JP5486836B2 - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and other photofabrication processes, and the same. The present invention relates to a pattern forming method. More specifically, the present invention is suitable for the case where far ultraviolet rays and electron beams of 250 nm or less, preferably 220 nm or less are used as an exposure light source, and an actinic ray-sensitive or radiation-sensitive resin composition suitable for microfabrication technology and The present invention relates to a pattern forming method using the same.

  In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.

  The chemically amplified resist composition generates an acid in the exposed area by irradiation with actinic rays or radiation such as far ultraviolet light, and a reaction solution using the acid as a catalyst to develop a developing solution for the irradiated and non-irradiated areas of the active light or radiation. It is a pattern forming material that changes the solubility in the substrate and forms a pattern on the substrate.

  When a KrF excimer laser is used as an exposure light source, a resin having a basic skeleton of poly (hydroxystyrene) having a small absorption mainly in the 248 nm region is used as a main component. A pattern is formed, which is a better system than the conventional naphthoquinone diazide / novolak resin system.

  On the other hand, when a further short wavelength light source, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group exhibits a large absorption in the 193 nm region. It wasn't.

  For this reason, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed.

  Furthermore, it has been found that the performance is improved by adding a surfactant to the resin having the alicyclic hydrocarbon structure. For example, as described in Patent Document 1 and the like, radial unevenness (striation) is prevented by adding a fluorine-based surfactant to a positive photoresist composition.

  Along with the miniaturization of semiconductor elements, the wavelength of the exposure light source and the numerical aperture (high NA) of the projection lens have increased, and the resolution between the projection lens and the sample has been increased with the aim of higher resolution by further shortening the wavelength. A so-called immersion method is known in which a liquid having a refractive index (hereinafter also referred to as “immersion liquid”) is used. The liquid immersion method is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

  Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. Explaining by taking a positive chemical amplification image forming method as an example, the acid generator in the exposed area is decomposed by exposure to generate an acid upon exposure, and the generated acid is reacted as a reaction catalyst by post exposure baking (PEB). Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.

  The ArF excimer laser (193 nm) resist using this chemical amplification mechanism is becoming mainstream at present, but when immersion exposure is performed, the formed line pattern collapses and becomes a defect during device manufacturing. However, the pattern collapse problem and the LWR (line width roughness) where the pattern side walls are rough were still insufficient.

  In addition, when a chemically amplified resist is applied to immersion exposure, the resist layer comes into contact with the immersion liquid during exposure, so that the resist layer is altered and components that adversely affect the immersion liquid are exuded from the resist layer. It has been pointed out to do. On the other hand, Patent Documents 2 to 5 describe examples in which exudation is suppressed by adding a resin containing silicon atoms or fluorine atoms.

  In the immersion exposure process, when exposure is performed using a scanning immersion exposure machine, the exposure speed decreases unless the immersion liquid moves following the movement of the lens. Concerned about giving. In the case where the immersion liquid is water, it is desirable that the resist film be hydrophobic because the water followability is good.

  Various compounds have also been found for basic compounds that are main constituents of chemically amplified resist compositions, and photosensitive compositions containing anilines, imidazoles, pyridines, and ammonia as basic compounds. Is disclosed.

  However, from the viewpoint of overall performance as a resist, it is actually difficult to find an appropriate combination of resin, photoacid generator, basic compound, surfactant, solvent, and the like to be used. However, there is a strong demand for both resolution performance, corner proximity, and development defect performance.

Japanese Patent Laid-Open No. 10-307385 Japanese Patent Laid-Open No. 5-127369 JP-A-6-266111 JP 2007-182488 A JP 2007-153982 A

  The object of the present invention is to provide an actinic ray having good corner proximity, capable of forming a pattern with few development defects, little acid elution into the immersion liquid, and good followability to the immersion liquid. A radiation sensitive resin composition and a pattern forming method using the same.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention shown below.
(1) (A) Resin whose solubility in an alkali developer is increased by the action of an acid, (B) A compound that generates an acid upon irradiation with actinic rays or radiation, (C) Alkaline development by being decomposed by the action of an alkali developer A resin containing a repeating unit having a polarity-converting group that increases solubility in a liquid and containing at least one of a fluorine atom and a silicon atom, and (D) a resin represented by the following general formula (1): An actinic ray-sensitive or radiation-sensitive resin composition comprising a nitrogen-containing organic compound having a nitrogen heterocycle.

(In the formula, R ¹ is a linear, branched or cyclic divalent substituent having 2 to 20 carbon atoms that forms a nitrogen-containing heteroaliphatic ring or a nitrogen-containing heteroaromatic ring together with nitrogen atoms bonded at both ends. Represents a group, and may include an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom, R ² represents a linear or branched alkylene group that may include a carbonyl group having 2 to 10 carbon atoms, and R ³ represents (Represents a saturated or unsaturated hydrocarbon group or acyl group which may contain a hydroxyl group, a carbonyl group, an ester group, an ether group steroid skeleton, a cyano group, or a combination of two or more thereof.)
(2) The actinic ray-sensitive or radiation-sensitive resin composition according to (1), wherein the resin (C) contains a repeating unit having two or more polar conversion groups.

  (3) The actinic ray or sensation according to (1) or (2), wherein the resin (C) contains a repeating unit having at least one of a fluorine atom and a silicon atom and a polar conversion group. Radiation resin composition.

(4) The nitrogen-containing organic compound (D) contains one or more nitrogen-containing organic compounds having nitrogen-containing heterocycles represented by the following general formulas (2) to (10). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (3).

(In the formula, each R ⁴ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms. R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a saturated or unsaturated hydrocarbon group which may contain a hydroxyl group, a carbonyl group, an ester group, an ether group, a cyano group or an acetal group, and R ⁷ represents Represents a single bond, a methylene group, an oxygen atom or a sulfur atom, R ⁸ represents a linear or branched alkylene group having 1 to 9 carbon atoms, R ⁹ represents a hydroxyl group, a carbonyl group, an ester group, an ether group or Represents a saturated or unsaturated hydrocarbon group which may contain a cyano group.)
(5) As the nitrogen-containing organic compound (D), one or more nitrogen-containing organic compounds having a nitrogen-containing heterocycle and a steroid skeleton represented by the following general formulas (2 ′) to (10 ′) are used. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (4), which is contained.

(In the formula, each R ⁴ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms. R ⁵ represents a hydrogen atom or a methyl group, and R ^{6 ′} represents a saturated or unsaturated hydrocarbon group which may contain a steroid skeleton-containing hydroxyl group, carbonyl group, ester group, ether group, cyano group or acetal group. R ⁷ represents a single bond, a methylene group, an oxygen atom or a sulfur atom, R ⁸ represents a linear or branched alkylene group having 1 to 9 carbon atoms, and R ^{9 ′} represents a hydroxyl group having a steroid skeleton. Represents a saturated or unsaturated hydrocarbon group which may contain a carbonyl group, an ester group, an ether group or a cyano group.)
(6) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5), wherein the resin (A) contains a repeating unit containing a lactone structure.

  (7) The sensation according to any one of (1) to (6), wherein the resin (A) contains a repeating unit having a monocyclic or polycyclic acid-decomposable group. An actinic ray or radiation sensitive resin composition.

  (8) A step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (7), and exposing and developing the coating film, Pattern forming method.

  (9) The pattern forming method according to (8), wherein the coating film is exposed through an immersion liquid.

  According to the present invention, it is possible to form a pattern with good corner proximity, less development defects, less acid elution into the immersion liquid, and good actinic ray or radiation sensitivity with good followability to the immersion liquid. A resin composition and a pattern forming method using the resin composition can be provided.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains, as a basic compound, (D) one or more nitrogen-containing organic compounds having a nitrogen-containing heterocycle as a quencher,
(A) a resin whose solubility in an alkaline developer is increased by the action of an acid, and
(B) a compound that generates an acid upon irradiation with actinic rays or radiation, and
(C) A resin containing a repeating unit having a polarity converting group and containing at least one of a fluorine atom and a silicon atom.

(D) Nitrogen-containing organic compound The composition of the present invention contains a nitrogen-containing organic compound having a nitrogen-containing heterocycle as a basic compound.
As the nitrogen-containing organic compound, a nitrogen-containing organic compound having a nitrogen-containing heterocycle represented by the following general formula (1), preferably a nitrogen-containing heterocycle represented by the following general formulas (2) to (10) Examples thereof include a nitrogen-containing organic compound having a ring or a nitrogen-containing organic compound having a nitrogen-containing heterocycle represented by the following general formulas (2 ′) to (10 ′) and having a steroid skeleton. Furthermore, the composition of the present invention can be suitably used for immersion exposure since there is little elution of the amine compound in water during immersion.

Here, the nitrogen-containing organic compound blended in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a nitrogen-containing organic compound having a nitrogen-containing heterocycle represented by the following general formula (1) as described above. A compound. A nitrogen-containing organic compound having a nitrogen-containing heterocycle represented by the following general formula (1) having a molecular weight of 380 or more is preferable.

In the formula, R ¹ is a linear, branched or cyclic divalent substituent having 2 to 20 carbon atoms which forms a nitrogen-containing heteroaliphatic ring or a nitrogen-containing heteroaromatic ring together with nitrogen atoms bonded at both ends. Represents an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. R ² represents a linear or branched alkylene group which may contain a carbonyl group having 2 to 10 carbon atoms. R ³ represents a hydroxyl group, a carbonyl group, an ester group, an ether group, a cyano group, a steroid skeleton, or a saturated or unsaturated hydrocarbon group or acyl group that may contain a combination of two or more thereof.

In general formula (1), R ¹ is a linear, branched or cyclic 2 having 2 to 20 carbon atoms that forms a nitrogen-containing heteroaliphatic ring or a nitrogen-containing heteroaromatic ring together with nitrogen atoms bonded at both ends. Represents a valent substituent and may contain an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. Specific examples of the nitrogen-containing heteroaliphatic ring formed by R ¹ together with the nitrogen atom bonded at both ends include aziridine, azetidine, pyrrolidine, piperidine, 2-imidazolidine, 2-pyrroline, pyrazolidine, piperazine, 3-pyrazoline, Examples thereof include morpholine, thiomorpholine, and alkyl or aryl substituents thereof. Specific examples of the nitrogen-containing heteroaromatic ring formed by R ¹ together with the nitrogen atom bonded at both ends include pyrrole, imidazole, pyrazole, triazole, Examples include, but are not limited to, tetrazole, benzimidazole, 1H-indazole, purine, perimidine, phenoxazine, phenothiazine, and their chain or cyclic alkyl, aryl, or aralkyl substituents.

In the general formula (1), R ² represents a linear or branched alkylene group that may contain a carbonyl group having 2 to 10 carbon atoms, specifically, an ethylene group, trimethylene group, tetramethylene group, pentamethylene. Groups, hexamethylene groups, heptamethylene groups, octamethylene groups, nonamethylene groups, decamethylene groups, propylene groups, ethylethylene groups, and oxo substituents thereof are not limited thereto.

In the general formula (1), R ³ represents a hydroxyl group, a carbonyl group, an ester group, an ether group, a cyano group, a steroid skeleton, or a saturated or unsaturated hydrocarbon group or acyl group that may contain a combination of two or more thereof. More specifically, it can be represented by the general formula —CO—R ⁶ , —CH ₂ —OR ⁶ or R ⁹ , —CO—R ^{6 ′} , —CH ₂ —OR ^{6 ′} or R ^{9 ′.} Among them, R ⁶ , R ⁹ , R ^{6 ′} and R ^{9 ′} will be described later.

Specific examples of the nitrogen-containing organic compound represented by the general formula (1) include specific examples of the nitrogen-containing organic compound represented by the following general formulas (2) to (10) and (2 ′) to (10 ′). In addition to the examples, the following can be exemplified, but the invention is not limited thereto.

In one embodiment, the nitrogen-containing organic compound blended in the composition of the present invention is a nitrogen-containing organic compound having a nitrogen-containing heterocycle represented by the following general formulas (2) to (10) as described above. is there. Preferred is a nitrogen-containing organic compound having a nitrogen-containing heterocycle and a molecular weight of 430 or more.

In the formula, each R ⁴ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms. . R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a saturated or unsaturated hydrocarbon group which may contain a hydroxyl group, a carbonyl group, an ester group, an ether group, a cyano group or an acetal group. R ⁷ represents a single bond, a methylene group, an oxygen atom or a sulfur atom. R ⁸ represents a linear or branched alkylene group having 1 to 9 carbon atoms. R ⁹ represents a saturated or unsaturated hydrocarbon group which may contain a hydroxyl group, a carbonyl group, an ester group, an ether group or a cyano group.

In the general formulas (2), (3), (5), (6), (8), (9), R ⁴ is independently a hydrogen atom, a linear, branched or cyclic group having 1 to 10 carbon atoms. Represents an alkyl group, an aryl group having 6 to 15 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclohexyl group. Decyl group, adamantyl group, phenyl group, naphthyl group, and benzyl group, particularly preferably a hydrogen atom, a methyl group, an ethyl group, and a phenyl group.

In general formulas (2) to (7), R ⁵ represents a hydrogen atom or a methyl group.
In general formulas (2) to (7), R ⁶ represents a saturated or unsaturated hydrocarbon group which may contain a hydroxyl group, a carbonyl group, an ester group, an ether group, a cyano group or an acetal group. The following can be illustrated. In the following formula, the broken line indicates the coupling position, and so on.

In the general formulas (4), (7) and (10), R ⁷ represents a single bond, a methylene group, an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

In the general formulas (8), (9) and (10), R ⁹ represents a saturated or unsaturated hydrocarbon group which may contain a hydroxyl group, a carbonyl group, an ester group, an ether group or a cyano group, specifically The following can be exemplified.

Specific examples of the nitrogen-containing organic compounds represented by the general formulas (2) to (10) include the following, but are not limited thereto. In the following formulae, Me represents a methyl group, Ph represents a phenyl group, and so forth.

In one aspect, the nitrogen-containing organic compound blended in the composition of the present invention has a nitrogen-containing organic ring having a nitrogen-containing heterocycle represented by the following general formulas (2 ′) to (10 ′) as described above. A compound. A nitrogen-containing organic compound having a molecular weight of 430 or more having a nitrogen-containing heterocycle represented by the following general formulas (2 ′) to (10 ′) is preferable.

In the formula, each R ⁴ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms. . R ⁵ represents a hydrogen atom or a methyl group. R ^{6 ′} represents a saturated or unsaturated hydrocarbon group which may contain a hydroxyl group, carbonyl group, ester group, ether group, cyano group or acetal group having a steroid skeleton. R ⁷ represents a single bond, a methylene group, an oxygen atom or a sulfur atom. R ⁸ represents a linear or branched alkylene group having 1 to 9 carbon atoms. R ^{9 ′} represents a saturated or unsaturated hydrocarbon group that may contain a hydroxyl group, carbonyl group, ester group, ether group or cyano group having a steroid skeleton.

In general formulas (2 ′) to (10 ′), R ⁴ , R ⁵ , R ⁷ and R ⁸ are the same as described above.
In the general formulas (2 ′) to (7 ′), R ^{6 ′} represents a saturated or unsaturated hydrocarbon group which may contain a steroid skeleton-containing hydroxyl group, carbonyl group, ester group, ether group, cyano group or acetal group. Specifically, the following structures can be exemplified, but are not limited thereto. In the following formula, Ac represents an acetyl group, and the same shall apply hereinafter.

In the general formulas (8 ′) to (10 ′), R ^{9 ′} represents a saturated or unsaturated hydrocarbon group that may contain a hydroxyl group, a carbonyl group, an ester group, an ether group or a cyano group having a steroid skeleton. Specifically, the following structures can be exemplified, but not limited thereto.

Specific examples of the nitrogen-containing organic compounds represented by the general formulas (2 ′) to (10 ′) include the following, but are not limited thereto.

According to the present invention, in these nitrogen-containing organic compounds having a nitrogen-containing heterocycle, the nitrogen-containing heterocycle structure and functional groups such as ether, ester, and acetal located in the vicinity have high affinity with acids, The rapid capture of the generated acid from the photoacid generator is realized, while the side chain portion having a high carbon number represented by R ³ in the general formula (1) is an actinic ray or sensitization of the nitrogen-containing organic compound. It is expected to have a great influence on distribution, diffusion, volatilization, water solubility, etc. in the radiation resin composition film, and as a result, high resolution in the photoresist to which the nitrogen-containing organic compound of the present invention is added It is considered that the dependency on the mask coverage is reduced, and in addition, it can be applied to immersion exposure. In addition, by selecting an appropriate structure from among the possible structures of the nitrogen-containing organic compound having a nitrogen-containing heterocycle of the present invention, the basicity of the nitrogen-containing organic compound of the present invention, the acid capture rate, The diffusion rate, water solubility, etc. can be adjusted appropriately according to the resist polymer, acid generator, exposure method used, etc., and as a result, the performance of the actinic ray-sensitive or radiation-sensitive resin composition such as the pattern shape is optimized. Can be adjusted.

  The nitrogen-containing organic compounds represented by the above formulas (1) to (10) and (2 ') to (10') are produced by selecting an optimum method according to the structure of the compound. Specifically, a method using an N-alkylation reaction of a nitrogen-containing heterocyclic compound having a hydrogen atom on the nitrogen atom, or O-acylation or O- of a nitrogen-containing heterocyclic compound having a hydroxyalkyl substituent on N Although the method using an alkylation reaction can be illustrated, it is not limited to these methods. This will be described in detail below.

First, as a first method, a production method by N-alkylation reaction of a nitrogen-containing heterocyclic compound having a hydrogen atom on a nitrogen atom can be mentioned, and this method is basically a general formula (1) to (10). And (2 ′) to (10 ′) are all applicable.

In the formula, R ¹ is a linear, branched or cyclic divalent substituent having 2 to 20 carbon atoms which forms a nitrogen-containing heteroaliphatic ring or a nitrogen-containing heteroaromatic ring together with nitrogen atoms bonded at both ends. Represents an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. R ² represents a linear or branched alkylene group which may contain a carbonyl group having 2 to 10 carbon atoms. R ³ represents a hydroxyl group, a carbonyl group, an ester group, an ether group, a cyano group, a steroid skeleton, or a saturated or unsaturated hydrocarbon group or acyl group that may contain a combination of two or more thereof. X represents a leaving group such as a halogen atom, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, or a hydroxyl group.

  The amount of the compound (12) used as the alkylating agent for this reaction is preferably 0.1 to 10 mol, particularly 0.3 to 2 mol, per 1 mol of the nitrogen-containing heterocyclic compound (11). The reaction is carried out without solvent or in a solvent. Solvents include alcohols such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol, ethylene glycol, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, diethyl ether, dibutyl ether, tetrahydrofuran, 1,4- Non-protons such as ethers such as dioxane and diglyme, chlorinated solvents such as methylene chloride, chloroform and 1,2-dichloroethylene, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone Polar solvents, carboxylic acids such as formic acid and acetic acid, esters such as ethyl acetate and butyl acetate, ketones such as acetone and 2-butanone, nitriles such as acetonitrile, pyridine, triethylamine and the like Min acids, out of the water by selecting the reaction conditions can be used alone or as a mixture. The reaction temperature is selected in the range from 0 ° C. to the reflux temperature of the solvent depending on the reaction rate. If necessary, a base may be added to the reaction. Examples of the base include amines such as pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, imidazole, sodium methoxide, sodium ethoxide, potassium t. -Metal alkoxides such as butoxide, carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, hydroxides such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium hydride, potassium hydride, etc. It can be selected from metal hydrides, organic metals such as butyllithium and ethylmagnesium bromide, and metal amides such as lithium diisopropylamide, depending on the reaction conditions, and can be used alone or in combination. Alternatively, the nitrogen-containing heterocyclic compound itself as a raw material can be used as a base. The amount of the base used is preferably 0.1 to 10 mol, particularly 0.5 to 5 mol, per 1 mol of the nitrogen-containing heterocyclic compound (11).

  In order to increase the reaction rate, the reaction may include iodide such as sodium iodide, lithium iodide and tetrabutylammonium iodide, and bromide such as sodium bromide, lithium bromide and tetrabutylammonium bromide. . When the catalyst is added, the addition amount is preferably 0.001 to 2 mol, particularly 0.005 to 0.5 mol, per 1 mol of the nitrogen-containing heterocyclic compound (11). The reaction time is preferably about 0.5 to 100 hours, although it is desirable in terms of yield to follow the reaction by gas chromatography (GC) or thin layer chromatography (TLC) to complete the reaction. The target product (1) is obtained from the reaction mixture by ordinary aqueous work-up. If necessary, compound (1) can be purified by conventional methods such as distillation, chromatography, recrystallization and the like. Alternatively, it may be possible to subject the salt produced in the reaction to filtration or to directly purify the reaction solution without performing an aqueous work-up.

  Depending on the structure of the target product, in addition, cyclic ethers such as oxirane and oxetane; α, β-unsaturated carbonyl compounds such as acrylic acid esters and vinyl ketones; addition reaction of nitrogen-containing heterocyclic compounds to cyclic carbonates It may be possible to obtain the object (1).

As a second method, a production method using an O-acylation or O-alkylation reaction of a nitrogen-containing heterocyclic compound having a hydroxyalkyl substituent on N can be mentioned. This method is particularly effective for producing nitrogen-containing organic compounds represented by the general formulas (2) to (7) and (2 ′) to (7 ′).

In the formula, R ¹ is a linear, branched or cyclic divalent substituent having 2 to 20 carbon atoms which forms a nitrogen-containing heteroaliphatic ring or a nitrogen-containing heteroaromatic ring together with nitrogen atoms bonded at both ends. Represents an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. R ² represents a linear or branched alkylene group which may contain a carbonyl group having 2 to 10 carbon atoms. R ³ represents a hydroxyl group, a carbonyl group, an ester group, an ether group, a cyano group, a steroid skeleton, or a saturated or unsaturated hydrocarbon group or acyl group that may contain a combination of two or more thereof. Y represents a leaving group such as a halogen atom, an alkyl or arylsulfonyloxy group, a hydroxyl group, an acyloxy group, a phenoxy group, and an alkoxy group.

The reaction is carried out by allowing the compound (14) which is an alkylating agent or acylating agent to act on the N- (hydroxyalkyl) nitrogen-containing heterocyclic compound (13) which can be produced by the above-described method, etc. Get. When R ³ is an alkyl group, compound (14) is an alkylating agent, and when R ³ is an acyl group, compound (14) is an acylating agent. The amount of compound (14) to be used is preferably 0.1 to 5.0 mol, particularly 0.3 to 2.0 mol, per 1 mol of N- (hydroxyalkyl) nitrogen-containing heterocyclic compound (13). . The reaction is carried out without solvent or in a solvent. Solvents include hexane, heptane, benzene, toluene, xylene and other hydrocarbons, diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, diglyme and other ethers, methylene chloride, chloroform, 1,2-dichloroethylene, etc. Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, carboxylic acids such as formic acid and acetic acid, ethyl acetate and butyl acetate Reaction conditions from esters, ketones such as acetone and 2-butanone, nitriles such as acetonitrile, amines such as pyridine and triethylamine, alcohols such as methanol, ethanol, 2-propanol and t-butyl alcohol, and water It can be used alone or in combination with more selective.

Basic compounds may be added to accelerate the reaction. Specifically, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydride, calcium hydride, potassium t-butoxide, lithium Alkali or alkaline earth metal salts such as t-butoxide, organometallics such as n-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazide, bromomagnesium diisopropylamide, pyridine, triethylamine, diisopropylethylamine, N, N -Organic amines such as dimethylaniline and 4-dimethylaminopyridine can be exemplified, but are not limited thereto. The basic compound can be used alone or in admixture of two or more, and the amount used is preferably 0.8 to 10 mol, particularly preferably 0.9 to 3.0 mol, per 1 mol of compound (14). . Although the reaction temperature can be selected in the range from -70 ° C to the reflux temperature of the solvent, it is particularly preferably carried out in the range of 0 to 50 ° C. When R ³ = acyl group and Y = alkoxy group, the compound (14) is a carboxylic acid ester compound, and this reaction is a transesterification reaction. In this case, 0.001 to 5.0 mol, especially 0.005 to 0.5 mol of the basic compound is used as a reaction catalyst with respect to 1 mol of the compound (14), and the alcohol (YH) produced by the reaction It is preferable to react while distilling off. The reaction time is preferably about 0.2 to 20 hours, although it is desirable in terms of yield to follow the reaction by gas chromatography (GC) or thin layer chromatography (TLC) to complete the reaction. The desired product (1) is obtained from the reaction mixture by ordinary aqueous work-up. If necessary, compound (1) can be purified by conventional methods such as distillation, chromatography, recrystallization and the like. Alternatively, it may be possible to subject the salt produced in the reaction to filtration or to directly purify the reaction solution without performing an aqueous work-up.

  The nitrogen-containing organic compound represented by the general formula (1) of the component (D) may be used alone or in combination of two or more kinds, and may be used in combination with other basic compounds as described below.

Other basic compounds In addition to the nitrogen-containing organic compound of the present invention, one or more quenchers such as nitrogen-containing organic compounds conventionally used as basic compounds can be used in combination.

Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

  About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.

  The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

  Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undecar 7-ene etc. are mentioned. Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris ( and t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. As the compound having an onium carboxylate structure, an anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

The amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate group, and the ammonium salt compound having a sulfonate group have at least one alkyl group bonded to a nitrogen atom. Is preferred. The alkyl chain preferably has an oxygen atom and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. -CH ₂ CH ₂ O Among the oxyalkylene group _{-, - CH (CH 3)} CH 2 O- or -CH ₂ CH ₂ CH ₂ O- structure is preferred.

  Specific examples of the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonic acid ester group, and the ammonium salt compound having a sulfonic acid ester group are exemplified in [0066] of US2007 / 0224539A. Examples thereof include, but are not limited to, compounds (C1-1) to (C3-3).

  The compounding ratio of the nitrogen-containing organic compound represented by the general formula (1) as the component (D) is 0.01 to 10 parts with respect to 100 parts (parts by mass) of the base resin of the component (A) described later. Is preferable, and 0.05 to 5 parts is particularly preferable. When other basic compounds are used in combination, the total compounding ratio of the basic compounds is preferably 0.01 to 10 parts, particularly 0.05 to 5 parts, relative to 100 parts of the base resin of the component (A). Preferably there is. If the amount is too small, there is no blending effect. If the amount is too large, the sensitivity may decrease too much.

  The use ratio of the acid generator and the total basic compound in the composition is preferably the sum of the acid generator / basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

(C) Resin containing a repeating unit having a polarity converting group and having at least one of a fluorine atom and a silicon atom The actinic ray-sensitive or radiation-sensitive resin composition of the present invention has at least one polarity converting group. A resin (C) containing the repeating unit (c) and having at least one of a fluorine atom and a silicon atom is contained. The resin (C) is hydrophobic, but the addition of the resin (C) is particularly preferable from the viewpoint of reducing development defects.

Here, the polar conversion group is a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer. For example, a lactone group, a carboxylic acid ester group (—COO—), an acid anhydride group (—C (O) OC (O) —), an acid imide group (—NHCONH—), a carboxylic acid thioester group (—COS—) , Carbonate ester group (—OC (O) O—), sulfate ester group (—OSO ₂ O—), sulfonate ester group (—SO ₂ O—) and the like.

  In addition, since the ester group directly bonded to the main chain of the repeating unit, such as in acrylate, has a poor function of being decomposed by the action of the alkali developer and increasing the solubility in the alkali developer, the polar group in the present invention Is not included.

Examples of the repeating unit (c) include a repeating unit represented by the formula (K0).

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group or a group containing a polarity converting group.

R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.

However, at least one of R _k1 and R _k2 has a polarity converting group.

  In addition, as described above, the ester group directly connected to the main chain of the repeating unit represented by the general formula (K0) is not included in the polar conversion group in the present invention.

The polar conversion group is preferably a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH—, Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.

Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.

The repeating unit (c) has a group having a partial structure represented by the general formula (KA-1) or (KB-1), and thus has a preferred polarity conversion group, but the general formula (KA-1 In the case where the partial structure does not have a bond as in the case of the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent, The group having a partial structure is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the partial structure. The partial structure represented by the general formula (KA-1) or (KB-1) is linked to the main chain of the resin (C) through a substituent at an arbitrary position.

  The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure with the group as X.

  X in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, or a carbonate ester group. More preferably, it is a carboxylic acid ester group.

The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .

Z _ka1 independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group, when there are a plurality of them.

Z _ka1 may be linked to form a ring. Examples of the ring formed by linking Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (such as a cyclic ether ring and a lactone ring).

  nka represents an integer of 0 to 10. Preferably it is an integer of 0 to 8, more preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

The electron withdrawing group as Z _{ka1 is the same} as the electron withdrawing group as Y ¹ and Y ² described later.

  The electron withdrawing group may be substituted with another electron withdrawing group.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron withdrawing group, more preferably an alkyl group, a cycloalkyl group, or an electron withdrawing group. The ether group is preferably an ether group substituted with an alkyl group or a cycloalkyl group, that is, an alkyl ether group. The electron withdrawing group has the same meaning as described above.

Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group as Z _ka1 may have a substituent and may be linear or branched. As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. As a branched alkyl group, Preferably it is C3-C30, More preferably, it is 3-20, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like. C1-C4 things, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, are preferable.

The cycloalkyl group as Z _ka1 may have a substituent, may be monocyclic, polycyclic, or bridged. For example, the cycloalkyl group may have a bridged structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, Examples thereof include a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetocyclododecyl group, an androstanyl group, and the following structures. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

  Preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin group, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecanyl group. And cyclododecanyl group. More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.

  Examples of the substituent of these alicyclic structures include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group. Preferred examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the substituent that the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).

  Further, further substituents that the above group may have include hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxy group. Alkoxy groups such as ethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, benzyl group and phenethyl group Aralkyl group such as cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, the above alkenyl group, vinyloxy group, propenyl Such as oxy group, allyloxy group, butenyloxy group, etc. Rukeniruokishi group, said aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

  X in the general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by the general formula (KA-1) is preferably a lactone ring, and more preferably a 5- to 7-membered lactone ring.

  In addition, as in the following (KA-1-1) to (KA-1-17), a 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1) has a bicyclo structure, a spiro It is preferred that other ring structures are condensed in a form that forms the structure.

  As for the peripheral ring structure to which the ring structure represented by the general formula (KA-1) may be bonded, for example, those in the following (KA-1-1) to (KA-1-17), or The thing according to can be mentioned.

As a structure containing a lactone ring structure represented by the general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. The lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14) and (KA-1-17).

  The structure containing the lactone ring structure may or may not have a substituent. Preferable substituents include those similar to the substituents that the ring structure represented by the general formula (KA-1) may have.

  Some lactone structures have optically active substances, but any optically active substance may be used. One optically active substance may be used alone or a plurality of optically active substances may be mixed and used. When one kind of optically active substance is mainly used, the optical purity (ee) is preferably 90 or more, more preferably 95 or more, and most preferably 98 or more.

  Preferred examples of X in the general formula (KB-1) include a carboxylic acid ester group (—COO—).

Y ¹ and Y ² in formula (KB-1) each independently represent an electron-withdrawing group.

The electron withdrawing group is a partial structure represented by the following formula (EW). * In the formula (EW) represents a bond directly connected to (KA-1) or a bond directly connected to X in (KB-1).

In formula (EW),
n _ew is the number of repeating linking groups represented by —C (R _ew1 ) (R _ew2 ) — and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond, indicating that Y _ew1 is directly bonded.

Y _ew1 represents a halogen atom, a cyano group, a nitrile group, a nitro group, a halo (cyclo) alkyl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , a haloaryl group, an oxy group, a carbonyl group, a sulfonyl group Examples thereof include a group, a sulfinyl group, and a combination thereof. The electron-withdrawing group may have the following structure, for example. The “halo (cyclo) alkyl group” represents an alkyl group or a cycloalkyl group that is at least partially halogenated. R _ew3 and R _ew4 each independently represent an arbitrary structure. R _ew3 and R _ew4 may have any structure, and the partial structure represented by the formula (EW) may have an electron withdrawing property, and may be linked to, for example, the main chain of the resin. An alkyl group and a fluorinated alkyl group;

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with an arbitrary atom or substituent. At least one group of Y _ew1 , R _ew1 , and R _ew2 may be connected to the main chain of the resin (C) through a further substituent.

Y _ew1 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 .

R _ew1 and R _ew2 each independently represents an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group. Represents a fluoromethyl group.

R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.

R _{f1 to} R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.

Examples of the (halo) alkyl group in R _{f1 to} R _f3 include the alkyl group in Z _ka1 described above and a structure in which this is halogenated.

Examples of the (per) halocycloalkyl group and the (per) haloaryl group in R _{f1 to} R _f3 or a ring formed by linking R _f2 and R _f3 include, for example, the above-described cycloalkyl group in Z _ka1 is a halogen atom. phased structure, more preferably _{-C (n) F (2n-} 2) fluoroalkyl group represented by H, and include perfluoro aryl group represented by _{-C (n) F (n-} 1) It is done. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.

The ring that may be formed by linking at least two of R _ew1 , R _ew2, and Y _ew1 is preferably a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).

  In the repeating unit (c), a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or a general formula (KA- You may have both the partial structure of 1) and general formula (KB-1).

Note that part or all of the partial structure of the general formula (KA-1) may also serve as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group functions as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). There is also a possibility.

  Even if the repeating unit (c) is a repeating unit (c ′) having at least one of a fluorine atom and a silicon atom and a polarity converting group on one side chain, it has a polarity converting group, and Even a repeating unit (c *) having no fluorine atom and silicon atom has a polarity converting group on one side chain, and on a side chain different from the side chain in the same repeating unit, Although it may be a repeating unit (c ″) having at least one of a fluorine atom and a silicon atom, the resin (C) more preferably has a repeating unit (c ′) as the repeating unit (c).

In addition, when resin (C) has a repeating unit (c *), it is preferable that it is a copolymer with the repeating unit (repeating unit (c1) mentioned later) which has at least any one of a fluorine atom and a silicon atom. In the repeating unit (c ″), the side chain having a polarity converting group and the side chain having at least one of a fluorine atom and a silicon atom are bonded to the same carbon atom in the main chain. It is preferable to have a positional relationship as shown in Formula 4. In the formula, B1 represents a partial structure having a polar conversion group, and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

  In the repeating unit (c *) and the repeating unit (c ″), the polar conversion group is more preferably a partial structure represented by —COO— in the structure represented by the general formula (KA-1).

  When the polarity conversion group is decomposed by the action of an alkali developer and converted in polarity, the receding contact angle with water of the resin composition film after alkali development can be lowered.

  The receding contact angle with water of the resin composition film after alkali development is preferably 50 ° or less, more preferably 40 ° or less at the temperature at the time of exposure, usually room temperature 23 ± 3 ° C. and humidity 45 ± 5%. More preferably, it is 35 ° or less, and most preferably 30 ° or less.

  The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.

  The hydrolysis rate of the resin (C) with respect to the alkaline developer is preferably 0.001 nm / sec or more, more preferably 0.01 nm / sec or more, and further preferably 0.1 nm / sec or more. Most preferably, it is 1 nm / sec or more.

  Here, the hydrolysis rate of the resin (C) with respect to the alkaline developer was 23.degree. C. TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%), and the resin film was formed only with the resin (C). This is the rate at which the film thickness decreases.

  The resin (C) of the present invention is preferably a resin (C1) containing a repeating unit (c) having at least two or more polar conversion groups and having at least one of a fluorine atom and a silicon atom. .

When the repeating unit (c) has at least two polar changing groups, the repeating unit (c) preferably has a group having a partial structure having two polar changing groups represented by the following general formula (KY-1). Note that when the structure represented by the general formula (KY-1) does not have a bond, it is a group having a monovalent or higher valent group in which at least one arbitrary hydrogen atom in the structure is removed.

In general formula (KY-1),
R _ky1 and R _ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and R _ky4 are bonded to the same oxygen atom to form a part of a carbonyl group (= O). May be formed.

R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ₁ and Y ₂ in the formula (KB-1), preferably a halogen atom or —C (R _f1 ) (R _f2 ) —R _f3 . And a halo (cyclo) alkyl group or a haloaryl group. Preferably R _ky3 halogen atom _{or,, -C (R f1) (} R f2) halo (cyclo) alkyl or haloaryl group represented by -R _f3, lactone ring linked R _ky2 and R _ky1 Or an electron withdrawing group having no halogen atom.

R _ky1 , R _ky2 and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.

Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka1 in formula (KA-1).

As the lactone ring formed by linking R _ky1 and R _ky2 , the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ₁ and Y ₂ in the formula (KB-1).

The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2). Note that the structure represented by the general formula (KY-2) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.

Two or more of R _{ky6 to} R _ky10 may be connected to each other to form a monocyclic or polycyclic structure.

R _ky5 represents an electron withdrawing group. Examples of the electron withdrawing group include the same groups as those described above for Y ₁ and Y ₂ , preferably a halogen atom or halo (cyclo) represented by —C (R _f1 ) (R _f2 ) —R _f3. An alkyl group or a haloaryl group;

Specific examples of R _{ky5 to} R _ky10 include the same groups as Z _ka1 in formula (KA-1).

The structure represented by the formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).

In formula (KY-3),
Z _ka1 and nka each have the same meaning as in the general formula (KA-1). R _ky5 is synonymous with the formula (KY-2).

L _ky represents an alkylene group, an oxygen atom or a sulfur atom. _Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

  The repeating unit (c) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation, etc., but is a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Preferably there is. Examples include acrylate-based repeating units (including those having substituents at the α-position and β-position), styrene-based repeating units (including those having substituents at the α-position and β-position), vinyl ether-based repeating units, norbornene-based Repeating units, maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), and the like, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units Preferred are acrylate repeat units, vinyl ether repeat units, and norbornene repeat units, with acrylate repeat units being most preferred.

The more specific structure of the repeating unit (c) is preferably a repeating unit having the partial structure shown below.

In general formulas (ca-2) and (cb-2),
Z ₁ each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
Z ₂ each independently represents a chain or cyclic alkylene group.
Ta and Tb are each independently an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group or an electron withdrawing group (Y ¹ and Y in the general formula (KB-1)). ² is synonymous with the electron withdrawing group as ² . When there are a plurality of Tas, Tas may be bonded to form a ring.
Tc represents a hydrogen atom, an alkyl group, a cycloalkyl group, a nitrile group, a hydroxyl group, an amide group, an aryl group or an electron withdrawing group (electron withdrawing as Y ¹ and Y ² in the general formula (KB-1)) It is synonymous with a sex group.
L each independently represents a carbonyl group, a carbonyloxy group or an ether group.

* Represents a bond to the main chain of the resin.
m represents an integer of 1 to 28.
n represents an integer of 0 to 11.
p represents an integer of 0 to 5.
q represents an integer of 0 to 5.
r represents an integer of 0 to 5.

In general formula (2),
R ₂ represents a chain or cyclic alkylene group, and when there are a plurality of R ₂ groups, they may be the same or different.
R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbons are substituted with fluorine atoms.
R ₄ represents a halogen atom, a cyano group, a hydroxy group, an amide group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, an acyl group, an alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). When there are a plurality of R _{4 s} , they may be the same or different, and two or more R ₄ may be bonded to form a ring.

X represents an alkylene group, an oxygen atom or a sulfur atom.
Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.
* Represents a bond to the main chain of the resin.
n represents the number of repetitions and represents an integer of 0 to 5.
m is the number of substituents and represents an integer of 0 to 7.
The structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) ₁ —COO— (l represents an integer of 1 to 5).
Although the specific example of the repeating unit (c) which has a polar conversion group is shown, it is not limited to these.
Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

Resin (C) contains a repeating unit having at least one of a fluorine atom and a silicon atom.
As a result, when the resin (C) is unevenly distributed on the surface layer of the actinic ray or radiation sensitive resin film and the immersion medium is water, the receding contact angle of the resist film surface with respect to water when the actinic ray or radiation sensitive resin film is used. It is possible to improve the immersion water followability.

The receding contact angle of the actinic ray-sensitive or radiation-sensitive resin film is preferably 60 ° to 90 °, more preferably 65 ° or more, and still more preferably 70 at the temperature during exposure, usually room temperature 23 ± 3 ° C. and humidity 45 ± 5%. More than 75 degree, Especially preferably, it is 75 degree or more.
The resin (C) is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and contributes to uniform mixing of polar / nonpolar substances. You don't have to.

  In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

  By having at least one of a fluorine atom and a silicon atom as the resin (C), the hydrophobicity (water followability) of the resist surface is improved, and the development residue (scum) is reduced.

  The partial structure of the repeating unit having a fluorine atom is preferably a repeating unit having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.

Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.
As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom, a group represented by any one of the following general formulas (F2) to (F4) is preferable. However, the present invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). Provided that at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ and at least one of R _{65 to} R ₆₈ are a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. (Preferably having 1 to 4 carbon atoms).

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably a fluoroalkyl group (preferably having 1 to 4 carbon atoms), more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

  Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

  Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 1,3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.
The partial structure containing fluorine may be directly bonded, and is further selected from the group consisting of an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a ureylene group. You may couple | bond together through the combination of single or 2 or more groups.
Preferred examples of the repeating unit having a fluorine atom include those shown below.

In the formula, R ₁₀ and R ₁₁ are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and particularly as an alkyl group having a substituent, Fluorinated alkyl group can be mentioned).
W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).
Besides these, resins having units as shown below are also applicable.

In the formula, R _{4 to} R ₇ are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and the alkyl group having a substituent is In particular, a fluorinated alkyl group can be mentioned). However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.
W ₂ represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or an alkyl group), —NHSO ₂ — or a divalent linking group formed by combining a plurality of these.

  The partial structure having a silicon atom in the repeating unit is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.

Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. As the divalent linking group, an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a ureylene group is used alone or in combination of two or more groups. A combination is mentioned.

  n represents an integer of 1 to 5.

The content of the repeating unit (c) in the resin (C) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to the total repeating unit in the resin (C). 100 mol%, most preferably 40 to 100 mol%.
The content of the repeating unit (c ′) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, and most preferably 40, based on all repeating units in the resin (C). ˜100 mol%.

The content of the repeating unit (c *) is preferably from 10 to 90 mol%, more preferably from 15 to 85 mol%, still more preferably from 20 to 80 mol%, most preferably from 25 to the total repeating units in the resin (C). -75 mol%. The content of the repeating unit having at least one of a fluorine atom and a silicon atom used together with the repeating unit (c *) is preferably 10 to 90 mol%, more preferably based on all repeating units in the resin (C). It is 15 to 85 mol%, more preferably 20 to 80 mol%, and most preferably 25 to 75 mol%.
The content of the repeating unit (c ″) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, and most preferably 40 to the total repeating units in the resin (C). ˜100 mol%.

The fluorine atom or silicon atom in the resin (C) may be contained in the main chain of the resin or may be substituted on the side chain.
The resin (C) may further contain a repeating unit (c1) having at least one of a fluorine atom and a silicon atom, which is different from the repeating units (c ′) and (c ″).

  The fluorine atom or silicon atom in the repeating unit having at least one of a fluorine atom and a silicon atom may be contained in the main chain of the resin or may be substituted with a side chain.

  Examples of the partial structure having a fluorine atom in the repeating unit (c1) include the same ones as described above, and preferred examples include groups represented by the general formulas (F2) to (F4).

Examples of the partial structure having a silicon atom in the repeating unit (c1) include the same ones as described above, and preferably include groups represented by the general formulas (CS-1) to (CS-3).
The repeating unit (c1) is preferably a (meth) acrylate repeating unit.

Hereinafter, although the specific example of a repeating unit (c1) is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ , and X ₂ represents —F or —CF ₃ .

Furthermore, the resin (C) may have at least one group selected from the following groups (x) and (z).
(X) an alkali-soluble group,
(Z) A group that decomposes by the action of an acid.

(X) Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.
Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

  Examples of the repeating unit having an alkali-soluble group (x) include a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a main group of the resin via a linking group. Examples include repeating units in which an alkali-soluble group is bonded to the chain. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be used at the time of polymerization to be introduced at the end of the polymer chain. Is also preferable.

The content of the repeating unit having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 30 mol%, based on all repeating units in the resin (C). is there.
Specific examples of the repeating unit having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto. In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  In the resin (C), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group described above for the resin of the component (A). . The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following general formula (CAI).

In the general formula (CAI),
Xa ₁ represents a hydrogen atom, a methyl group or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group or a — (CH ₂ ) ₃ — group.
The alkyl group of Rx _{1 to} Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.

Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, A polycyclic cycloalkyl group such as an adamantyl group is preferred.
It is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group.

  Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, An alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.

  In the resin (C), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10%, based on all repeating units in the resin (C). It is -80 mol%, More preferably, it is 20-60 mol%. (Z) LWR can be improved by having a group that decomposes by the action of an acid.

  Resin (C) may further have other repeating units. Preferred examples of other repeating units include the following.

  (Cy1) A repeating unit having a fluorine atom and / or a silicon atom, stable to an acid, and hardly soluble or insoluble in an alkali developer.

  (Cy2) A repeating unit which does not have a fluorine atom or a silicon atom, is stable to an acid, and hardly soluble or insoluble in an alkali developer.

  (Cy3) A repeating unit having a fluorine atom and / or a silicon atom and having a polar group other than the above (x) and (z).

  (Cy4) A repeating unit having no fluorine atom or silicon atom and having a polar group other than the above (x) and (z).

  In the repeating unit of (cy1) and (cy2), insoluble or insoluble in an alkali developer is a group in which (cy1) and (cy2) generate an alkali-soluble group by the action of an acid or an alkali developer. (For example, an acid-decomposable group or a polar converting group) is not contained.

  The repeating units (cy1) and (cy2) preferably have an alicyclic hydrocarbon structure having no polar group.

  The preferred embodiments of the repeating units (cy1) to (cy4) are shown below.

The repeating units (cy1) and (cy2) are preferably repeating units represented by the following general formula (CIII).

In general formula (CIII):
R _c31 represents a hydrogen atom, an alkyl group _optionally substituted with a fluorine atom, a cyano group, or a —CH ₂ —O—Rac ₂ group. Wherein, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group. These groups may be substituted with a fluorine atom or a silicon atom.
L _c3 represents a single bond or a divalent linking group.

In general formula (CIII), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.

The divalent linking group of L _c3 is preferably an ester group, an alkylene group (preferably having a carbon number of 1 to 5), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).

The repeating units (cy1) and (cy2) are preferably repeating units represented by the following general formula (C4) or (C5).

In general formula (C4), R _c5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Rac represents a hydrogen atom, an alkyl group which may be substituted with a fluorine atom, a cyano group or a —CH ₂ —O—Rac ₂ group. Wherein, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. Rac is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R _c5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms and a cycloalkenyl group having 3 to 12 carbon atoms. A preferable monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms.

  The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the bridged cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. The bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring (for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed). Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and the substituent that may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino protected with a protecting group The group can be mentioned.

  Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

In General Formula (C5), R _c6 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxycarbonyl group, or an alkylcarbonyloxy group. These groups may be substituted with a fluorine atom or a silicon atom.

The alkyl group for R _c6 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

  The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.

  The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 20 carbon atoms.

n represents an integer of 0 to 5. When n is 2 or more, the plurality of R _c6 may be the same or different.

R _c6 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom, particularly preferably a trifluoromethyl group or a t-butyl group.

(Cy1) and (cy2) are preferably repeating units represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

  Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

The general formula (CII-AB) is more preferably the following general formula (CII-AB1) or general formula (CII-AB2).

In the formulas (CII-AB1) and (CII-AB2),
Rc ₁₃ '~Rc _16' each independently represent a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group.

It is also possible to form at least two members to the ring of Rc _l3 '~Rc _16'.

  n represents 0 or 1.

Specific examples of (cy1) and (cy2) are listed below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

  (Cy3) and (cy4) are preferably repeating units having a hydroxyl group or a cyano group as a polar group. This improves developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornyl group. Preferred examples of the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group include a monohydroxyadamantyl group, a dihydroxyadamantyl group, a monohydroxydiamantyl group, a dihydroxyadamantyl group, and a norbornyl group substituted with a cyano group.

Examples of the repeating unit having the atomic group include repeating units represented by the following general formulas (CAIIa) to (CAIId).

In the general formulas (CAIIa) to (CAIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. In the general formula (CAIIa), more preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the rest are hydrogen atoms.
Specific examples of the repeating unit represented by (cy3) and (cy4) are given below, but the present invention is not limited thereto.

  The content of the repeating units represented by (cy1) to (cy4) is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 10%, based on all repeating units in the resin (C). 25 mol%.

  Resin (C) may have a plurality of repeating units represented by (cy1) to (cy4).

  When resin (C) has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the molecular weight of the resin (C). Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% with respect to all the repeating units in resin (C), and it is more preferable that it is 30-100 mass%.

  When resin (C) has a silicon atom, it is preferable that the content rate of a silicon atom is 2-50 mass% with respect to the molecular weight of resin (C), and it is more preferable that it is 2-30 mass%. Moreover, it is preferable that it is 10-90 mass% with respect to all the repeating units of resin (C), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-80 mass%.

  The weight average molecular weight of the resin (C) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.

  The content of the resin (C) in the actinic ray or radiation sensitive resin composition can be appropriately adjusted and used so that the receding contact angle of the actinic ray or radiation sensitive resin film falls within the above range. It is preferable that it is 0.01-10 mass% on the basis of the total solid of a radiation sensitive resin composition, More preferably, it is 0.1-9 mass%, More preferably, it is 0.5-8 mass% is there.

  The resin (C), like the resin of the component (A) described later, naturally has few impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably. Is more preferably 0 to 5% by mass and 0 to 1% by mass. Thereby, a resist having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

  As the resin (C), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and cyclohexanone is mentioned. More preferably, the polymerization is carried out using the same solvent as that used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. The concentration of the reaction is usually 5 to 50% by mass, preferably 30 to 50% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

  The resin may be once deposited and separated, and then dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

Specific examples of the resin (C) are shown. The table below shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn).

Resin (C) can be used individually by 1 type or in combination of 2 or more types.
Moreover, it is preferable to use it combining with resin (CP) which has at least any one of a fluorine atom or a silicon atom different from resin (C).
(CP) Resin having at least one of fluorine atom and silicon atom The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains at least one of fluorine atom and silicon atom separately from the resin (C). You may further contain resin (CP) which has. By containing the resin (C) / resin (CP), the resin (C) / resin (CP) is unevenly distributed in the surface layer of the film, and when the immersion medium is water, the resist film surface with respect to water when used as a film The receding contact angle can be improved, and the immersion water followability can be improved. The receding contact angle of the film is preferably 60 ° to 90 °, more preferably 70 ° or more. The resin (CP) content can be appropriately adjusted and used so that the receding contact angle of the film falls within the above range, but 0.01% based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is preferable that it is -10 mass%, More preferably, it is 0.01-5 mass%, More preferably, it is 0.01-4 mass%, Most preferably, it is 0.01-3 mass%. The resin (CP) is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and contributes to uniform mixing of polar / nonpolar substances. You don't have to.

The fluorine atom or silicon atom in the resin (CP) having at least one of a fluorine atom and a silicon atom may be present in the main chain of the resin or may be substituted with a side chain.
The resin (CP) is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.

Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.
Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom preferably include groups represented by general formulas (F2) to (F4) in the resin (C). However, the present invention is not limited to this.

In this invention, it is preferable that group represented by general formula (F2)-(F4) is contained in a (meth) acrylate type repeating unit.
Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .
X ₂ represents —F or —CF ₃ .

  The resin (CP) is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.

  Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by general formulas (CS-1) to (CS-3) in the resin (C).

Furthermore, the resin (CP) may further have at least one group selected from the following groups (x) and (z).
(X) an alkali-soluble group,
(Z) A group that decomposes by the action of an acid.

  Specific examples of these groups include the same groups as those in the resin (C).

In the resin (CP), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group described above for the resin of the component (A). . The content of the repeating unit having a group (z) that decomposes by the action of an acid in the resin (CP) is preferably from 1 to 80 mol%, more preferably 10%, based on all repeating units in the resin (CP). It is -80 mol%, More preferably, it is 20-60 mol%.
The resin (CP) may further have a repeating unit represented by the general formula (CIII) in the resin (C).

  When resin (CP) has a fluorine atom, it is preferable that the content rate of a fluorine atom is 5-80 mass% with respect to the molecular weight of resin (CP), and it is more preferable that it is 10-80 mass%. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% with respect to all the repeating units in resin (CP), and it is more preferable that it is 30-100 mass%.

  When resin (CP) has a silicon atom, it is preferable that the content rate of a silicon atom is 2-50 mass% with respect to the molecular weight of resin (CP), and it is more preferable that it is 2-30 mass%. Moreover, it is preferable that the repeating unit containing a silicon atom is 10-100 mass% with respect to all the repeating units of resin (CP), and it is more preferable that it is 20-100 mass%.

  The weight average molecular weight of the resin (CP) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.

  The resin (CP), like the resin of the component (A), is naturally low in impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably 0. -5 mass%, 0-1 mass% is still more preferable. As a result, an actinic ray-sensitive or radiation-sensitive resin composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

  As the resin (CP), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). Specifically, it can be synthesized in the same manner as the resin (C).

Specific examples of the resin (CP) having at least one of a fluorine atom and a silicon atom are shown below. The table below shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn).

  The film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is filled with a liquid (immersion medium) having a higher refractive index than air between the film and the lens when irradiated with actinic rays or radiation. Exposure (immersion exposure) may be performed. Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.

  The immersion liquid used for the immersion exposure will be described below.

  The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the resist film. Is an ArF excimer laser (wavelength; 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-mentioned viewpoints.

  Further, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, the surface tension of the water is decreased and the surface activity is increased, so that the resist film on the wafer is not dissolved and the influence on the optical coating on the lower surface of the lens element can be ignored. An additive (liquid) may be added in a small proportion. The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specifically includes methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained. On the other hand, when an opaque material or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light, the optical image projected on the resist film is distorted. . Further, pure water filtered through an ion exchange filter or the like may be used.

  The electrical resistance of water is desirably 18.3 MQcm or more, the TOC (organic substance concentration) is desirably 20 ppb or less, and deaeration treatment is desirably performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

  An immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) may be provided between the film of the composition of the present invention and the immersion liquid so that the film does not directly contact the immersion liquid. Good. The necessary functions for the top coat are suitability for application to the upper layer of the resist, radiation, especially transparency to 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the resist upper layer.

  From the viewpoint of 193 nm transparency, the top coat is preferably a polymer that does not contain abundant aromatics. Specifically, the polymer contains a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, and silicon. Examples thereof include a polymer and a fluorine-containing polymer. The above-mentioned hydrophobic resins (C) and (CP) are also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

  When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. In terms of being able to perform the peeling process simultaneously with the film development process, it is preferable that the peeling process can be performed with an alkaline developer. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the film.

  The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. In the case of using water as the immersion liquid in an ArF excimer laser (wavelength: 193 nm), the top coat for ArF immersion exposure is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.

  The top coat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Furthermore, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

(A) Resin whose solubility in an alkaline developer is increased by the action of an acid The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin (A) whose dissolution rate in an alkaline developer is increased by the action of an acid. contains.
Resins that increase the dissolution rate in an alkaline developer due to the action of an acid (acid-decomposable resins) are decomposed into the main chain or side chain of the resin, or both the main chain and side chains by the action of an acid, and are alkali-soluble. It has a group that generates a group (hereinafter also referred to as “acid-decomposable group”).
The resin (A) is preferably insoluble or hardly soluble in an alkali developer.

The acid-decomposable group preferably has a structure in which an alkali-soluble group is protected with a group capable of decomposing and leaving by the action of an acid.
The alkali-soluble group is not particularly limited as long as it is a group that dissociates and becomes an ion in an alkali developer, but a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (Alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) ) Imido group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group and the like.

Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

  The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

The repeating unit having an acid-decomposable group that can be contained in the resin (A) is preferably a repeating unit represented by the following general formula (AI).

In general formula (AI),
Xa ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, More preferred is a methyl group. Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group or a — (CH ₂ ) ₃ — group.
The alkyl group of Rx _{1 to} Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.

Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, A polycyclic cycloalkyl group such as an adamantyl group is preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are combined to form the cycloalkyl group described above is preferred.

  Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, An alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.

  The content of the repeating unit having an acid-decomposable group as a total is preferably 20 to 70 mol%, more preferably 30 to 50 mol%, based on all repeating units in the resin.

  Although the specific example of the repeating unit which has a preferable acid-decomposable group is shown below, this invention is not limited to this.

In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. p represents 0 or a positive integer.

Resin (A) is at least one of the repeating unit represented by general formula (AI-1) and the repeating unit represented by general formula (AI-2) as a repeating unit represented by general formula (AI). More preferably, the resin has

In the formulas (AI-1) and (AI-2),
R ₁ and R ₃ have the same meaning as Xa ₁ in formula (AI), and are a hydrogen atom, a methyl group, a trifluoromethyl group, or —CH ₂ —R ₉ (R ₉ represents a hydroxyl group or a monovalent organic group. .) Represents a group represented by
R ₂ represents an alkyl group, a cycloalkyl group, or an aryl group.

R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
R ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The alkyl group in R ₂ may be linear or branched, and may have a substituent.
The cycloalkyl group in R ₂ may be monocyclic or polycyclic and may have a substituent.
The aryl group for R ₂ may have a substituent.
R ₂ is preferably an alkyl group, more preferably one having 1 to 10 carbon atoms, still more preferably 1 to 5, and examples thereof include a methyl group and an ethyl group.

  R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R is preferably a monocyclic or polycyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6.

R ₃ is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
The alkyl group in R ₄ , R ₅ and R ₆ may be linear or branched and may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

The repeating unit represented by the general formula (AI-1) is preferably a repeating unit represented by the following general formula (AI-3).

In the formula, R ₁₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R ₁₂ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R _{13 to} R ₁₈ , R ₂₁ and R ₂₂ each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, and R ₁₉ and R _{20 each} represent a hydrogen atom. Alternatively, R ₁₃ and R ₁₄ , R ₁₅ and R ₁₇ , or R ₁₆ and R ₁₈ may be bonded to each other to form a ring, and in that case, a hetero atom having 1 to 15 carbon atoms may be included. A divalent hydrocarbon group is shown. R ₁₅ and R ₁₇ may be bonded to adjacent carbons without any intervention to form a double bond.

Although the specific example of the unit represented by (AI-3) is shown below, it is not limited to this.

(R ₁ and R ₃ represent the same substituents as described above.)
Preferred combinations when the resin (A) uses an acid-decomposing repeating unit are listed below.

The resin (A) preferably contains a repeating unit having a lactone structure.
Any lactone group can be used as long as it has a lactone structure, but it is preferably a 5- to 7-membered ring lactone structure, and forms a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure. The other ring structure is preferably condensed. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and (LC1-17). By using this lactone structure, LWR and development defects are improved.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

The resin (A) preferably contains a repeating unit having a lactone structure represented by the following general formula (5).

In formula (5),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof independently when there are a plurality of R ₀ .
When there are a plurality of Z, each independently represents an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, and is preferably an ether bond or an ester bond.
R ₈ represents a monovalent organic group having a lactone structure.

n is the repeating number of the structure represented by —R ₀ —Z— in the repeating unit represented by the formula (5), and represents an integer of 0 to 5. n is preferably 1.
R ₉ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent.

The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group for R ₉ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group in R ₉ may be substituted, and examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t -Alkoxy groups such as butoxy group and benzyloxy group, acyl groups such as acetyl group and propionyl group, and acetoxy groups. R ₉ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

Preferable chain alkylene group in R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. Preferred cycloalkylene is cycloalkylene having 3 to 20 carbon atoms, and examples thereof include cyclohexylene, cyclopentylene, norbornylene, adamantylene and the like. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is further preferable.

The substituent having a lactone structure represented by R ₈ is not limited as long as it has a lactone structure, and is represented by the general formulas (LC1-1) to (LC1-17) described above as specific examples. Among them, the structure represented by (LC1-4) is particularly preferable. Further, n ₂ in (LC1-1) to (LC1-17) is more preferably 2 or less.

R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or a monovalent organic group having a lactone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) as is more preferable.

Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (5) are shown below, but the present invention is not limited thereto.
In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, and preferably a hydrogen atom, a methyl group, a hydroxymethyl group which is an alkyl group having a substituent, acetoxy Represents a methyl group.

As the repeating unit having a lactone structure, a repeating unit represented by the following general formula (5-1) is more preferable.

In general formula (5-1),
R ₉ , A, R ₀ , Z, and n have the same meaning as in the general formula (5).
R ₁₀ independently represents an alkyl group, a cycloalkyl group, an acyloxy group, —CO ₂ R ₇ , a cyano group, a hydroxyl group, or an alkoxy group when there are a plurality of R _{10 s, and} when there are a plurality of R _{10 s,} two R ₁₀ May combine to form a ring. R ₇ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group.

X represents an alkylene group, an oxygen atom or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5. m is preferably 0 to 1.

The alkyl group for R ₁₀ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Acyloxy groups include formyloxy, acetoxy, propionyloxy, butyryloxy, isobutyryloxy, valeryloxy, pivaloyloxy, hexanoyloxy, octanoyloxy, decanoyloxy, lauroyloxy, myristoyloxy, palmitoyloxy, stearoyloxy, trifluoro Examples include acetoxy, pentafluoropropionyloxy, heptafluorobutyryloxy and the like. Examples of —CO ₂ R ₇ include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, a hexafluoroisopropyloxy group, etc. are mentioned. These groups as R ₁₀ may have a substituent, and examples of the substituent include an alkoxy group such as a hydroxy group, a methoxy group and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom. . R ₁₀ is preferably —CO ₂ R ₇ , particularly preferably a methoxycarbonyl group.

When m is 1 or more, at least one of R ₁₀ is preferably at the α-position or β-position of the carbonyl group of the lactone, particularly preferably at the α-position.
Examples of the alkylene group for X include a methylene group and an ethylene group. X is preferably a methylene group or an oxygen atom.

Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (5-1) are shown below, but the present invention is not limited thereto. In the formula, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, and preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

  The content of the repeating unit represented by the general formula (5) is preferably from 15 to 60 mol%, more preferably from 20 to 60 mol%, still more preferably based on the total repeating units in the resin when a plurality of types are contained. Is 30-50 mol%.

  Resin (A) may contain the repeating unit which has a lactone group other than the unit represented by General formula (5).

As the repeating unit having a lactone structure other than the unit represented by the general formula (5), a repeating unit represented by the following general formula (AII ′) is also preferable.

In general formula (AII ′),
Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group represented by Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferred.

V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).
Specific examples of the repeating unit having a lactone group other than the unit represented by the general formula (5) are given below, but the present invention is not limited thereto. In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ . By selecting an optimal lactone group, the pattern profile and the density dependency are improved.

  The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.

  The content of the repeating unit having a lactone other than the repeating unit represented by the general formula (5) is preferably 15 to 60 mol% in total with respect to all the repeating units in the resin when more than one type is contained, more preferably It is 20-50 mol%, More preferably, it is 30-50 mol%.

  In order to enhance the effect of the present invention, two or more lactone repeating units selected from the above general formula (5) can be used in combination. When using together, it is preferable to select and use 2 or more types from the lactone repeating unit in which n is 1 in general formula (5). Moreover, it is also preferable to use together the lactone repeating unit selected from general formula (AII '), and the lactone repeating unit whose n is 1 among general formula (5).

The resin (A) preferably has a repeating unit other than the repeating unit represented by the general formula described above, which has a hydroxyl group or a cyano group. This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

In general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the remaining are hydrogen atoms.

Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ (VIIc), same meanings as R ₂ c~R ₄ c.

The content of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (A).
Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

  The resin used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron withdrawing group at the α-position. It is more preferable to have a repeating unit. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

As a preferred embodiment of the repeating unit having an alkali-soluble group, a repeating unit represented by the following general formula (6) can be mentioned.

In the general formula (6), R ₁₃ represents a hydrogen atom or a methyl group which may have a substituent. n represents 1 or 2.

When n = 1, X ₂ is a single bond, —O—, —C (═O) —O—R ₁₄ — or —C (═O) —NH—R ₁₄ —, R ₁₄ is a single bond, It is a C1-C4 linear or branched alkylene group or a cycloalkylene group, and may have an ester group or an ether group.

When n = 2, X ₂ is

R _14a is a linear or branched alkylene group having 1 to 10 carbon atoms, or a group in which one hydrogen atom is eliminated from a cycloalkylene group, and may have an ester group or an ether group. Good.

R ₁₁ is a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a cycloalkylene group, and R ₁₂ is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or a difluoromethyl group, Alternatively, it may form a ring having 3 to 10 carbon atoms (excluding an aromatic ring) together with the carbon atom to which R ₁₁ is bonded to these, and is an alkylene substituted with an ether group or fluorine in the ring It may have a group.

Examples of the alkylene group in R ₁₄ , R _14a , and R ₁₁ include a methylene group, an ethylene group, and a propylene group. The cycloalkylene is preferably a cyclic alkylene having 3 to 20 carbon atoms, and examples thereof include cyclohexylene, cyclopentylene, norbornylene, and adamantylene.
As for the content rate of the repeating unit which has an alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.
Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.

Furthermore, although the specific example of the monomer corresponding to the repeating unit which has an alkali-soluble group is shown below, this invention is not limited to this.

The resin (A) of the present invention can further have a repeating unit that has an alicyclic hydrocarbon structure having no polar group and does not exhibit acid decomposability. Examples of such a repeating unit include a repeating unit represented by the general formula (7).

In General Formula (7), R ₅ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group. Groups. Preferable monocyclic hydrocarbon groups are monocyclic hydrocarbon groups having 3 to 7 carbon atoms, and more preferable examples include a cyclopentyl group and a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and the substituent that may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino protected with a protecting group The group can be mentioned.

  Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The content of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability is preferably 0 to 40 mol%, more preferably, based on all repeating units in the resin (A). 0 to 20 mol%.
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  Resins used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention include, in addition to the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resists. Various repeating structural units can be included for the purpose of adjusting required properties such as resolution, heat resistance, and sensitivity.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, the performance required for the resin used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the content molar ratio of each repeating structural unit is resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, Furthermore, it is appropriately set in order to adjust the resolution, heat resistance, sensitivity, etc., which are general required performances of the resist.

Resin used for the actinic ray-sensitive or radiation-sensitive resin composition of the present invention from the viewpoint of transparency to ArF light when the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure (A) preferably has no aromatic group.
Moreover, it is preferable that the resin (A) of this invention does not contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin (C) mentioned above.

  The resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units. More preferably, the (meth) acrylate repeating unit having an acid-decomposable group is 20 to 50 mol%, the (meth) acrylate repeating unit having a lactone group is 20 to 50 mol%, and the alicyclic ring is substituted with a hydroxyl group or a cyano group. It is a copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a hydrocarbon structure and further 0 to 20 mol% of another (meth) acrylate-based repeating unit.

  The resin (A) of the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

The weight average molecular weight of the resin (A) of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3, as a polystyrene conversion value by GPC method. 000 to 15,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
The dispersity (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 2.0. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

The blending amount of the resin (A) of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention in the entire composition is preferably 50 to 99% by mass, more preferably 60 to 98% by mass in the total solid content. is there.
Moreover, the resin (A) of the present invention may be used alone or in combination.

(B) Compound that generates acid upon irradiation with actinic ray or radiation The composition of the present invention contains a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter also referred to as “acid generator”).

Although it will not specifically limit as an acid generator if it is a well-known thing, Preferably the compound represented by the following general formula (ZI), (ZII), (ZIII) can be mentioned.

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.

Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

  The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.

  The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, and the like.
Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
Examples of other Z ⁻ include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Z ⁻ includes an aliphatic sulfonate anion substituted with at least α-position of sulfonic acid with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group substituted with a fluorine atom. Bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.
From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), and a cycloalkyl group (having 3 carbon atoms). ~ 15 are preferred).

The alkyl group or cycloalkyl group as R _201, R ₂₀₂ and R _203, e.g., a methyl group, an ethyl group, a propyl group, n- butyl group, sec- butyl group, t- butyl group, cyclopropyl group, cyclobutyl Group, cyclohexyl group and the like. The alkyl group and the cycloalkyl group may have a substituent, and examples of the substituent include the same groups as the substituents that the aryl group shown below may have.

Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used. These aryl groups may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

Two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like, but are not limited thereto.

Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0047 and 0048 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, Compounds exemplified as formulas (I-1) to (I-70) in US2003 / 0224288A1, specification (IA-1) to (IA-54), formula (IB- Examples thereof include cationic structures such as compounds exemplified as 1) to (IB-24).

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).
Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Examples of the substituent include those that the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the above-described compound (ZI) may have.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).
Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the composition is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 15% by mass, based on the total solid content of the composition. %.

Surfactant It is preferable that the composition of the present invention further contains a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.
Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in US 2008/0248425 A1 after [0273].

Surfactants may be used alone or in combination of two or more.
The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total solid content of the composition.

Solvent The solvent that can be used in preparing the composition is not particularly limited as long as it dissolves each component. For example, alkylene glycol monoalkyl ether carboxylate (such as propylene glycol monomethyl ether acetate), alkylene glycol monoalkyl Ether (such as propylene glycol monomethyl ether), alkyl lactate (such as ethyl lactate and methyl lactate), cyclic lactone (such as γ-butyrolactone, preferably 4 to 10 carbon atoms), chain or cyclic ketone (2-heptanone, cyclohexanone) Etc., preferably 4 to 10 carbon atoms), alkylene carbonate (ethylene carbonate, propylene carbonate, etc.), alkyl carboxylate (preferably alkyl acetate such as butyl acetate), alkoxyacetic acid Like alkyl (ethoxy ethyl propionate). Examples of other usable solvents include those described in US 2008/0248425 A1 [0244] and thereafter.

  Of the above, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.

  These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40.

  The solvent having a hydroxyl group is preferably an alkylene glycol monoalkyl ether, and the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate.

Other components In addition to the components described above, the composition of the present invention includes a carboxylic acid onium salt, a dissolution inhibiting compound having a molecular weight of 3000 or less, a dye, a plasticizer, and the like described in Proceeding of SPIE, 2724, 355 (1996), etc. A photosensitizer, a light absorber and the like can be appropriately contained.

<Pattern formation method>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used at a film thickness of 30 to 250 nm, more preferably at a film thickness of 30 to 200 nm, from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the actinic ray-sensitive or radiation-sensitive resin composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property. .
The total solid concentration in the actinic ray-sensitive or radiation-sensitive resin composition is generally 1 to 10% by mass, more preferably 1 to 8.0% by mass, and still more preferably 1.0 to 6.0% by mass. It is.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is prepared by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and then applying the solution on a predetermined support as follows. Use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon.

For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied on a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements by a suitable application method such as a spinner or coater, and dried. Then, a resist film is formed.
The resist film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., preferably 250 nm or less, more preferably 220 nm or less, particularly Preferably, far ultraviolet light having a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, electron beam, etc., ArF excimer Laser, F ₂ excimer laser,
EUV (13 nm) is preferred.

  In the present invention, electromagnetic waves such as ultraviolet light and X-rays are included in the radiation.

  Before forming the resist film, an antireflection film may be coated on the substrate in advance.

  As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

In the development step, an alkaline developer is used as follows. Examples of the alkali developer for the positive resist composition include inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Alkaline aqueous solutions of cyclic amines such as quaternary ammonium salts such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.

The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.
As the rinsing liquid, pure water can be used, and an appropriate amount of a surfactant can be added.

  Further, after the development process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
[Synthesis example]
The nitrogen-containing organic compound of the present invention was synthesized by the following method.
Synthesis Example 1 Synthesis of behenic acid [2- (1H-imidazol-1-yl) -1-methylethyl] (quencher 1)

  To a mixture of 12.6 g of 1- (1H-imidazol-1-yl) -2-propanol (15) and 50 g of dimethylformamide, 35.9 g of behenic acid chloride (16) was added under ice-cooling and stirring. For 2 hours. Following toluene addition and neutralization, normal aqueous work-up was performed, followed by purification by column chromatography, 41.3 g of behenic acid [2- (1H-imidazol-1-yl) -1-methylethyl] (quencher 1) was obtained.

[Synthesis Example 2] Synthesis of behenic acid (2-morpholinoethyl) (quencher 2)

  A mixture of 35.5 g (18) of methyl behenate, 19.7 g (17) of 2-morpholinoethanol, 270 mg of sodium methoxide and 150 g of toluene was heated to reflux for 6 hours while distilling off the methanol produced by the reaction. After cooling, normal aqueous work-up was performed, and then toluene was distilled off to obtain 41.3 g of behenic acid (2-morpholinoethyl) (quencher 2).

[Synthesis Examples 3, 5, 6]
The quenchers 3, 5, and 6 were synthesized using the same method.

[Synthesis Example 4] Synthesis of cholic acid triformate (2-morpholinoethyl) ester (quencher 4) A mixture of 49.3 g of cholic acid triformate (22), 12.7 g of oxalic acid chloride and 500 g of toluene was stirred at 50 ° C for 3 hours. The mixture was ice-cooled, 28.9 g of 2-morpholinoethanol (21) was added dropwise, and then the mixture was stirred at room temperature for 3 hours. After normal aqueous work-up, purification was performed by silica gel column chromatography to obtain 43.0 g of cholic acid triformate (2-morpholinoethyl) ester (quencher 4).

[Synthesis Example 7] Synthesis of salsasapogenin [3- (thiomorpholino) propionate] (quencher 7)

  10.3 g of thiomorpholine (27) was added dropwise to a mixture of 47.1 g of sarsasapogenin acrylate (28) and 200 g of tetrahydrofuran, and the mixture was stirred at room temperature for 3 hours. Tetrahydrofuran was distilled off and purified by silica gel column chromatography to obtain 56.2 g of sarsasapogenin [3- (thiomorpholino) propionate] (quencher 7).

Synthesis of Resin (A) <Synthesis of Resin (RA-1)>
Under a nitrogen stream, 60.32 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. To this, 12.37 g of monomer A, 14.01 g of monomer B, 2.95 g of monomer C, 1.08 g of monomer D and 1.44 g of initiator V-601 (5.0 mol% with respect to the monomer, Wako Pure Chemical) Solution) was added dropwise over 6 hours to 112.02 g of cyclohexanone. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixed solution of 900 ml of methanol / 100 ml of water over 20 minutes. The precipitated powder was collected by filtration and dried to obtain 18 g of Resin (RA-1). The weight average molecular weight of the obtained resin was 10700 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.81.

<Synthesis of Resins (RA-2) to (RA-9)>
Other resins (RA-2) to (RA-9) were synthesized using the same method. The weight average molecular weight was prepared by changing the amount of initiator.

The repeating unit (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) in each resin are shown below.

<Resist preparation>
The components shown in Table 3 below were dissolved in a solvent to prepare a solution having a solid content concentration of 5% by mass, and this was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a positive resist solution. The prepared positive resist solution was evaluated by the following method, and the results are shown in the same table.

<Resist evaluation>
An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. A positive resist composition prepared thereon was applied, and baked at 130 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. Using an ArF excimer laser immersion scanner (XTML1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection manufactured by ASML), the obtained wafer was 6% of 65 nm 1: 1 line and space pattern. Exposure was through a halftone mask. Ultra pure water was used as the immersion liquid. Thereafter, heating was performed at 130 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.

[Corner proximity]
The developed wafer is observed with a sky SEM (scanning electron microscope) to resolve a 65 nm 1: 1 dense line and space pattern in the dark region (dark field, high mask coverage region). With respect to the exposure amount (optimum exposure amount), the line dimensions were measured at the center portion of the evaluation pattern and the end portion of the evaluation pattern. Those having a dimensional difference of less than 3 nm between the central part and the end part are indicated by double circles, those having a size of 3 nm or more and less than 6 nm, and those having a size difference of 6 nm or more by X. A smaller value indicates better performance.

[Development defects]
Using a defect inspection device KLA2360 (trade name) manufactured by KLA-Tencor, Inc., setting the pixel size of the defect inspection device to 0.16m and the threshold value to 20, and measuring in random mode, a comparison image And the number of development defects per unit area was calculated. A value of less than 0.5 was rated as ◯, a value of 0.5 or more and less than 0.8 as Δ, and a value of 0.8 or more as x. A smaller value indicates better performance.

<Other performance tests>
[Generated acid elution amount]
The prepared positive resist composition was applied onto an 8-inch silicon wafer and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 160 nm. Next, the entire surface of the 8-inch wafer was exposed at 30 mJ / cm 2 using an ArF excimer laser exposure machine (manufactured by ASML, PAS5500 / 1100). The wafer was immersed in a quartz container to which 100 mL of pure water deionized using an ultrapure water production apparatus (Nippon Millipore, Milli-Q) was added, and the eluate collected in water was collected. The amount of acid eluted into this aqueous solution was quantified by LC-MS.

LC device: 2695 manufactured by Waters
MS device: esquire 3000 manufactured by Brucker Daltonics
The detection intensity of ion species having a mass of 299 (corresponding to nonaflate anion) was measured with the LC-MS apparatus, and the elution amount of nonafluorobutanesulfonic acid was calculated. Similarly, the amount of elution was calculated for other anions. × The elution amount is ^{1.0 × 10 -10 mol / cm 2} / sec or ^{more, 1.0 × 10 -10 mol / cm} 2 /sec~1.0×10 -12 mol / cm to less than 2 / sec △ 1.0 × 10 ⁻¹³ mol / cm ² / sec.

[Backward contact angle]
The prepared positive resist composition was applied onto a silicon wafer and baked at 120 ° C. for 60 seconds to form a 160 nm thick resist film. The receding contact angle of water droplets was measured by an expansion / contraction method using a dynamic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) at a room temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%. An initial droplet size of 35 μL was sucked at a speed of 6 L / sec for 5 seconds, and a value with a stable dynamic contact angle during suction was defined as a receding contact angle. The larger the value of the receding contact angle, the more water can follow the higher scanning speed.
Each component used is as follows.

[Photoacid generator]
PAG1 and PAG2 shown below were used.

[Resin (A)]
Resins (RA-1) to (RA-9) were prepared as described above.

[Hydrophobic resin (C)]
Resin C in the examples used the following. The molar ratio of the repeating units is as shown in Table 1 above.

[Basic compound (D)]
Quencher-1 to Quencher-7 are those exemplified above.

Quencher-8 to Qunecher-10 used the following.

[Surfactant]
W-1 :: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
〔solvent〕
S1: Propylene glycol methyl ether acetate (PGMEA)
S2: cyclohexanone

Claims (11)

(A) a resin whose solubility in an alkali developer is increased by the action of an acid, (B) a compound that generates an acid upon irradiation with actinic rays or radiation, (C) at least one of a fluorine atom and a silicon atom, and an alkali developer resins having free a repeating unit having a polarity conversion group which exhibits increased solubility in an alkali developing solution is decomposed by the action, and a nitrogen-containing organic having a nitrogen-containing hetero ring represented by (D) the following general formula (1) An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound , wherein the polar conversion group is a group represented by X in a partial structure represented by the following general formula (KB-1) .

(In the formula, R ¹ is a linear, branched or cyclic divalent substituent having 2 to 20 carbon atoms that forms a nitrogen-containing heteroaliphatic ring or a nitrogen-containing heteroaromatic ring together with nitrogen atoms bonded at both ends. Represents a group, and may include an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom, R ² represents a linear or branched alkylene group that may include a carbonyl group having 2 to 10 carbon atoms, and R ³ represents (Represents a saturated or unsaturated hydrocarbon group or acyl group which may contain a hydroxyl group, a carbonyl group, an ester group, an ether group, a cyano group, a steroid skeleton, or a combination of two or more thereof.)
Y ¹ -XY ² (KB-1)
(In the formula, X represents a carboxylic acid ester group, an acid anhydride group, an acid imide group, a carboxylic acid thioester group, a carbonic acid ester group, a sulfuric acid ester group, or a sulfonic acid ester group. Y ¹ and Y ² represent an electron demand. Represents an attractive group.)   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (C) contains a repeating unit having two or more polar conversion groups. The nitrogen-containing organic compound (D) contains one or more nitrogen-containing organic compounds having nitrogen-containing heterocycles represented by the following general formulas (2) to (10). Item 3. The active light-sensitive or radiation-sensitive resin composition according to Item 1 or 2 .

(In the formula, each R ⁴ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms. R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a saturated or unsaturated hydrocarbon group which may contain a hydroxyl group, a carbonyl group, an ester group, an ether group, a cyano group or an acetal group, and R ⁷ represents Represents a single bond, a methylene group, an oxygen atom or a sulfur atom, R ⁸ represents a linear or branched alkylene group having 1 to 9 carbon atoms, R ⁹ represents a hydroxyl group, a carbonyl group, an ester group, an ether group or Represents a saturated or unsaturated hydrocarbon group which may contain a cyano group.) As the nitrogen-containing organic compound (D), one or more of nitrogen-containing organic compounds having a nitrogen-containing heterocycle and a steroid skeleton represented by the following general formulas (2 ′) to (10 ′) are contained. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3 .

(In the formula, each R ⁴ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms. R ⁵ represents a hydrogen atom or a methyl group, and R ^{6 ′} represents a saturated or unsaturated hydrocarbon group which may contain a steroid skeleton-containing hydroxyl group, carbonyl group, ester group, ether group, cyano group or acetal group. R ⁷ represents a single bond, a methylene group, an oxygen atom or a sulfur atom, R ⁸ represents a linear or branched alkylene group having 1 to 9 carbon atoms, and R ^{9 ′} represents a hydroxyl group having a steroid skeleton. Represents a saturated or unsaturated hydrocarbon group which may contain a carbonyl group, an ester group, an ether group or a cyano group.) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4 , wherein the resin (A) contains a repeating unit containing a lactone structure. The actinic ray-sensitive or radiation-sensitive ray according to any one of claims 1 to 5 , wherein the resin (A) contains a repeating unit having a monocyclic or polycyclic acid-decomposable group. Resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 6, wherein the resin (A) contains a repeating unit represented by the following general formula (AI-3).

(Wherein R ₁₁ Represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R ₁₂ Represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ₁₃ ~ R ₁₈ , R _{twenty one} And R _{twenty two} Each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms; ₁₉ , R ₂₀ Represents a hydrogen atom. Or R ₁₃ And R ₁₄ , R ₁₅ And R ₁₇ Or R ₁₆ And R ₁₈ May be bonded to each other to form a ring, and in this case, represents a divalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms. Also R ₁₅ And R ₁₇ May be bonded to each other adjacent to carbons without intervening to form a double bond. ) The actinic ray-sensitive or radiation-sensitive resin composition according to claim 6, wherein the resin (A) contains a repeating unit represented by the following general formula (AI-1).

(Wherein R ₁ , R _Three Xa in general formula (AI) ₁ And a hydrogen atom, a methyl group, a trifluoromethyl group, or —CH ₂ -R ₉ (R ₉ Represents a hydroxyl group or a monovalent organic group. ) Represents a group represented by R ₂ Represents an alkyl group, a cycloalkyl group or an aryl group. R _Four , R _Five , R ₆ Each independently represents an alkyl group or a cycloalkyl group. R represents an atomic group necessary for forming a monocyclic cycloalkyl group together with a carbon atom. ) The content of the resin (C) is 0.01 to 10% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, according to any one of claims 1 to 8. The radiation-sensitive resin composition described in 1. A pattern forming method comprising: forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9 , and exposing and developing the coating film. The pattern forming method according to claim 10 , wherein the coating film is exposed through an immersion liquid.