotripropylamine;
In addition to fluorine-containing solvents such as fluorine-substituted cyclic hydrocarbons such as 2,4-difluorotoluene, perfluorodecalin, perfluoro (1,2-dimethylcyclohexane), and perfluoro (1,3-dimethylcyclohexane),

n-propanol, i-propanol, n-butanol, t-butanol, 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 acetate, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol Toluene mono-n-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl- 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, Methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, ethyl benzyl acetate, benzoate, diethyl oxalate, diethyl maleate, .gamma.-butyrolactone, ethylene carbonate, propylene carbonate and the like.

  These solvents can be used alone or as a mixture of two or more. Among them, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, Preferred are alkyl hydroxypropionates, alkyl 3-alkoxypropionates, and fluorine-containing solvents.

-Method of forming resist pattern-
In the radiation-sensitive resin composition of the present invention, an acid is generated from the acid generator by exposure, and the acid dissociable group in the polysiloxane (A1) is dissociated by the action of the acid, for example, a phenolic hydroxyl group. To form an alcoholic hydroxyl group or a carboxyl group. As a result, the solubility of the exposed portion of the resist in an alkali developing solution is increased, and the exposed portion is dissolved and removed by the alkali developing solution to obtain a positive resist pattern. .
When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution is coated with an appropriate coating means such as spin coating, casting coating, roll coating, for example, a silicon wafer, coated with aluminum. A resist film is formed by applying the resist film on a wafer or a substrate on which an underlayer film has been formed in advance, and after a heat treatment (hereinafter referred to as “PB”) in some cases, a predetermined resist pattern is formed. The resist coating is exposed to form. The radiation used at this time includes an ArKr excimer laser (wavelength 134 nm), a Kr ₂ excimer laser (wavelength 147 nm), an F ₂ excimer laser (wavelength 157 nm), an ArF excimer laser (wavelength 193 nm), or a KrF excimer laser (wavelength 248 nm). Is preferred.
In the present invention, it is preferable to perform a heat treatment (hereinafter, referred to as “PEB”) after the exposure. By this PEB, the dissociation reaction of the acid dissociable group in the polysiloxane (A1) proceeds smoothly. The heating conditions for PEB vary depending on the composition of the resist composition, but are usually 30 to 200 ° C, preferably 50 to 170 ° C.

  In the present invention, in order to maximize the potential of the radiation-sensitive resin composition, an organic or inorganic underlayer film is formed on a substrate to be used (for example, see Patent Document 5). In order to prevent the influence of basic impurities and the like contained in the environmental atmosphere, a protective film can be provided on the resist film, or these techniques can be used together (for example, see Patent Document 6). You can also.

Japanese Patent Publication No. 6-12452 JP-A-5-188598

Next, a predetermined resist pattern is formed by developing the exposed resist film.
Examples of a 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 alkaline compound such as [4.3.0] -5-nonene is dissolved is preferable.
The concentration of the alkaline aqueous solution is usually 10% by weight or less. In this case, if the concentration of the alkaline aqueous solution exceeds 10% by weight, unexposed portions may be dissolved in the developer, which is not preferable.

Further, an organic solvent, for example, can be added to the developer composed of the alkaline aqueous solution.
Examples of the organic solvent include ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methanol, ethanol, alcohols such as n-propanol, i-propanol, n-butanol, t-butanol, cyclopentanol, cyclohexanol, 1,4-hexanediol, and 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 can be used alone or in combination of two or more.
The amount of the organic solvent used is preferably 100% by volume or less based on the alkaline aqueous solution. In this case, if the amount of the organic solvent used exceeds 100% by volume, the developability may be reduced and the undeveloped portion of the exposed portion may be increased.
In addition, an appropriate amount of a surfactant or the like can be added to a developer composed of an alkaline aqueous solution.
After development with a developing solution composed of an alkaline aqueous solution, the film is generally washed with water and dried.

The polysiloxane (A) of the present invention is particularly useful as a resin component in a radiation-sensitive resin composition suitable as a resist for fine processing using radiation such as far ultraviolet rays, electron beams, and X-rays.
The radiation sensitive resin composition of the present invention using polysiloxane (A) is, ArF excimer laser (wavelength 193 nm) or F ₂ excimer laser effective wavelength 200nm or less of the radiation far ultraviolet typified by (wavelength 157 nm) High sensitivity to radiation, high transparency to radiation, excellent resolution, easy control of the solubility of resin components in alkaline developer, and excellent sensitivity, developability, dry etching resistance, etc. It can be used very favorably in the manufacture of LSIs, which are expected to be further miniaturized.
The silicon-containing compound (a) of the present invention is particularly useful as a raw material for synthesizing a polysiloxane (A), and the norbornene-based compound (α) of the present invention is particularly useful as a raw material for synthesizing a silicon-containing compound (a). .

Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments.
Each measurement and evaluation in Examples and Comparative Examples was performed in the following manner.
Mw:
Monodisperse polystyrene was used as a standard under the analysis conditions of Tosoh Corp. GPC columns (two G2000HXL, one G3000HXL, one G4000HXL), a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C. It was measured by gel permeation chromatography (GPC).
Absorption coefficient:
Each polysiloxane was dissolved in 2-heptanone to prepare a resin solution having a solid content concentration of 5%. Thereafter, each of the resin solutions was applied on a magnesium fluoride substrate by spin coating, and heated on a hot plate maintained at 110 ° C. or 140 ° C. for 90 seconds to form a film having a thickness of 1,000 °. Thereafter, the extinction coefficient of this film at 157 nm and 193 nm was measured.

Example 1 (Synthesis of norbornene compound (α))
A solution in which 80 g of pentafluoropropen-2-yl benzoate was dissolved in 100 ml of diethyl ether was charged into a 300 ml autoclave, 21 g of cyclopentadiene was added, and the mixture was reacted by heating at 140 ° C. for 10 hours. After completion of the reaction, diethyl ether was distilled off, and then 500 ml of tetrahydrofuran and 200 ml of a 20% by weight aqueous solution of sodium hydroxide were added, and the mixture was heated at 80 ° C. for 3 hours to react. Then, after adding 500 ml of diethyl ether, the aqueous layer was separated with a separating funnel, and the aqueous layer was washed again with 500 ml of diethyl ether. Thereafter, 500 ml of diethyl ether was added to the aqueous layer, and a 10% by weight aqueous solution of sulfuric acid was added until the aqueous layer became acidic. Then, the ether layer was separated and washed twice with water. Then, after distilling off the solvent from the obtained ether layer, the residue was subjected to fractional distillation to obtain 20.5 g of the component (A) having a boiling point of 42 to 66 ° C (pressure 7.5 mmHg) and a boiling point of 75 to 83 ° C. 15.6 g of the component (B) having a pressure of 0.75 mmHg was obtained.
The obtained components were analyzed by ¹ H and ¹⁹ F NMR analysis and gas chromatography-mass spectrometry (GC-MS), and the results were as follows. The component (A) was 3,3-difluoro-2- ( Trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ol (norbornene compound (α-1)), wherein component (B) is 5,5-difluoro-4- (trifluoro Methyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-en-4-ol (norbornene-based compound (α-2)).

Component (A):
¹ H-NMR spectrum (δ; unit ppm):
1.4 to 2.2 (CH ₂ part);
2.4 to 2.7, 2.8, 3.0 (above, bridgehead);
5.6, 6.0, 6.2 to 6.4 (or more, carbon-carbon double bond part);
7.2 (OH group).
¹⁹ F-NMR spectrum (δ; unit ppm):
-121 to -119, -111 to -108 (or more, ₂ parts of CF);
-76, -73 (above, ₃ parts of CF).
GC-MS (m / e) CI [M + H ⁺ ]:
215.

Component (B):
¹ H-NMR spectrum (δ; unit ppm):
1.2-3.3 (CH ₂ part and bridgehead);
5.6 to 6.4 (carbon-carbon double bond);
7.2 (OH group).
¹⁹ F-NMR spectrum (δ; unit ppm):
-121 to -117, -111 to -108 (or more, ₂ parts of CF);
-76, -73 (above, ₃ parts of CF).
GC-MS (m / e) CI [M + H ⁺ ]:
281.

Example 2 (Synthesis of silicon-containing compound (a))
In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 24 g of triethoxysilane and 3,3-difluoro-2- (trifluoromethyl) bicyclo [2.2.1] obtained in Example 1 were added. After charging 20.5 g of hept-5-en-2-ol and stirring at room temperature, 0.2 ml of a 0.2 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added, and the reaction was performed. And heated at 80 ° C. for 18 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered through a suction funnel covered with celite, and the obtained filtrate was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was purified by distillation to obtain 19.2 g of a compound as a fraction having a boiling point of 95 to 98 ° C. at 0.75 mmHg.
This compound was analyzed by ¹ H, ¹³ C, ¹⁹ F and ²⁹ Si for NMR analysis (chemical shift δ) and gas chromatography-mass spectrometry (GC-MS). -1) (hereinafter, referred to as "silicon-containing compound (a-1)").
¹ H-NMR spectrum and ¹³ C-NMR spectrum of this compound are shown in FIG. 1 and FIG.
FIG. 3 shows the ¹⁹ F-NMR spectrum and FIG. 4 shows the ²⁹ Si-NMR spectrum.

¹ H-NMR spectrum (δ; unit ppm):
1.4 to 2.5 (norbornene ring);
1.6 (CH ₃ part);
2.8-3.4 (bridge head);
4.2 (CH ₂ part).
¹³ C-NMR spectrum (δ; unit ppm):
14 to 15.5 (carbon atom bonded to silicon atom);
18 (CH ₃ parts);
22～24,31～34 (above, CH ₂ parts of norbornene ring);
42-47 (bridge head);
59 ( ₂ parts of O-CH);
78 to 82 ( ₃ parts of CF);
122~129 (CF ₂ parts and C (CF ₃₎ OH unit).
¹⁹ F-NMR spectrum (δ; unit ppm):
-123 to -121, -120 to -116, -111 to -108
(Above, ₂ parts of CF);
-77 to -72 ( ₃ parts of CF).
²⁹ Si-NMR spectrum (δ; unit ppm):
-48 to -51.
GC-MS (m / e) CI [M + H ⁺ ]:
379.

Example 3 (Synthesis of silicon-containing compound (a))
In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 14 g of triethoxysilane and 5,5-difluoro-4- (trifluoromethyl) tetracyclo [6.2.1. ^13-6 . 0 ^2,7 ] dodec-9-en-4-ol was stirred at room temperature, and then 0.2 ml of a 0.2 mol i-propyl alcohol solution of chloroplatinic acid was added. Started and heated at 80 ° C. for 18 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered through a suction funnel covered with celite, and the obtained filtrate was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude distillation product was purified to obtain 11.1 g of a compound as a fraction having a boiling point of 135 to 138 ° C. at 0.38 mmHg.
This compound was analyzed by ¹ H, ¹³ C, ¹⁹ F and ²⁹ Si for NMR analysis (chemical shift δ) and gas chromatography-mass spectrometry (GC-MS). -1) (hereinafter, referred to as "silicon-containing compound (a-2)").
The ¹ H-NMR spectrum and ¹³ C-NMR spectrum of this compound are shown in FIG. 5 and FIG.
FIG. 7 shows the ¹⁹ F-NMR spectrum and FIG. 8 shows the ²⁹ Si-NMR spectrum.

¹ H-NMR spectrum (δ; unit ppm):
1.2 to 3.4 (norbornene ring);
1.6 (CH ₃ part);
4.2 (CH ₂ part).
¹³ C-NMR spectrum (δ; unit ppm):
18 (CH ₃ parts);
18.5 to 20 (carbon atom bonded to silicon atom);
24 to 30 (CH ₂ part of a norbornene ring);
39 to 43 (CH ₂ part and CH part of norbornene ring);
44 to 47 (CH part of norbornene ring);
59 ( ₂ parts of O-CH);
79 to 83 ( ₃ parts of CF);
122~129 (CF ₂ parts and C (CF ₃₎ OH unit).
¹⁹ F-NMR spectrum (δ; unit ppm):
-120 to -117, -111 to -107 (above, ₂ parts of CF);
-76 to -75, -72 (above, ₃ parts of CF).
²⁹ Si-NMR spectrum (δ; unit ppm):
-52.
GC-MS (m / e) CI [M + H ⁺ ]:
445.

Examples 4 to 12 (Production of polysiloxane (A))
A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with a silicon-containing compound shown in Table 1, a 1.75% by weight aqueous oxalic acid solution, and 30 g of 4-methyl-2-pentanone (MIBK), followed by stirring. While reacting at 80 ° C. for 6 hours. After that, the reaction vessel is cooled with ice to stop the reaction, the reaction solution is transferred to a separating funnel, the aqueous layer is discarded, and ion-exchanged water is further added and washed with water to make the reaction solution neutral. The washing with water was repeated until. Thereafter, the organic layer was distilled off under reduced pressure to obtain polymers having the yields shown in Tables 1-1 and 1-2.

  The structures of the silicon-containing compounds (3-1) to (3-6) used in Examples 4 to 12 are as follows.

  Next, each of the obtained polymers was dissolved in the amount of 4-methyl-2-pentanone (MIBK) shown in Table 2, and the amounts of distilled water and triethylamine shown in Table 2 were added. After stirring for an hour, the mixture was ice-cooled, an aqueous solution in which 8.0 g of oxalic acid was dissolved in 300 g of distilled water was added, and the mixture was further stirred. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The water washing was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain a polysiloxane (A) having a yield and a molecular weight (Mw) shown in Table 2. About each obtained polysiloxane (A), the extinction coefficient was evaluated. The evaluation results are also shown in Table 2.

Examples 13 to 21 (Evaluation of radiation-sensitive resin composition)
A mixture of 100 parts by weight of each of the polysiloxanes (A) obtained in Examples 4 to 12 and an acid generator shown in Table 3 and 2-phenylbenzimidazole in an amount of 8 mol% based on the total amount of the acid generator. Was dissolved in a solvent shown in Table 3 and filtered through a membrane filter having a pore size of 0.45 μm to prepare a composition solution.
Next, each composition solution was applied by spin coating on the substrate on which the lower layer film (β-1) obtained in the following Production Example was formed, and PB was performed for 90 seconds on a hot plate maintained at 140 ° C. As a result, a resist film having a thickness of 1,200 ° was formed. Thereafter, for each resist film, ArF excimer laser (wavelength 193 nm, a numerical aperture of 0.55) through or F ₂ excimer laser (wavelength 157 nm, numerical aperture 0.60) a reticle, after exposure, respectively by changing the amount of exposure PEB was performed for 90 seconds on a hot plate maintained at 100 ° C. and 100 ° C., respectively. Thereafter, development was performed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to form a line and space pattern (1L1S), and the resolution was evaluated. The evaluation results are also shown in Table 3. In Table 3, ArF is ArF excimer laser, F2 means F ₂ excimer laser.

Production example (formation of lower layer film)
Under a nitrogen atmosphere, 100 parts by weight of acenaphthylene, 78 parts by weight of toluene, 52 parts by weight of dioxane, and 3 parts by weight of azobisisobutyronitrile were charged into a separable flask equipped with a thermometer, and stirred at 70 ° C. for 5 hours. Thereafter, 5.2 parts by weight of p-toluenesulfonic acid monohydrate and 40 parts by weight of paraformaldehyde were added, and the mixture was heated to 120 ° C. and further stirred for 6 hours. Thereafter, the reaction solution was poured into a large amount of isopropanol, and the precipitated polymer was separated by filtration and dried at 40 ° C. under reduced pressure to obtain a polymer.
This polymer had an Mw of 22,000, and as a result of ¹ H-NMR analysis, it was confirmed that the polymer had a structural unit represented by the following formula.

10 parts by weight of the obtained polymer, 0.5 parts by weight of bis (4-t-butylphenyl) iodonium 10-camphor-sulfonate, 4,4 '-[1- {4- (1- [4-hydroxyphenyl]- After uniformly mixing 0.5 part by weight of [1-methylethyl) phenyl {ethylidene] bisphenol and 89 parts by weight of cyclohexanone, the mixture was filtered through a membrane filter having a pore size of 0.1 μm to prepare a composition for forming an underlayer film.
Next, the obtained composition for forming an underlayer film is applied on a silicon wafer by spin coating so as to obtain a 300 nm-thick underlayer film, and then on a hot plate at 180 ° C. for 60 seconds, and then. Baking was performed at 300 ° C. for 120 seconds to form a lower layer film (β-1).

The acid generators and solvents in Table 3 are as follows.
Acid generator B-1: triphenylsulfonium trifluoromethanesulfonate B-2: triphenylsulfonium nonafluoro-n-butanesulfonate B-3: triphenylsulfonium 2-norbornyl-1,1,2,2-tetrafluoroethane- 1-sulfonate B-4: triphenylsulfonium 10-camphorsulfonate
Solvent PGMEA: propylene glycol monomethyl ether acetate MAK: 2-heptanone EL: ethyl lactate FAL: 2,2,3,3,4,4,5,5-octafluoro-1-pentanol

FIG. 3 is a view showing a ¹ H-NMR spectrum of a silicon-containing compound (a-1). FIG. 3 is a view showing a ¹³ C-NMR spectrum of a silicon-containing compound (a-1). FIG. 3 is a view showing a ¹⁹ F-NMR spectrum of a silicon-containing compound (a-1). FIG. 3 is a view showing a ²⁹ Si-NMR spectrum of a silicon-containing compound (a-1). FIG. 3 is a view showing a ¹ H-NMR spectrum of a silicon-containing compound (a-2). FIG. 3 is a view showing a ¹³ C-NMR spectrum of a silicon-containing compound (a-2). FIG. 3 is a view showing a ¹⁹ F-NMR spectrum of a silicon-containing compound (a-2). FIG. 3 is a view showing a ²⁹ Si-NMR spectrum of a silicon-containing compound (a-2).

Claims (4)

A norbornene-based compound represented by the following general formula (α).

[In the general formula (α), n is 0 or 1. ] A silicon-containing compound represented by the following general formula (1) or (2).

[In the general formula (1), X ¹ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom or a primary or secondary group. Or a tertiary amino group, a plurality of X ¹ may be the same or different, and Y ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogen group having 1 to 20 carbon atoms. A plurality of Y ^{1 s} may be the same or different from each other, x is an integer of 0 to 2, and n is 0 or 1.
In the general formula (2), X ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a primary, secondary or A tertiary amino group; n is 0 or 1; ] It has at least one selected from the group consisting of a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and has a weight average molecular weight in terms of polystyrene of 500 by gel permeation chromatography (GPC). ~ 1,000,000 polysiloxane.

[In the general formula (I), n is 0 or 1.
In the general formula (II), X is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a primary, secondary or tertiary group. And n represents 0 or 1. ]   (A) Among the polysiloxanes according to claim 3, an alkali-insoluble or poorly alkali-soluble resin having an acid-dissociable group, the resin becoming alkali-soluble when the acid-dissociable group is dissociated, and ( B) A radiation-sensitive resin composition containing a radiation-sensitive acid generator.

Images