KR101657983B1 - Active ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

[PROBLEMS] To provide a sensitizing actinic ray or radiation-sensitive resin composition which is excellent in line width roughness (LWR) performance and can form a pattern in which coating defects are suppressed, and a pattern forming method using the same .
[MEANS FOR SOLVING PROBLEMS] A sensitizing actinic radiation-sensitive or radiation-sensitive resin composition, which comprises the following (A) to (D).
(A) a resin which increases the solubility in an alkali developing solution by the action of an acid, (B) a resin which generates an acid by irradiation with an actinic ray or radiation represented by the following general formula (1-1) or (1-2) (C) a resin having at least one of a fluorine atom and a silicon atom, and a polarity-converting group decomposed by the action of an alkali developer to increase solubility in an alkali developing solution, and (D) a mixed solvent comprising two or more kinds of solvents , And a mixed solvent containing at least one solvent selected from the group consisting of the following formulas (S1) to (S4), wherein the total content of the solvents is 1 to 20 mass% in the total solvent. The symbols have the meanings given in the specification and claims.)

Description

TECHNICAL FIELD [0001] The present invention relates to an active radiation-sensitive or radiation-sensitive resin composition and a pattern forming method using the same. More particularly, the present invention relates to a radiation-

The present invention relates to a sensitizing actinic radiation or radiation-sensitive resin composition and a pattern forming method using the same, and more particularly to a process for producing a semiconductor such as an IC, a circuit substrate such as a liquid crystal or a thermal head, and other photofabrication processes , And a pattern forming method using the same. More specifically, the present invention relates to a sensitizing actinic ray-sensitive or radiation-sensitive resin composition, which is preferable when ultraviolet rays and electron beams of 250 nm or less, preferably 220 nm or less, are used as exposure light sources, and a pattern forming method using the same .

In the present invention, the term " actinic ray " or " radiation " means, for example, a line spectrum of mercury or the like, far ultraviolet ray, extreme ultraviolet ray, X-ray or electron ray typified by an excimer laser. In the present invention, light means an actinic ray or radiation.

When an ArF excimer laser (wavelength: 193 nm) is used as a light-sensitive composition such as a chemically amplified resist composition for use in a photolithography process of a semiconductor or the like, a resin having an alicyclic hydrocarbon group is preferred from the viewpoints of transparency and dry etching resistance .

A photosensitive composition containing a resin having an alicyclic hydrocarbon group requires a stronger acid and a compound that generates a perfluoroalkylsulfonic acid such as triphenylsulfonium trifluoromethanesulfonate is used.

However, the perfluoroalkylsulfonic acid has a high hydrophobicity, and the photosensitive composition using the acid generator that generates the perfluoroalkylsulfonic acid has a low affinity to an aqueous developer, resulting in deterioration in sensitivity due to deterioration of developability or development defects.

On the other hand, a photosensitive composition using a compound capable of generating a specific acid containing a fluorine atom is described in Patent Document 1.

However, with the finer patterning of the pattern, there has been a need for better performance of various performances, especially exposure latitude and line edge roughness.

In addition, when the chemical amplification resist is applied to liquid immersion lithography, it has been pointed out that the resist layer comes into contact with the immersion liquid at the time of exposure, and the components that adversely affect the immersion liquid from the resist layer flow out. Patent Document 2 discloses an example in which resist performance is changed by immersing a resist for ArF exposure in water before and after exposure, and this is pointed out as a problem in liquid immersion lithography.

Patent Document 3 describes an example of using an acid generator having a specific sulfonimide structure in liquid immersion exposure.

On the other hand, when triarylsulfonium salts such as triphenylsulfonium salts are applied to ArF excimer lasers, the transmittance of light decreases toward the bottom of the resist film due to the strong absorption due to the benzene ring, (Tapered) shape due to the presence of a large number of protrusions. For this reason, a number of attempts have been made with respect to a photoresist photoacid generator having high sensitivity at a wavelength of 193 nm and having high transparency.

As an example thereof, a sulfonium salt compound having an alkoxynaphthalene skeleton in Patent Document 4 has been proposed. Patent Document 5 proposes a sulfonium cation salt having an alkoxynaphthalene skeleton in which sulfonimide is used as a counter anion. However, these compounds have high transparency in the far ultraviolet region, but are not satisfactory in terms of lithography performance.

Japanese Patent Application Laid-Open No. 2004-2252 WO 04/068242 Japanese Patent Application Laid-Open No. 2006-84530 Japanese Patent Application Laid-Open No. 10-232490 Japanese Patent Application Laid-Open No. 2004-12554

It is an object of the present invention to provide an actinic ray-sensitive or radiation-sensitive resin composition having a good line width roughness (LWR) performance and capable of forming a pattern in which coating defects are suppressed, and a pattern forming method using the same .

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have completed the present invention described below.

(1) A sensitizing actinic radiation-sensitive or radiation-sensitive resin composition, which comprises the following (A) to (D).

(A) a resin having an increased solubility in an alkali developing solution by the action of an acid,

(B) a compound represented by the following general formula (1-1) or (1-2)

(C) a resin having at least one of a fluorine atom and a silicon atom, and a polarity-converting group decomposed by the action of an alkali developer to increase the solubility in an alkali developing solution, and

(D) at least one solvent selected from the group consisting of the following formulas (S1) to (S4), wherein the total content of the solvents is 1 To 20% by mass.

In the general formula (1-1)

R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.

R _14, when present in plural, independently represent an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group or a group having a monocyclic or polycyclic cycloalkyl skeleton.

R ₁₅ independently represent an alkyl group, a cycloalkyl group or a naphthyl group. Two R < ₁₅ > may be bonded to each other to form a ring.

and l represents an integer of 0 to 2.

r represents an integer of 0 to 8;

X ^- represents an acetylenic anion.

In the general formula (1-2)

M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when having a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbon-carbon double bond.

R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

R _x and R _y may combine to form a ring.

At least two of M, R _1c and R _2c may combine to form a ring, and the ring structure may contain a carbon-carbon double bond.

X ^- represents an acetylenic anion.

In the formula (S1) ~ (S3), R 1 ~R 7 is an aryl group which may have a cycloalkyl group, or a substituent which may have an alkyl group which may have a substituent, each independently. R ₁ and R ₂ , R ₃ and R ₄ , or R ₆ and R ₇ may be connected to form a ring.

In the general formula (S4), R ₈ and R ₉ each independently represent an alkyl group which may have a substituent, and the two groups may be connected to each other to form a ring.

(2) The actinic ray-sensitive or radiation-sensitive resin composition according to (1), wherein the resin (A) contains a repeating unit containing a lactone structure.

(3) The actinic ray or radiation-sensitive resin composition according to (1) or (2), wherein the resin (A) contains a repeating unit having an acid-decomposable group containing a monocyclic or polycyclic alicyclic structure .

(4) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (3), wherein immersion exposure is applied.

(5) The positive active radiation-sensitive or radiation-sensitive resin composition according to any one of (1) to (4), wherein the content of the compound (B) is 10 to 30 mass% Composition.

(6) A process for forming a film, comprising the steps of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5) Pattern formation method.

(7) The pattern forming method according to (6), wherein the exposure is liquid immersion exposure.

(Effects of the Invention)

The present invention makes it possible to provide a sensitizing actinic radiation-sensitive or radiation-sensitive resin composition capable of inhibiting coating defects and capable of forming a pattern having excellent LWR performance, and a pattern forming method using the same. Further, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferable as a positive resist composition.

Hereinafter, the best mode for carrying out the present invention will be described.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term " exposure " in this specification means not only exposure by deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also exposure by means of particle beams such as electron beams and ion beams .

[1] A compound which generates an acid upon irradiation with an actinic ray or radiation

The composition of the present invention contains a compound which generates an acid upon irradiation with an actinic ray or radiation (hereinafter also referred to as " acid generator ").

The composition of the present invention contains at least a compound represented by the following general formula (1-1) or (1-2) (hereinafter also referred to as "compound (B)") as an acid generator. The content of the compound (B) is preferably from 10 to 30 mass%, more preferably from 20 to 30 mass%, and still more preferably from 20 to 26 mass%, based on the total solid content of the composition of the present invention.

These compounds can maintain the transmittance of ArF light with a wavelength of 193 nm at a high level even if the added amount is in the above range, and for example, when the transmittance of light with a wavelength of 193 nm is 60% or more and 85% . The high transmittance to ArF light results in good performance in patterning with ArF light.

The transmittance with respect to light having a wavelength of 193 nm can be measured by, for example, applying a sensitizing actinic ray or radiation-sensitive resin composition onto a quartz glass substrate by spin coating and prebaking at 100 캜 to form a film having a film thickness of 100 nm , And the absorbance at a wavelength of 193 nm of the film is measured by an ergonomometer EPM-222 (manufactured by JAI URBAN CO., LTD.).

It is preferable to contain the compound represented by the general formula (1-1) or (1-2) in an amount of 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass Do.

In the general formula (1-1)

R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.

R ₁₄ , when present in plural, independently represent an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group or a group having a monocyclic or polycyclic cycloalkyl skeleton.

R ₁₅ independently represent an alkyl group, a cycloalkyl group or a naphthyl group. Two R < ₁₅ > may be bonded to each other to form a ring.

and l represents an integer of 0 to 2.

r represents an integer of 0 to 8;

X ^- represents an acetylenic anion.

In the general formula (1-2)

M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when having a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbon-carbon double bond.

R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

R _x and R _y may combine to form a ring. At least two of M, R _1c and R _{2c may} combine to form a ring, and the ring structure may contain a carbon-carbon double bond.

X ^- represents an acetylenic anion.

First, the general formula (1-1) will be described in detail.

The alkyl group represented by R ₁₃ , R ₁₄ and R _{15 in} the general formula (1-1) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, an n- Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2- Ethylhexyl group, n-nonyl group, n-decyl group and the like. Of these alkyl groups, methyl, ethyl, n-butyl and t-butyl are preferred.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, T-butyl group, and the like. Cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl are particularly preferable.

The alkoxy group represented by R ₁₃ and R ₁₄ is preferably a straight chain, branched or cyclic group having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, Propyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-hexyloxy group, A 2-ethylhexyloxy group, an n-nonyloxy group, a n-decyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. Of these alkoxy groups, methoxy group, ethoxy group, n-propoxy group, n-butoxy group and the like are preferable.

The alkoxycarbonyl group for R ₁₃ and R ₁₄ is preferably a linear or branched group having 2 to 11 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n An n-pentyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-heptyloxycarbonyl group, an n-heptyloxycarbonyl group, a n-pentyloxycarbonyl group, Octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyloxycarbonyl group. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group and the like are preferable.

Examples of the group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

As the monocyclic or polycyclic cycloalkyloxy group of R ₁₃ and R _14, the total number of carbon atoms is preferably 7 or more, more preferably 7 or more and 15 or less, and further preferably monocyclic cycloalkyl skeleton. Examples of the monocyclic cycloalkyloxy group having 7 or more carbon atoms as the total carbon atoms include cycloalkyloxy groups such as cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclopentyloxy group, cyclooctyloxy group and cyclododecanyloxy group An ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a dodecyl group, a 2-ethylhexyl group, an isopropyl group, a sec- A halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, a methoxy group, an ethoxy group, a hydroxyethoxy group, An alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, an acyl group such as a formyl group, an acetyl group or a benzoyl group, an acyloxy group such as an acetoxy group or a butyryloxy group, A substituent such as a carboxy group And cycloalkyloxy groups having a monocyclic, indicates that the small number of bullets combined with any of the substituents on the cycloalkyl group 7 or more.

Examples of the polycyclic cycloalkyloxy group having a total carbon number of 7 or more include a norbornyloxy group, a tricyclodecanyloxy group, a tetracyclodecanyloxy group, and an adamantanetyloxy group, and they may have the above-mentioned substituent .

As the alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R _{14, the total number} of carbon atoms is preferably 7 or more, more preferably 7 or more and 15 or less, and the alkoxy group having a monocyclic cycloalkyl skeleton . Examples of the alkoxy group having a monocyclic cycloalkyl skeleton having a total carbon number of 7 or more include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, Isobutoxy, isopropoxy, sec-butoxy, t-butoxy, iso-amyloxy and the like, substituted with a monocyclic cycloalkyl group which may have the above-mentioned substituent, and the number of the total carbon atoms including substituents is 7 or more. For example, a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group and the like, and a cyclohexylmethoxy group is preferable.

Examples of the alkoxy group having a polycyclic cycloalkyl skeleton having a total carbon number of 7 or more include a norbornylmethoxy group, a norbornylethoxy group, a tricyclodecanylmethoxy group, a tricyclodecanylethoxy group, a tetracyclodecanylmethoxy group , Tetracyclodecanylethoxy group, adamantanetylmethoxy group, adamantanethylethoxy group and the like, and among them, a norbornylmethoxy group and a norbornylethoxy group are preferable. These may have the above-mentioned substituent.

As the alkyl group of the alkylcarbonyl group of R ₁₄ , specific examples such as the alkyl groups as R ₁₃ to R ₁₅ described above may be mentioned.

The alkylsulfonyl group and cycloalkylsulfonyl group for R ₁₄ are preferably linear, branched or cyclic, and preferably have 1 to 10 carbon atoms, and examples thereof include a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, Butanesulfonyl group, n-pentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group, An n-decylsulfonyl group, a cyclopentanesulfonyl group, and a cyclohexanesulfonyl group. Of these alkylsulfonyl and cycloalkylsulfonyl groups, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, and a cyclohexanesulfonyl group are preferable.

The substituent may be a halogen atom (e.g., fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, .

Examples of the alkoxy group include a methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, Branched or cyclic alkoxy groups having 1 to 20 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group.

Examples of the alkoxyalkyl group include straight chain, branched or cyclic alkyl groups having 2 to 21 carbon atoms such as methoxymethyl, ethoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, Branched or cyclic alkoxyalkyl groups, and the like.

Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, Branched or cyclic alkoxycarbonyl groups having 2 to 21 carbon atoms such as cyclopentyloxycarbonyl, butoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl and the like.

Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, a n-butoxycarbonyloxy group, A linear, branched or cyclic alkoxycarbonyloxy group having 2 to 21 carbon atoms such as a t-butoxycarbonyloxy group, a cyclopentyloxycarbonyloxy group and a cyclohexyloxycarbonyloxy group, .

As the ring structure in which two R < ₁₅ > may be bonded to each other, the two divalent R < ₁₅ > s may be a 5- or 6-membered ring formed together with the sulfur atom in the general formula (1-1) (I.e., a tetrahydrothiophene ring), and may be ring-opened with an aryl group or a cycloalkyl group. The divalent group R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group and an alkoxycarbonyloxy group.

R _{15 is preferably a} methyl group, an ethyl group, a naphthyl group, or a divalent group in which two R _{15 s} are bonded together to form a tetrahydrothiophene ring structure together with a sulfur atom.

The substituent which R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group or a halogen atom (in particular, a fluorine atom).

l is preferably 0 or 1, and more preferably 1.

As r, 0 to 2 is preferable.

Examples of the salt represented by the general formula (1-1) of the present invention include the following specific examples.

In the formula, X ^- represents a counter anion.

Next, the general formula (1-2) will be described.

In the formulas, R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when having a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbon-carbon double bond.

R _x and R _y may combine to form a ring. At least two of M, R _1c and R _2c may be bonded to form a ring or may contain a carbon-carbon double bond in the ring structure.

The alkyl group as M may be straight chain or branched and is, for example, an alkyl group having 1 to 20 carbon atoms, preferably a straight chain or branched alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, Propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group.

The cycloalkyl group as M is a cyclic alkyl group having from 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group.

The aryl group as M preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

Each group as M may have a cycloalkyl group, an alkoxy group, a halogen atom, a phenylthio group and the like as a substituent. The cycloalkyl group and the aryl group as M may further have an alkyl group as a substituent. The carbon number of the substituent is preferably 15 or less.

When M is a phenyl group, those having at least one straight-chained, branched, cyclic alkyl group, linear, branched, cyclic alkoxy, or phenylthio group as a substituent are preferable, and the sum of the carbon numbers of the substituent is more preferably 2 to 15. As a result, the solvent solubility is further improved, and generation of particles during storage is suppressed.

Examples of the alkyl group as R _1c and R _{2c include} an alkyl group having 1 to 12 carbon atoms, preferably a linear and branched alkyl group having 1 to 5 carbon atoms (e.g., a methyl group, an ethyl group, a linear or branched propyl group).

The cycloalkyl group as R _1c and R _2c is, for example, a cycloalkyl group having 3 to 12 carbon atoms, and preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The aryl group as R _1c and R _2c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The ring structure formed by bonding at least two of M, R _1c and R _2c is preferably a 3 to 12-membered ring, more preferably a 3-membered to 10-membered ring, still more preferably a 3 to 6-membered ring. The ring skeleton may have a carbon-carbon double bond.

When R _1c and R _2c are combined to form a ring, the group formed by combining R _1c and R _2c is preferably an alkylene group having 2 to 10 carbon atoms, and examples thereof include an ethylene group, a propylene group, a butylene group, A methoxy group, a methoxy group, a methoxy group, a methoxy group, The ring formed by combining R _1c and R _2c may have a hetero atom such as an oxygen atom in the ring.

_Examples of the alkyl group as R _x and R _y include the same alkyl groups as R _1c and R _2c .

The cycloalkyl group is preferably a cycloalkyl group having from 3 to 8 carbon atoms, and examples thereof include a cyclopentyl group and a cyclohexyl group.

The 2-oxoalkyl group includes a group having > C = O at two positions of the alkyl group as R _1c and R _2c .

The alkoxy group in the alkoxycarbonylalkyl group may be any of linear, branched and cyclic, and includes, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a straight chain and branched alkoxy group having 1 to 5 carbon atoms A linear or branched butoxy group, a straight chain or branched pentoxy group), and a cyclic alkoxy group having 3 to 8 carbon atoms (e.g., a cyclopentyloxy group, a cyclohexyloxy group). have. Examples of the alkyl group in the alkoxycarbonylalkyl group include an alkyl group having 1 to 12 carbon atoms, preferably a straight chain having 1 to 5 carbon atoms (e.g., methyl group and ethyl group).

The allyl group is not particularly limited, but is preferably an allyl group substituted by an unsubstituted or monocyclic or polycyclic cycloalkyl group.

The vinyl group is not particularly limited, but is preferably a vinyl group substituted with an unsubstituted or monocyclic or polycyclic cycloalkyl group.

As the ring structure which may be formed by bonding R _x and R _y to each other, bivalent R _x and R _y (for example, methylene group, ethylene group, propylene group, etc.) are formed together with sulfur atom in the general formula (1-2) A 5-membered or 6-membered ring, particularly preferably a 5-membered ring (i.e., a tetrahydrothiophene ring).

R _x and R _y are preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups.

Examples of the cation of the compound represented by the general formula (1-2) of the present invention include the following specific examples.

Examples of the counter ion represented by X < ^- > in formulas (1-1) and (1-2) include a structure represented by the following formula (II).

In the general formula (II), A represents an oxygen atom, a nitrogen atom, or a carbon atom.

R ₁ represents a monovalent organic group having a fluorine atom, and preferably represents a monovalent organic group having a total mass of fluorine atoms / (mass of total atoms contained) = 0.35 or less.

R ₂ represents a fluorine atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.

N + m = 2 when A is a nitrogen atom, n = 1 or 2, m = 0 or 1 when A is an oxygen atom, n + m = 3 when A is a carbon atom n is an integer of 1 to 3, and m is an integer of 0 to 2. When n is 2 or more, R ₁ may be the same or different, and R ₁ may combine with each other to form a ring.

The general formula (II) will be described in more detail.

R ₁ is a monovalent organic group containing a fluorine atom and is preferably a monovalent organic group having a fluorine content of 0.35 or less represented by (mass of total fluorine atoms contained) / (mass of total atoms contained). The fluorine content of R ₁ is more preferably 0.30 or less, and particularly preferably 0.25 or less.

Examples of the monovalent organic group containing a fluorine atom represented by R ₁ include an organic group containing an alkylene moiety substituted with at least one fluorine atom bonded to a sulfonyl group and the alkylene moiety is a perfluoroalkylene group Is more preferable. The terminal thereof is preferably substituted with a group having a cyclic structure and may be substituted through a linking group. From the viewpoint of the low fluorine content rate, it is preferable that the group having the cyclic structure does not contain a fluorine atom. The monovalent organic group represented by R ₁ includes, in one form, a structure corresponding to R ₁ represented by the general formula (III) which will be described later.

R ₂ represents an alkyl group, a cycloalkyl group, an aryl group, a branched alkyl group, a monocyclic alkyl group, a polycyclic hydrocarbon group, or a monocyclic aryl group, and the chain alkyl group, the monocyclic alkyl group, the polycyclic hydrocarbon group, The aryl group may have a substituent. The substituent preferably has a fluorine atom.

The chain alkyl group may be straight chain or branched chain and may be branched or straight chain such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, 2-ethylhexyl, isopropyl, sec-butyl, .

The alkyl group may have a substituent and examples of the substituent include hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamide group, methyl group, an alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group and a butoxy group, an alkoxy group such as a methoxy group, an ethoxy group, An alkoxycarbonyl group such as an ethoxycarbonyl group and an ethoxycarbonyl group, an acyl group such as formyl group, acetyl group and benzoyl group, an acyloxy group such as acetoxy group and butyryloxy group, and a carboxy group.

Examples of the monocyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, and cyclooctadienyl. Particularly, cyclopropyl, cyclo Pentyl, cyclohexyl, and cyclooctyl are preferred.

The monocyclic alkyl group may have a substituent and examples of the substituent include halogen atoms (fluorine, chlorine, bromine and iodine), nitro group, cyano group, amide group, sulfonamide group, methyl group, ethyl group, an alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group and a butoxy group, an alkoxy group such as a methoxy group, an ethoxy group, An alkoxycarbonyl group such as an ethoxycarbonyl group and an ethoxycarbonyl group, an acyl group such as formyl group, acetyl group and benzoyl group, an acyloxy group such as acetoxy group and butyryloxy group, and a carboxy group.

Examples of the polycyclic hydrocarbon group include bicyclo [4.3.0] nonanyl, decahydronaphthalenyl, tricyclo [5.2.1.0 (2,6)] decanyl, boronyl, isobornyl, Trimethyltricyclo [2.2.1.0 ^2,6 ] heptanyl, 3,7,7-trimethylbicyclo [4.1.0] heptanyl, and the like. Particularly, ≪ / RTI > aryl, heteroaryl, heteroaryl, heteroaryl, heteroaryl,

Examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine and iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, a methyl group, an alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, a butoxy group, etc. may be substituted with an alkyl group such as an n-propyl group, An alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, an acyl group such as a formyl group, an acetyl group or a benzoyl group, an acyloxy group such as an acetoxy group or a butyryloxy group, or a carboxy group.

R ₂ preferably has an electron-attracting group from the viewpoint of acid strength. Examples of the electron donating group include, but are not limited to, cyano group, trifluoromethyl group, nitro group, carboxyl group, ketone group, acyloxy group, hydroxyl group, perfluoroalkyl group, methoxy group, ethoxy group, an alkoxy group such as a t-butoxy group and a benzyloxy group, a halogen atom such as a fluorine atom and a chlorine atom, and particularly preferably a fluorine atom. More preferably, R ₂ is a group having a fluorine atom with a molecular weight of 220 or less, and in particular, R ₂ is preferably a trifluoromethyl group.

The counter anion represented by the general formula (II) is preferably a structure represented by the following general formula (III).

In the general formula (III), A, R ₂ , m and n are the same as those in the general formula (II).

R _3, when there are a plurality of R _{3 s,} independently represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent or an aryl group which may have a substituent, and R ₄ represents a hydrogen atom.

L represents a single bond or a linking group.

p1 represents an integer of 1 to 8, p2 represents 1 or 2, and p3 represents 0 or 1.

When p2 = 2, two R ₃ may combine with each other to form a ring structure, and when n = 2 or more, plural R ₃ may combine with each other to form a ring structure.

Specific examples of the alkyl group, cycloalkyl group and aryl group represented by R ₃ include groups similar to those exemplified for each of R ₂ .

It is preferable that R ₃ does not have a fluorine atom from the viewpoint of the low fluorine content.

L is a single bond, an oxygen atom (-O-), a sulfur atom (-S-), a nitrogen atom (> N-), a carboxyl group (-OC = O-, O-), and a sulfonamide group (> NSO ₂ -). In particular, p2 = 2 and the two R ₃ In this case, to form a ring by combining to each other, L is preferably connected to group having a nitrogen atom such as an amide group, a sulfonamide group, and this time, the two R ₃ are bonded to each other to To form a cyclic amine residue having a nitrogen atom in the ring on the L-phase.

Examples of the cyclic amine residue structure include aziridine, azetidine, pyrrolidine, piperidine, hexamethyleneimine, heptamethyleneimine, piperazine, decahydroquinoline, decahydroquinoline, 8-azabicyclo [3.2.1] , Oxazolidine, thiazolidine, 2-azanorbornane, 7-azanorbornane, morpholine, thiamorpholine and the like, and they may have a substituent. Examples of the substituent include hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamide group, methyl group, ethyl group, An alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group and a butoxy group, an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group, An acyl group such as a carbonyl group, a formyl group, an acetyl group, a benzoyl group, and a carbonyl group on a carbon to form a ring, an acyloxy group such as an acetoxy group and a butyryloxy group, and a carboxy group.

Examples of the counter anion structure represented by the general formula (II) of the present invention include the following specific examples.

The compound (B) represented by the general formula (1-1) for generating an acid includes the following compounds, but is not limited thereto.

As the compound (B) represented by the general formula (1-2) for generating an acid, there may be mentioned the following compounds, but it is not limited thereto.

The acid generators (B) represented by the general formulas (1-1) and (1-2) may be used singly or in combination.

The compound (B) photoacid generator is preferably contained in an amount of from 10 to 60 mass%, more preferably from 20 to 50 mass%, based on the total solid content in the composition of the present invention together with other photoacid generators shown below, And particularly preferably from 20 to 35 mass%.

Further, the compound (B) is preferably contained in an amount of 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, in the total amount of the photoacid generator.

[Other photoacid generators]

In the present invention, in addition to the photoacid generator (B), a compound which is decomposed by irradiation with an actinic ray or radiation to generate an acid may be used in combination. Examples of such usable photoacid generators include photoinitiators for photocationic polymerization, photoinitiators for photo radical polymerization, photochromic agents for dyes, photochromic agents, and known compounds that generate an acid by irradiation with an actinic ray or radiation, And a mixture thereof can be appropriately selected and used.

Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oxime sulfonates, diazodisulfone, disulfone and o-nitrobenzylsulfonate.

Examples of the compound capable of generating an acid upon irradiation with these actinic rays or radiation include compounds in which the compound is introduced into the main chain or side chain of the polymer such as those described in U.S. Patent No. 3,849,137, German Patent No. 3914407, Japanese Patent Application Laid-Open Nos. 63-26653, 55-164824, 62-69263, 63-146038, 63-163452, Compounds described in JP-A-62-153853 and JP-A-63-146029 can be used.

Compounds which generate an acid by the light described in U.S. Patent No. 3,779,778, European Patent No. 126,712, and the like can also be used.

As preferable compounds in the acid generator, compounds represented by the following general formulas (ZI), (ZII) and (ZIII) can be given.

In the above general formula (ZI)

R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

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

Also, R ₂₀₁ ~R by combining two of the dog ₂₀₃ may be bonded to form a ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, a carbonyl group in the ring. R ₂₀₁ ~R The group formed by combining two of the dog ₂₀₃ may be mentioned an alkylene group (e.g. a butylene group, a pentylene group).

Z ^- represents an unconjugated anion.

Examples of the non-nucleophilic anion as Z ^- include a sulfonic acid anion, a carboxylic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

Non-nucleophilic anions are anions that have a remarkably low ability to cause nucleophilic reactions, and are anions that can inhibit aging degradation due to intramolecular nuclear reactions. This improves the stability with time of the active radiation-sensitive or radiation-sensitive resin composition.

Examples of the sulfonic acid anion include an aliphatic sulfonic acid anion, an aromatic sulfonic acid anion, and a camphorsulfonic acid anion.

Examples of the carboxylic acid anion include an aliphatic carboxylic acid anion, an aromatic carboxylic acid anion, and an aralkylcarboxylic acid anion.

The aliphatic moiety in the aliphatic sulfonic acid anion may be either an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms such as a methyl group, an ethyl group, a propyl group, a decyl group, an undecyl group, a tridecyl group, a tetradecyl group, a tetradecyl group, a tetradecyl group, a hexadecyl group, a hexadecyl group, a heptyl group, an octyl group, A cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group and a boronyl group, and the like can be given as examples of the cyclic group-containing cyclic group-containing cyclic group-containing cyclic group- .

The aromatic group in the aromatic sulfonic acid 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 in the aliphatic sulfonic acid anion and the aromatic sulfonic acid anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonic acid anion and the aromatic sulfonic acid anion include a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), a carboxyl group, An alkoxy group (preferably having from 1 to 15 carbon atoms), an alkoxy group (preferably having from 1 to 15 carbon atoms), a cycloalkyl group (preferably having from 3 to 15 carbon atoms), an aryl group (preferably having from 6 to 14 carbon atoms) (Preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (Preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms), an alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms) Alkylaryloxysulfonyl group (preferably (Preferably having from 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having from 5 to 20 carbon atoms), and a cycloalkylalkyloxyalkyloxy group (preferably having from 8 to 20 carbon atoms). As the aryl group and the ring structure of each group, an alkyl group (preferably having 1 to 15 carbon atoms) may be mentioned as a substituent.

Examples of the aliphatic moiety in the aliphatic carboxylic acid anion include an alkyl group and a cycloalkyl group such as those having an aliphatic sulfonic acid anion.

Examples of the aromatic group in the aromatic carboxylic acid anion include aryl groups such as those in the aromatic sulfonic acid anion.

The aralkyl group in the aralkylcarboxylic acid anion is preferably an aralkyl group having 6 to 12 carbon atoms such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylbutyl group.

The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylic acid anion, aromatic carboxylic acid anion and aralkylcarboxylic acid anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylic acid anion, aromatic carboxylic acid anion and aralkylcarboxylic acid anion include halogen atoms such as those in the aromatic sulfonic acid anion, , A cycloalkyl group, an alkoxy group, an alkylthio group and the like.

The sulfonylimide anion includes, for example, a saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, An isobutyl group, a sec-butyl group, a pentyl group, and a neopentyl group. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkyl aryloxysulfonyl group. Alkyl groups are preferred.

Examples of other non-nucleophilic anions include phosphorus fluoride, boron fluoride, antimony fluoride, and the like.

Examples of the non-nucleophilic anion of Z ^- include an aliphatic sulfonic acid anion in which the alpha position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, a bis (alkylsulfonyl) imide anion in which the alkyl group is substituted with a fluorine atom, Tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom is preferable. The non-nucleophilic anion is preferably a perfluoro aliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, a pentafluoro anion, Benzenesulfonic acid anion, and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

The non-nucleophilic anion of Z ^- may be a structure represented by the following formula (Xa) or formula (Xb).

In the general formula (Xa), R represents a hydrogen atom or an organic group, preferably an organic group having 1 to 40 carbon atoms, more preferably an organic group having 3 to 20 carbon atoms, an organic group represented by the following formula (XI) Is most preferable.

The organic group of R may include at least one carbon atom. Preferably, the atom bonded to the oxygen atom in the ester bond represented by formula (Xa) is a carbon atom, and examples thereof include an alkyl group, a cycloalkyl group, An aralkyl group, or a group having a lactone structure, and may have a hetero atom such as an oxygen atom or a sulfur atom in the chain. These groups may be substituted with each other or may have a substituent such as a hydroxyl group, an acyl group, an acyloxy group, an oxy group (= O), or a halogen atom.

- (CH ₂ ) _n -R c - (Y) _m ????? (XI)

In the formula (XI), Rc represents a monocyclic or polycyclic cyclic organic group having 3 to 30 carbon atoms which may contain cyclic ether, cyclic thioether, cyclic ketone, cyclic carbonate ester, lactone or lactam structure. Y represents a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, An alkoxycarbonyl group, an acyloxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a halogenated alkyl group having 1 to 8 carbon atoms. m = 0 to 6, and when plural Ys exist, they may be the same or different. n = 0 to 10.

The total number of carbon atoms constituting the R group represented by the formula (XI) is preferably 40 or less.

n = 0 to 3, and Rc is a monocyclic or polycyclic cyclic organic group having 7 to 16 carbon atoms.

In the general formula (Xb), Rb represents a hydrogen atom or an organic group, preferably a hydrogen atom or an organic group having 1 to 40 carbon atoms, more preferably a hydrogen atom or an organic group having 3 to 20 carbon atoms. The R < b > s may be different from each other and may be bonded to each other to form a ring. The organic group of Rb may contain at least one carbon atom. Preferably, the atom bonded to the nitrogen atom in the amide bond represented by formula (Xb) is a carbon atom, and examples thereof include an alkyl group, a cycloalkyl group, An aralkyl group, or a group having a lactone structure, and may have a hetero atom such as an oxygen atom or a sulfur atom in the chain. These groups may be substituted with each other or may have a substituent such as a hydroxyl group, an acyl group, an acyloxy group, an oxy group (= O), or a halogen atom.

The molecular weight of the non-nucleophilic anion site represented by the general formula (Xa) and the general formula (Xb) is generally 300 to 1000, preferably 400 to 800, and more preferably 500 to 700.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the following compounds (ZI-1), (ZI-2) and (ZI-3).

Further, a compound having a plurality of structures represented by the general formula (ZI) may be used. For example, the general formula (ZI) having an R ₂₀₁ ~R structure ₂₀₃ of the at least one dog and at least one combination of the general formula (ZI) indicated one more compound, R ₂₀₁ ~R ₂₀₃ which in the compound represented by compound .

More preferred examples of the component (ZI) include the compounds (ZI-1), (ZI-2) and (ZI-3) described below.

The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in the general formula (ZI) is an aryl group, that is, a compound in which arylsulfonium is a cation.

In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, and some of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an aryldicycloalkylsulfonium compound.

The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom and the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by disappearance of one hydrogen atom from pyrrole), a furan residue (a group formed by eliminating one hydrogen atom from furan), a thiophene residue (The group formed by eliminating one hydrogen atom from the indole), a benzofuran residue (a group formed by eliminating one hydrogen atom from the benzofuran), a benzothiophene residue (a group formed by eliminating one hydrogen atom from the benzofuran), an indole residue (A group formed by eliminating one hydrogen atom from benzothiophene), and the like. When the arylsulfonium compound has two or more aryl groups, two or more aryl groups may be the same or different.

The alkyl group or cycloalkyl group which the arylsulfonium compound optionally has is preferably a straight chain or branched alkyl group having from 1 to 15 carbon atoms and a cycloalkyl group having from 3 to 15 carbon atoms, and examples thereof include a methyl group, ethyl group, Butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

R ₂₀₁ an aryl group, an alkyl group, a cycloalkyl group ~R ₂₀₃ include an alkyl group (for example, 1 to 15 carbon atoms), cycloalkyl groups (e.g. 3 to 15 carbon atoms), an aryl group (e.g. having 6 to 14 carbon atoms), an alkoxy Group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group. Preferred examples of the substituent include a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, 4 < / RTI > The substituent may be substituted with any one of three R ₂₀₁ to R ₂₀₃ , or may be substituted with all three of R ₂₀₁ to R ₂₀₃ . When R ₂₀₁ to R ₂₀₃ are aryl groups, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) is described.

The compound (ZI-2) is a compound in which each of R ₂₀₁ to R ₂₀₃ in the formula (ZI) independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group containing no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R ₂₀₁ ~R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, a vinyl group, and more preferably a straight chain or branched 2-oxoalkyl group, a 2-oxo-cycloalkyl group, an alkoxycarbonylmethyl group, and particularly preferably in the Is a straight chain or branched 2-oxoalkyl group.

R ₂₀₁ The alkyl group and cycloalkyl group of ~R _203, preferably a straight chain or branched alkyl group (e.g. methyl, ethyl, propyl, butyl, pentyl), a cycloalkyl group of 3 to 10 carbon atoms having 1 to 10 carbon atoms ( A cyclopentyl group, a cyclohexyl group, and a norbornyl group). The alkyl group is more preferably a 2-oxoalkyl group or an alkoxycarbonylmethyl group. As the cycloalkyl group, more preferred is a 2-oxocycloalkyl group.

The 2-oxoalkyl group may be either a straight chain or a branched group, and preferably a group having > C = O at two positions of the alkyl group.

The 2-oxocycloalkyl group is preferably a group having > C = O at the 2-position of the cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

R ₂₀₁ to R ₂₀₃ may be further substituted by a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

The compound (ZI-3) is a compound represented by the following general formula (ZI-3) and having a phenacylsulfonium salt structure.

In the general formula (ZI-3)

R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.

R _6c and R _7c each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y may combine with each other to form a ring structure, and the ring structure may be an oxygen atom, a sulfur atom, an ester bond, . Examples of the group formed by combining any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.

Zc ^- represents an unconjugated anion and includes non-nucleophilic anions such as Z ^- in general formula (ZI).

The alkyl group as R _1c to R _7c may be either a straight chain or a branched chain, and examples thereof include an alkyl group having 1 to 20 carbon atoms, preferably a straight chain and branched alkyl group having 1 to 12 carbon atoms (e.g., A propyl group, a straight chain or branched butyl group, and a straight chain or branched pentyl group). Examples of the cycloalkyl group include a cycloalkyl group having 3 to 8 carbon atoms (e.g., a cyclopentyl group and a cyclohexyl group) .

The alkoxy group as R _1c to R _{5c may} be any of linear, branched and cyclic, and includes, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a straight chain and branched alkoxy group having 1 to 5 carbon atoms (e.g., A straight chain or branched butoxy group, a straight chain or branched pentoxy group), and a cyclic alkoxy group having 3 to 8 carbon atoms (e.g., cyclopentyloxy group, cyclohexyloxy group).

Preferably, any one of R _1c to R _5c is a straight chain or branched alkyl group, a cycloalkyl group, or a straight chain, branched or cyclic alkoxy group, more preferably the sum of the carbon numbers of R _1c to R _5c is 2 to 15. As a result, the solvent solubility is further improved, and generation of particles during storage is suppressed.

The alkyl group and the cycloalkyl group as R _x and R _{y include} an alkyl group and a cycloalkyl group as in R _1c to R _7c , and a 2-oxoalkyl group, a 2-oxocycloalkyl group and an alkoxycarbonylmethyl group are more preferable.

The 2-oxoalkyl group and the 2-oxocycloalkyl group include a group having &_gt; C = O at two positions of an alkyl group and a cycloalkyl group as R _1c to R _7c .

Alkoxycarbonyl groups for alkoxy in the group may be an alkoxy group such as those of the R _1c ~R _5c.

R _x and R _y are preferably an alkyl group or a cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl or cycloalkyl groups.

Among the general formulas (ZII) and (ZIII)

Each of R ₂₀₄ to R ₂₀₇ independently represents an aryl group, an alkyl group or a cycloalkyl group.

The aryl group represented by R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R ₂₀₄ to R _{207 may be} an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom and the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by disappearance of one hydrogen atom from pyrrole), a furan residue (a group formed by eliminating one hydrogen atom from furan), a thiophene residue (The group formed by eliminating one hydrogen atom from the indole), a benzofuran residue (a group formed by eliminating one hydrogen atom from the benzofuran), a benzothiophene residue (a group formed by eliminating one hydrogen atom from the benzofuran), an indole residue (A group formed by eliminating one hydrogen atom from benzothiophene), and the like.

Examples of the alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (such as a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group) An alkyl group (cyclopentyl group, cyclohexyl group, norbonyl group).

The aryl group, alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent which the aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms) An alkoxy group (for example, having from 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group, and the like.

Z ^- represents an unconjugated anion, and the same as the non-nucleophilic anion of Z ^{- in} the general formula (ZI).

Examples of the acid generator include compounds represented by the following general formulas (ZIV), (ZV) and (ZVI).

Among the general formulas (ZIV) to (ZVI)

Ar ₃ and Ar ₄ each independently represent an aryl group. R ₂₀₈ , R ₂₀₉ and R ₂₁₀ independently represent an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkylene group, an alkenylene group or an arylene group.

Among the acid generators, compounds represented by formulas (ZI) to (ZIII) are more preferable.

Further, as the acid generating agent, a compound which generates a sulfonic acid group or an acid having one imide group is preferable, more preferably a compound which generates a monovalent perfluoroalkanesulfonic acid, or a compound which generates a monovalent fluorine atom or a fluorine atom- Or a compound capable of generating an imidic acid substituted with a group containing a monovalent fluorine atom or a fluorine atom, more preferably a fluorine-substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted imine Or a sulfonium salt of a fluorine-substituted methide acid. The acid generator which can be used is particularly preferably a fluorinated alkanesulfonic acid, a fluorinated substituted benzenesulfonic acid or a fluorinated substituted imidic acid whose pKa of the generated acid is not more than pKa = -1, and the sensitivity is improved.

Particularly preferred examples among the acid generators are exemplified below.

[2] Solvent

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a mixed solvent (D) containing at least one solvent selected from the group consisting of the following formulas (S1) to (S4).

In the mixed solvent (D), the total amount (total amount) of the solvent represented by any one of formulas (S1) to (S4) is 1 to 20 mass%, preferably 1 to 10 mass%, of the total solvent.

Of the general formulas (S1) to (S3)

R ₁ to R ₇ each independently represent an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent or an aryl group which may have a substituent. R ₁ and R ₂ , R ₃ and R ₄ , or R ₆ and R ₇ may be connected to form a ring.

R ₁ to R ₇ in formulas (S1) to (S3) are preferably an alkyl group, and R ₁ and R ₂ , R ₃ and R ₄ , or R ₆ and R ₇ are connected to each other to form a ring Is more preferable.

The alkyl group of R ₁ to R ₇ includes, for example, an alkyl group having 1 to 4 carbon atoms. Examples of the cycloalkyl group include a cycloalkyl group (monocyclic or polycyclic) having 3 to 6 carbon atoms, and examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Hydroxyl group.

When R ₁ and R ₂ , R ₃ and R ₄ , and R ₆ and R ₇ are connected to form a ring (heterocycle), R ₁ and R ₂ , R ₃ and R ₄ , R ₆ and R ₇ Is preferably an alkylene group having 2 to 6 carbon atoms.

In the general formula (S4), R ₈ and R ₉ each independently represent an alkyl group which may have a substituent, and two groups may be connected to each other to form a ring.

Examples of the alkyl group for R ₈ and R ₉ include an alkyl group having 1 to 5 carbon atoms.

It is preferable that R ₈ and R ₉ are connected to each other to form a ring, and preferably form a 5- to 8-membered ring. The general formula (S4) is more preferably represented by the following general formula (s4). In the formula, n is an integer of 1 to 4.

As the solvent having the structure represented by the general formulas (S1) to (S4), the boiling point (1 atm) is preferably 150 to 250 占 폚, and more preferably 180 to 250 占 폚. For example, a solvent having a lactone structure such as? -Butyrolactone, a solvent having a cyclic ketone structure such as cyclopentanone or cyclohexanone, N-methylpyrrolidone, propylene carbonate and the like are preferable, Lactone and cyclohexanone are particularly preferable, and gamma -butyrolactone is most preferable.

As a solvent which is not preferable for use in the present invention, a protic solvent can be mentioned.

Examples of the protonic solvent include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether (PGME, alias 1-methoxy-2-propanol), propylene glycol monoethyl ether , Ethyl lactate, and the like.

The non-protonic solvent which is preferably used in combination with the solvent represented by the above formulas (S1) to (S4) as the solvent (D) of the present invention is not particularly limited, but propylene glycol monomethyl ether acetate (PGMEA) , And a mixed solvent containing 50 mass% or more of PGMEA.

As a preferable example of the mixed solvent (D), a mixed solvent containing at least one solvent selected from the group represented by the general formulas (S1) to (S4) and propylene glycol monomethyl ether acetate (PGMEA) have.

[3] Resin which increases the solubility in an alkali developing solution by the action of an acid

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin (hereinafter sometimes referred to as "resin (A)" or "acid-decomposable resin (A)" or the like) whose solubility in an alkali developer is increased by the action of an acid Lt; / RTI >

The acid-decomposable resin (A) has a group (hereinafter also referred to as an " acid-decomposable group ") which decomposes in the main chain and / or side chain of the resin by the action of an acid to generate an alkali-soluble group.

The resin (A) is preferably insoluble or sparingly soluble in an alkali developer.

The acid-decomposable group preferably has a structure protected by a group capable of decomposing and releasing an alkali-soluble group by the action of an acid.

The alkali-soluble group is not particularly limited as long as it is a group decomposed in the alkali developer to form an ion, and preferable examples of the alkali-soluble group include a carboxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol) and a sulfonic acid group.

Preferred as the acid-decomposable group is a group in which the hydrogen atom of the alkali-soluble group is substituted with a group capable of leaving by an acid.

The group to elimination with an acid, for example, _{-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 represent 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 to R ₀₂ each independently represent 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, or a tertiary alkyl ester group. More preferably a tertiary alkyl ester group.

The repeating unit having an acid-decomposable group which the resin (A) may contain is preferably a repeating unit represented by the following general formula (AI).

In the general formula (AI)

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 of the organic group include an alkyl group and an acyl group having 5 or less carbon atoms, 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 chain or branched chain) 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 of 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 a single bond or -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.

As the alkyl group of Rx _{1 to} Rx ₃ , 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-

As the cycloalkyl group represented by R x _{1 to} R x ₃ , a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group is preferable .

Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group A polycyclic cycloalkyl group is preferred.

Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are combined to form the above-mentioned cycloalkyl group.

Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms) And the number of carbon atoms is preferably 8 or less.

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

Specific examples of the preferable repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto.

In the specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent group containing a polar group, and represents a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, or a linear or branched alkyl group or cycloalkyl group having any one of them. When there are a plurality of them, they are independent of each other. p represents 0 or a positive integer.

It is more preferable that the resin (A) is a resin having at least any one of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2) as the repeating unit represented by the formula (AI). In another embodiment, the resin (A) is more preferably a resin having at least two repeating units represented by the general formula (1) as a repeating unit represented by the general formula (AI) in the other form, 1) and at least one of repeating units represented by the general formula (2).

Among the formulas (1) and (2)

R ₁ and R ₃ each independently represent 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.

R ₂ , R ₄ , R ₅ and R ₆ each independently represent 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 or may have a substituent.

The cycloalkyl group for R ₂ may be monocyclic or polycyclic, or may have a substituent.

R ₂ is preferably an alkyl group, more preferably from 1 to 10 carbon atoms, and still more preferably from 1 to 5 carbon atoms, 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 alicyclic structure, and its carbon number 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 or 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-

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.

As the repeating unit represented by the general formula (1), there may be mentioned a repeating unit represented by the following general formula (1-a).

Wherein R ₁ and R ₂ are the same as those in the general formula (1), respectively.

The repeating unit represented by the general formula (2) is preferably a repeating unit represented by the following general formula (2-1).

In formula (2-1)

R ₃ to R ₅ are the same as those in the general formula (2).

R ₁₀ represents a substituent group containing a polar group. When a plurality of R < ₁₀ > exist, they may be the same or different. The substituent containing a polar group includes, for example, a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, or a linear or branched alkyl group or cycloalkyl group having any one of them, Lt; / RTI > More preferably a branched alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.

p represents an integer of 0 to 15; p is preferably 0 to 2, more preferably 0 or 1.

As preferred combinations when the resin (A) is used in combination with the acid decomposing repeating unit, the following examples are preferable. In the formula, each R independently represents a hydrogen atom or a methyl group.

The resin (A) preferably contains a repeating unit having a lactone group.

As the lactone group, any lactone structure can be used, but it is preferable to have a 5- to 7-membered cyclic lactone structure and a cyclic structure in which a cyclic structure and a spiro structure are formed in the 5 to 7-membered ring lactone structure . It is more preferable to have a repeating unit having a lactone structure represented by any one 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), (LC1-17) Structure, LWR and development defects are improved.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred examples of the substituent (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, a carboxyl group, a halogen atom, a hydroxyl group, And the like. More preferably an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group. n ₂ represents an integer of 0 to 4; When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) present may be the same or different. Further, plural substituents (Rb ₂ ) may be bonded to form a ring.

The repeating unit having a lactone structure is preferably a repeating unit represented by the following formula (AII).

Among the general formula (AII)

Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. The preferable substituent which the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. And is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group formed by combining these groups. Preferably a single bond, or a divalent linking group represented by -Ab ₁ -CO ₂ -. Ab ₁ is a straight chain, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

V represents a group having a lactone structure. Specific examples thereof include groups having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).

Of the units represented by the general formula (AII), particularly preferred when the Ab is a single bond, the repeating unit having a lactone group includes the following repeating units. In embodiments, R x represents H, CH ₃ , CH ₂ OH, or CF ₃ . By selecting the optimum lactone group, the pattern profile and the density dependency are improved.

The resin (A) preferably contains a repeating unit having a lactone structure represented by the following general formula (3).

In the formula (3)

A represents a group represented by an ester bond (a group represented by -COO-) or -CONH-.

When there are a plurality of R ₀ , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

When Z is plural, each independently represents an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond.

R ₈ represents a monovalent organic group having a lactone structure.

n is a repetition number of the structure represented by -R ₀ -Z- in the repeating unit represented by the formula (3), and represents an integer of 1 to 5.

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and the cyclic alkylene group of 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 represented by R ₇ 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 ₇ may be substituted. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxyl group, a methoxy group, an ethoxy group, An alkoxy group such as a butoxy group or a benzyloxy group, or an acetoxy group such as an acetyl group or a propionyl group. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

As the preferable chain alkylene group in R ₀ , a straight chain alkylene group having 1 to 10 carbon atoms is preferable, and more preferred is a group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group and a propylene group . Preferable cyclic alkylene is cyclic alkylene having 1 to 20 carbon atoms, and examples thereof include cyclohexylene, cyclopentylene, norbornylene, adamantylene and the like. A chain alkylene group is more preferable for manifesting the effect of the present invention, and a methylene group is particularly preferable.

The substituent having a lactone structure represented by R ₈ is not limited as long as it has a lactone structure, and specific examples thereof include a lactone structure represented by the general formulas (LC1-1) to (LC1-17) LC1-4) is particularly preferable. In addition, n ₂ of the (LC1-1) ~ (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, and a lactone structure having a cyano group as a substituent Norbornene) is more preferable.

Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (3) 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, preferably a hydrogen atom, a methyl group, or a hydroxymethyl group or an acetoxymethyl group which is an alkyl group having a substituent.

The repeating unit having a lactone structure is more preferably a repeating unit represented by the following formula (3-1).

In the general formula (3-1)

R ₇ , A, R ₀ , Z, and n are as defined in the general formula (3).

R ₉ may be an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group when plural R _{9 s} are present, and two R _{9 s} may be combined to form a ring when there are a plurality of R _{9 s} .

X represents an alkylene group, an oxygen atom or a sulfur atom.

m is the number of the substituent, and represents an integer of 0 to 5; m is preferably 0 or 1.

The alkyl group represented by R ₉ 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. Examples of the ester group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the substituent include a halogen atom such as a hydroxy group, an alkoxy group such as a methoxy group or an ethoxy group, a cyano group or a fluorine atom.

R ₉ is more preferably a methyl group, a cyano group or an alkoxycarbonyl group, more preferably a cyano group.

Examples of the alkylene group of X include a methylene group and an ethylene group. X is preferably an oxygen atom or a methylene group, more preferably a methylene group.

When m = 1, R ₉ is preferably substituted at the α-position or β-position of the carbonyl group of the lactone, particularly preferably at the α-position.

Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (3-1) are shown, but the present invention is not limited thereto. In the formulas, R represents a hydrogen atom, an alkyl group which may have a substituent or a halogen atom, preferably a hydrogen atom, a methyl group, or a hydroxymethyl group or an acetoxymethyl group which is an alkyl group having a substituent.

The repeating unit having a lactone group usually has an optical isomer, but any of the optical isomers may be used.

The content of the repeating unit having a lactone group is preferably from 15 to 60 mol%, more preferably from 20 to 50 mol%, and still more preferably from 30 to 50 mol%, based on the total repeating units in the resin.

In order to enhance the effect of the present invention, it is also possible to use two or more kinds of lactone repeating units selected from the general formula (3) in combination. When used in combination, two or more lactone repeating units having n = 1 in the general formula (3) are preferably selected and used in combination. It is also preferable to use a lactone repeating unit in which Ab is a single bond in the general formula (AII) and a lactone repeating unit in which n is 1 in the general formula (3).

The resin (A) does not contain a repeating unit having a hydroxyl group or a cyano group (the repeating unit represented by the above-mentioned formula (3) or formula (AI) has a hydroxyl group or a cyano group. . This improves substrate adhesion and 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, a norbornyl group substituted with a cyano group, and the like. .

Examples of the repeating unit having an atomic group include repeating units represented by the following 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 each independently represent a hydrogen atom, a hydroxyl group or a cyano group. However, R ₂ c~R ₄ c at least one of represents a hydroxyl group or a cyano group. Preferably one or two of R ₂ c to R ₄ c is a hydroxyl group and the remainder is a hydrogen atom. In formula (VIIa), _two of R ₂ c to R ₄ c are more preferably a hydroxyl group and the remainder are hydrogen atoms.

The content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, and still more preferably 10 to 25 mol% based on the total repeating units in the resin (A) .

Specific examples of the repeating unit having a hydroxyl group or a cyano group are illustrated below, but the present invention is not limited thereto.

The resin used in the active radiation-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 bisulfonylimide group, and an aliphatic alcohol in which an alpha -position is substituted with an electron-withdrawing group (for example, a hexafluoroisopropanol group) Is more preferable. By including a repeating unit having an alkali-soluble group, the resolution in the contact hole application is increased. Examples of the repeating unit having an alkali-soluble group 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 derived from acrylic acid or methacrylic acid or a repeating unit in which an alkali- A polymerization initiator having an alkali-soluble group or a chain transfer agent is preferably used at the time of polymerization to introduce it to the end of the polymer chain, and the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. Particularly preferred is a repeating unit derived from acrylic acid or methacrylic acid.

The content of the repeating unit having an alkali-soluble group is preferably 0 to 20 mol%, more preferably 3 to 15 mol%, and still more preferably 5 to 10 mol% based on the total repeating units in the resin (A).

Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto. In embodiments, R x represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The resin (A) of the present invention preferably has an alicyclic hydrocarbon structure having no polar group and a repeating unit which does not exhibit acid decomposability. As a result, the elution of the low-molecular component from the film formed by the actinic ray-sensitive or radiation-sensitive resin composition into the immersion liquid can be reduced during liquid immersion lithography. As such a repeating unit, there may be mentioned a repeating unit represented by the general formula (4).

In the general formula (4), 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 of R ₅ 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 cyclic hydrocarbon group and a crosslinked 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 crosslinked cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

These alicyclic hydrocarbon groups may have a substituent. Preferable examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group. Preferable examples of the halogen atom include bromine, chlorine and fluorine, and preferable alkyl groups include methyl, ethyl, butyl and t-butyl. The alkyl group may further have a substituent. Examples of the substituent which may be further include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group.

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 examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms, and preferable examples of the substituted methyl group include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl and 2-methoxyethoxymethyl groups. Preferable examples of the substituted ethyl group include 1-ethoxyethyl Methyl-1-methoxyethyl, and preferred examples of the acyl group include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, An alkoxycarbonyl group having 1 to 4 carbon atoms, and the like.

The content of the repeating unit having an alicyclic hydrocarbon structure having no polar group and exhibiting no acid decomposability is preferably from 0 to 40 mol%, more preferably from 0 to 20 mol%, based on the total repeating units in the resin (A) .

Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and exhibiting no acid decomposability are illustrated below, but the present invention is not limited thereto. In the formula, Ra represents an _{H, CH 3, CH 2 OH} , or CF _3.

The resin used in the active radiation-sensitive or radiation-sensitive resin composition of the present invention may contain, in addition to the above repeating structural units, the dry etching resistance, the standard developer suitability, the substrate adhesion, the resist profile, And the like.

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

(1) the solubility in a coating solvent, (2) the film-forming property (glass transition point), (3) the ability to form a film, ) Alkali developability, (4) film reduction (selectable for salinity, alkali soluble group), (5) adhesion of the unexposed portion to the substrate, and (6) dry etching resistance.

Examples of such monomers include compounds having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like .

In addition, an addition-polymerizable unsaturated compound capable of copolymerizing with the monomer corresponding to the various repeating structural units may be copolymerized.

In the resin (A) used in the active radiation-sensitive or radiation-sensitive resin composition of the present invention, the molar ratio of each repeating structural unit is preferably in the range of from 0.01 to 10 parts by weight, It is appropriately set in order to control the general required performance such as resolution, heat resistance, sensitivity, and the like.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is used for ArF exposure, the resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention from the viewpoint of transparency to ArF light, .

From the viewpoint of compatibility with the hydrophobic resin (C) to be described later, it is preferable that the resin (A) does not contain a fluorine atom and a silicon atom.

As the resin (A) used in the active radiation-sensitive or radiation-sensitive resin composition of the present invention, all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, all of the repeating units are composed of methacrylate repeating units and acrylate repeating units Can be used, but it is preferable that the acrylate-based repeating unit is 50 mol% or less of the total repeating units.

(Meth) acrylate-based repeating unit having an acid-decomposable group and 20 to 50 mol% of a (meth) acrylate-based repeating unit having a lactone group, an alicyclic hydrocarbon structure having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group (Meth) acrylate repeating unit in an amount of 5 to 30 mol%, and further containing 0 to 20 mol% of other (meth) acrylate repeating units.

The resin (A) of the present invention can be synthesized according to a conventional method (for example, radical polymerization). Examples of the general synthesis method include a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and heated to effect polymerization, a dropwise polymerization method in which a solution of a monomer species and an initiator is added dropwise over 1 to 10 hours to a heating solvent And a dropwise polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethylformamide, dimethyl Amide solvents such as acetamide, and solvents for dissolving the composition of the present invention such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone described later. More preferably, the polymerization is carried out by using the same solvent as the solvent used in the composition of the present invention. This makes it possible to suppress the generation of particles at the time of storage.

The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, polymerization is initiated using a commercially available radical initiator (azo-based initiator, peroxide, etc.). As the radical initiator, an azo-based initiator is preferable, and an azo-based initiator having an ester group, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis (2-methylpropionate). An initiator is added according to a desired amount or added in portions, and after completion of the reaction, the polymer is added to a solvent to recover a desired polymer by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50 mass%, preferably 10 to 30 mass%. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, and more preferably 60 ° C to 100 ° C.

The weight average molecular weight of the resin (A) of the present invention is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000, still more preferably from 3,000 to 15,000, particularly preferably from 3,000 to 15,000, in terms of polystyrene, 3,000 to 10,000. By setting the weight average molecular weight within the above range, improvement in heat resistance, prevention of deterioration of dry etching resistance, deterioration of developability and deterioration of film formability due to increase in viscosity can be prevented.

The dispersion degree (molecular weight distribution) is usually from 1 to 3, preferably from 1 to 2.6, more preferably from 1 to 2, and particularly preferably from 1.4 to 2.0. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the sidewall of the resist pattern is smooth and the roughness is excellent.

The blending amount of the resin (A) in the composition of the present invention sensitive active ray-sensitive or radiation-sensitive resin composition is preferably 50 to 80 mass%, more preferably 60 to 80 mass%, of the total solid content.

The resin (A) of the present invention may be used singly or in combination.

[3] A resin composition comprising at least one of a fluorine atom and a silicon atom, and a resin having a polarity-converting group decomposed by the action of an alkali developer to increase the solubility in an alkali developer

The active ray or radiation sensitive resin composition of the present invention contains a resin (C) containing a repeating unit (c) having at least one polarity converting group and at least any one of a fluorine atom and a silicon atom. The resin (C) has hydrophobicity, but the addition of the resin (C) is particularly preferable from the viewpoint of reduction of development defects.

Here, the polarity converter is a group which is decomposed by the action of an alkali developing solution and whose solubility in an alkali developer is increased. 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 (-OCO-), a carbonate ester group (-OC (O) O-), a sulfuric acid ester group (-OSO ₂ O-), and a sulfonic acid ester group (-SO ₂ O-).

The ester group directly bonded to the main chain of the repeating unit such as an acrylate or the like is not included in the polarity converter of the present invention because the ester group is decomposed by the action of an alkaline developer and the solubility of the alkenyl developer is increased .

As the repeating unit (c), there may be mentioned, for example, a repeating unit represented by the formula (K0).

In the formulas, 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 converter.

The ester group directly bonded to the main chain of the repeating unit represented by the general formula (K0) is not included in the polarity converting unit in the present invention as described above.

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

In the general formula (KA-1) or (KB-1), X represents 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-, a carbonate ester group: -OC (O) O-, a sulfuric acid ester group: -OSO ₂ O-, and a sulfonic acid ester group: -SO ₂ O-.

Y ¹ and Y ^{2, which} may be the same or different, each represent an electron-withdrawing group.

The repeating unit (c) has a preferred polarity converter by having a group having a partial structure represented by the general formula (KA-1) or (KB-1), but the partial structure represented by the general formula (KA- When the partial structure does not have a binding hand, as in the case of the partial structure represented by (KB-1) when Y ¹ and Y ² are unity, the group having the partial structure may have an arbitrary Is a group having at least one hydrogen atom excluding at least one hydrogen atom. The partial structure represented by the general formula (KA-1) or (KB-1) is connected 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 forming a ring structure together 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. And more preferably a carboxylic acid ester group.

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

When there are a plurality of Z _ka1 , each 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.

Z _ka1 may be connected to form a ring. Examples of the ring formed by connecting Z _ka1 to each other include a cycloalkyl ring and a heterocycle (cyclic ether ring, lactone ring, etc.).

nka represents an integer of 0 to 10; Preferably an integer of 0 to 8, more preferably an integer of 0 to 5, still 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 alkyl group or a cycloalkyl group, that is, an alkyl ether group. The electronic recruitment group is synonymous with the 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 either straight chain or branched. The straight-chain alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include a methyl group, ethyl group, n-propyl group, n-butyl group, sec- Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decanyl group. The branched alkyl group preferably has 3 to 30 carbon atoms and more preferably 3 to 20 carbon atoms, and examples thereof include i-propyl, i-butyl, t-butyl, i- -Hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group and t-decanoyl group. It is preferably 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl.

The cycloalkyl group as Z _ka1 may have a substituent, may be a single ring, may be polycyclic, or may be a polycyclic. For example, the cycloalkyl group may have a crosslinked structure. The monocyclic group 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 group include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include an adamantyl group, a norbornyl group, an isoboronyl group, A dicyclopentyl group, an? -Pinel group, a tricyclodecanyl group, a tetracyclododecyl group, and an ornistannyl group, or the following structures. Further, a part of the carbon atoms in the cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.

Preferable 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 sidolyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cyclodecanyl group, and a cyclododecanyl group. More preferably an adamantyl group, a decalin group, a norbornyl group, a sidolyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group or a tricyclodecanyl group.

Examples of the substituent of the alicyclic structure 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, more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. The alkoxy group is preferably one 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 which the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms) and the like.

Examples of the substituent which the group may have include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, Alkoxy groups such as a 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, phenethyl group, An acyl group such as an aralkyl group such as an aralkyloxy group, a formyl group, an acetyl group, a butyryl group, a benzoyl group, a cyanamyl group and a valeryl group, an acyloxy group such as a butyryloxy group, Alkenyloxy groups such as phenyloxy group, allyloxy group and butenyloxy group, aryloxy groups such as aryl group and phenoxy group, aryloxycarbonyl groups such as benzoyloxy group and the like.

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 is preferably a 5- to 7-membered ring lactone ring.

Further, as in the following (KA-1-1) to (KA-1-17), a cyclic structure having a bicyclo structure and a spiro structure in a 5- to 7-membered ring lactone ring as a partial structure represented by the general formula (KA- It is preferable that other ring structures are coaxially formed.

Examples of the peripheral ring structure to which the ring structure represented by the general formula (KA-1) may be bonded include those represented by the following formulas (KA-1-1) to (KA-1-17) I can say that.

As the 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. (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6) , (KA-1-17).

The structure containing the lactone ring structure may or may not have a substituent. Preferred examples of the substituent include the same substituent which the ring structure represented by the general formula (KA-1) may have.

The optically active substance may be present in the lactone structure, but any optically active substance may be used. Further, one kind of optically active substance may be used singly or a plurality of optically active substances may be used in combination. When one kind of optically active substance is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more, and most preferably 98 or more.

X of the formula (KB-1) is preferably a carboxylic acid ester group (-COO-).

Y ¹ and Y ² in the general 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 bonding hand directly connected to (KA-1) or a bonding hand directly connected to X in (KB-1).

In formula (EW)

n _ew is the number of repeating _units represented by -C (R _ew1 ) (R _ew2 ) - and represents an integer of 0 or 1. When n _ew is 0, it indicates a single bond, and indicates that Y _ew1 is directly bonded.

_Ew1 Y is a halogen atom, a cyano group, a nitrile group, a nitro group, -C (R _f1), (R _f2) halo (cyclo) alkyl group, a haloaryl group, an oxy group represented by -R _f3, carbonyl group, sulfonyl group, a sulfinyl And a combination thereof, and the electron-withdrawing group may be, for example, the following structure. The "halo (cyclo) alkyl group" refers to an alkyl group and a cycloalkyl group at least partially halogenated. R _ew3 and R _ew4 each independently represent an arbitrary structure. R _ew3 and R _ew4 in any structure have electron _attractions and may be connected to the main chain of the resin, preferably alkyl groups, cycloalkyl groups, and fluorinated alkyl groups.

When Y _ew1 is a group having a _valence of 2 or more, the remaining bonding hands form a bond with any atom or substituent. At least any one of Y _ew1 , R _ew1 and R _ew2 may be connected to the main chain of the resin (C) through a new substituent.

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

R _ew1 and R _ew2 each independently represent an arbitrary substituent and represents, 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 form a ring.

Wherein 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, more preferably a fluorine atom or a tri 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 connected to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. It is more preferable that R _f2 represents the same group as R _f1 or forms a ring in connection with R _f3 .

R _f1 to R _f3 may form a ring, and examples of the ring to be formed include (halo) cycloalkyl ring and (halo) aryl ring.

Examples of the (halo) alkyl group in R _f1 to R _f3 include an alkyl group in Z _ka1 described above and a structure in which the alkyl group is halogenated.

R _{f1 f3} ~R in, or R _f2 and R _f3 is in a ring form by connecting (per) halo-cycloalkyl and (per) halo-aryl group includes, for example, a cycloalkyl in the above-described Z _ka1 A fluoroalkyl group represented by -C _(n) F _(2n-2) H, and a perfluoroaryl group represented by -C _(n) F _(n-1) . Here, the carbon number n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

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

A plurality of partial structures represented by the general formula (KA-1) and a plurality of partial structures represented by the general formula (KB-1) or a partial structure represented by the general formula (KA-1) And may have both partial structures of the general formula (KB-1).

A 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) It is possible.

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 unit on one side chain, the repeating unit having a polar group and having no fluorine atom and silicon atom (c *), A repeating unit (c ") having a polarity transducer on one side chain and having at least either a fluorine atom or a silicon atom on the side chain other than the side chain in the same repeating unit may be used, It is more preferable to have the repeating unit (c ') as the repeating unit (c).

When the resin (C) has the repeating unit (c *), it is preferably a copolymer with a repeating unit having at least any one of a fluorine atom and a silicon atom (a repeating unit (c1) described later). The side chain having a polarity converting group in the repeating unit (c ") and the side chain having at least any one of a fluorine atom and a silicon atom bonded to the same carbon atom in the main chain, that is, a positional relationship In the formulas, B1 represents a partial structure having a polarity converting group, and B2 represents a partial structure having at least any one of a fluorine atom and a silicon atom.

In the repeating unit (c *) and the repeating unit (c "), it is more preferable that the polarity converter is a partial structure represented by -COO- in the structure represented by the general formula (KA-1).

The polarity transducer is decomposed by the action of the alkali developing solution to perform the polarity conversion, whereby the receding contact angle of the resin composition film after the alkaline development with water can be lowered.

The receding contact angle of the resin composition film after alkali development with water is preferably not more than 50 deg., More preferably not more than 40 deg., More preferably not more than 50 deg. At the temperature during exposure, usually at room temperature 23 +/- 3 deg. 35 DEG or less, and most preferably 30 DEG or less.

The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface retreats, and it is generally known that it is useful when simulating the ease of movement of a droplet in a dynamic state. It can be simply defined as the contact angle when the liquid droplet ejected from the tip of the needle is ejected onto the substrate and then the interface of the liquid droplet is retracted when the droplet is again sucked by the needle. The contact angle can be measured using a measuring method of the contact angle.

The hydrolysis rate of the resin (C) to the alkali developing solution is preferably 0.001 nm / sec or more, more preferably 0.01 nm / sec or more, further preferably 0.1 nm / sec or more, most preferably 1 nm / sec or more Do.

The hydrolysis rate of the resin (C) to the alkali developing solution was decreased with respect to the film thickness when the resin film was formed only of the resin (C) with respect to TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass% Speed.

The resin (C) of the present invention is preferably a resin (C1) containing a repeating unit (c) having at least two polarity-converting groups and having at least any one of a fluorine atom and a silicon atom.

When the repeating unit (c) has at least two polarity transducers, it is preferable to have a group having a partial structure having two polarity transducers represented by the following general formula (KY-1). When the structure represented by the general formula (KY-1) does not have a bonding hand, it is a group having a monovalent or more group excluding at least one arbitrary hydrogen atom in the structure.

In the general formula (KY-1)

R _ky1 and R _ky4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an amide group or an aryl group. Alternatively, R _ky1 and R _ky4 may combine with the same atom to form a double bond. For example, R _ky1 and R _ky4 may combine with the same oxygen atom to form a part (= O) of a carbonyl group.

R _ky2 and R _ky3 are each independently an electron-withdrawing group, or R _ky1 and R _ky2 are connected to form a lactone ring, and R _ky3 is an electron- _accepting group. As the lactone ring to be formed, the structures of (KA-1-1) to (KA-1-17) are preferable. Examples of the electron-attracting group include the same groups as Y ¹ and Y ^{2 in the} above formula (KB-1), preferably a halogen atom or a group represented by -C (R _f1 ) (R _f2 ) -R _f3 Halo (cyclo) alkyl group or haloaryl group. Preferably, R _ky3 is a halogen atom, or a halo (cyclo) alkyl group or a haloaryl group represented by -C (R _f1 ) (R _f2 ) -R _f3 , and R _ky2 is linked with R _ky1 to form a lactone ring , And an electron-withdrawing group having no halogen atom.

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

R _ky1 and R _ky4 are specifically the same groups as Z _ka1 in the formula (KA-1).

As the lactone ring formed by connecting R _ky1 and R _ky2 , the structures of (KA-1-1) to (KA-1-17) are preferable. Examples of the electron-attracting group include the same groups as 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). The structure represented by the general formula (KY-2) is a group having a monovalent or higher group excluding at least one arbitrary hydrogen atom in the above structure.

Among the formula (KY-2)

R _ky6 ~R _ky10 are independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, carbonyloxy group, oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an amide group, or an aryl, respectively.

R _ky6 ~R _ky10 is to two or more connected to each other may form a monocyclic or polycyclic structure.

R _ky5 represents an electron- _attracting group. Examples of the electron-attracting group are the same as those in Y ¹ and Y ² , preferably a halogen atom, or a halo (cyclo) alkyl group represented by -C (R _f1 ) (R _f2 ) -R _f3 or halo Lt; / RTI >

R _ky5 ~R _ky10 may include groups, such as Z _ka1 Specifically, in the formula (KA-1).

It is more preferable that the structure represented by the formula (KY-2) is a partial structure represented by the following formula (KY-3).

Among the formula (KY-3)

Z _ka1 and nka are the same as in the above general formula (KA-1). R _{ky5 agrees} with the above formula (KY-2).

L _ky represents an alkylene group, an oxygen atom or a sulfur atom. _Examples of the alkylene group of L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, 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 and addition condensation, but is preferably a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Examples of the repeating unit include an acrylate-based repeating unit (including a group having a substituent at the? -Position and? -Position), a styrene-based repeating unit (including a group having a substituent at? And repeating units of maleic acid derivatives (maleic anhydride or derivatives thereof, maleimide and the like). Examples of the repeating unit include an acrylate-based repeating unit, a styrene-based repeating unit, a vinyl ether-based repeating unit, a norbornene- More preferably an acrylate-based repeat unit, a vinyl ether-based repeat unit or a norbornene-based repeat unit, and most preferably an acrylate-based repeat unit.

The repeating unit (c) may be a repeating unit having a partial structure shown below.

In the general formula (cc)

Z ₁ each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and preferably represents an ester bond.

Z ₂ each independently represents a straight or cyclic alkylene group, preferably an alkylene group having 1 or 2 carbon atoms or a cycloalkylene group having 5 to 10 carbon atoms.

Ta each independently represents 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 [electron-withdrawing groups (Y ¹ and Y ²⁾ And is preferably an alkyl group, a cycloalkyl group, or an electron-withdrawing group, and more preferably an electron-withdrawing group. When there are a plurality of Ta, the Ta may combine to form a ring.

L ₀ represents a single bond or an (m + 1) -valent hydrocarbon group (preferably 20 carbon atoms or less), preferably a single bond. The single bond as L ₀ is when m is 1. The m + 1 -valent hydrocarbon group as L _{0 represents} , for example, an (m + 1) -valent hydrocarbon group excluding m-1 arbitrary hydrogen atoms from an alkylene group, a cycloalkylene group, a phenylene group or a combination thereof. When k is 2, two L _{0 s} may combine to form a ring.

L each independently represents a carbonyl group, a carbonyloxy group or an ether group.

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 [the electron-withdrawing group as Y ¹ and Y ^{2 in} the general formula (KB- .

* Represents a bond of the resin to the main chain or side chain. That is, the partial structure represented by the formula (cc) may be directly bonded to the main chain, or the partial structure represented by the formula (cc) may be bonded to the side chain of the resin. In addition, a bonding hand to a main chain is a binding hand of a reactor existing in a bond constituting a main chain, and a bonding hand to a side chain is a bonding hand of a reactor existing in a bond other than a bond constituting the main chain.

m represents an integer of 0 to 28, preferably an integer of 1 to 3, and more preferably 1.

k represents an integer of 0 to 2, preferably 1;

q represents an integer of 0 to 5, preferably 0 to 2;

r represents an integer of 0 to 5;

Further, -L ₀ - (Ta) m may be substituted for - (L) r -Tc.

(Fluorine atom) at the end of the ternary ligand and a fluorine atom on the side chain other than the side chain on the side of the tonicity side in the same repeating unit (repeating unit (c)).

As a more specific structure of the repeating unit (c), a repeating unit having a partial structure shown below is preferable.

In the general formula (ca-2) and the general formula (cb-2)

Z ₁ , Z ₂ , Tc, Ta, L, q and r are the same as those in the general formula (cc).

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 fanny [electron withdrawing as Y ¹ and Y ² in the general formula (KB-1) Sex and consent].

* Represents a bond of the resin to the main chain or side chain. That is, the partial structure represented by the formula (ca-2) or (cb-2) may be directly bonded to the main chain or the partial structure represented by the formula (ca-2) May be combined.

m represents an integer of 1 to 28, preferably an integer of 1 to 3, and more preferably 1.

n represents an integer of 0 to 11, preferably an integer of 0 to 5, more preferably 1 or 2.

p represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 1 or 2.

In the general formula (2)

R ₂ represents a straight chain or cyclic alkylene group, and when there are plural groups, they may be the same or different.

R ₃ represents a linear, branched or cyclic hydrocarbon group in which some or all of the hydrogen atoms on the constituent carbon atoms are substituted with fluorine atoms.

R ₄ represents a group represented by 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 RC (= O) - or RC And R represents an alkyl group or a cycloalkyl group). When there are a plurality of R ₄ , 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 plural are present, they may be the same or different.

* Represents the bonding hands of the resin to the main chain.

n represents a repetition number and represents an integer of 0 to 5;

m is the number of the substituent, and represents an integer of 0 to 7;

The structure of -R ₂ -Z- is preferably a structure represented by - (CH ₂ ) _l -COO- (1 represents an integer of 1 to 5).

Specific examples of the repeating unit (c) having a polarity converting group are shown, but are not limited thereto.

Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

The resin (C) contains a repeating unit having at least any one of a fluorine atom and a silicon atom.

As a result, the receding contact angle of the surface of the resist film with respect to the water when the resin (C) is uniformalized in the surface layer of the actinic ray or radiation-sensitive resin film and water is the actinic ray or radiation- It is possible to improve the liquid immersion water follow-up property.

The receding contact angle of the actinic ray or radiation sensitive resin film is preferably 60 ° to 90 °, more preferably 65 ° or more, more preferably 60 ° to 90 ° at a temperature during exposure, usually at room temperature of 23 ± 3 ° C and humidity of 45 ± 5% Is at least 70 DEG, particularly preferably at least 75 DEG.

Unlike the surfactant, the resin (C) is not necessarily required to have a hydrophilic group in the molecule, and may not contribute to uniformly mixing a polar / non-polar substance, unlike the surfactant.

In the liquid immersion lithography process, since the immersion liquid needs to move on the wafer in order to cope with the movement in which the exposure head scans the wafer at high speed to form the exposure pattern, the contact angle of the immersion liquid with respect to the resist film in the dynamic state And it is required to have a capability of harvesting a high-speed scan of the exposure head without remaining a droplet.

Having at least one of a fluorine atom and a silicon atom as the resin (C) improves the hydrophobicity (water followability) of the resist surface and reduces the development residue (scum).

It is preferable that the partial structure of the repeating unit having a fluorine atom is 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 straight chain or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another 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 in an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may have another substituent.

The alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom is preferably a group represented by any one of the following general formulas (F2) to (F4) But is not limited thereto.

Among the general formulas (F2) to (F4)

Each of R ₅₇ to R ₆₈ independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight chain 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 is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom 1 to 4 carbon atoms).

It is preferable that all of R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably a fluoroalkyl group (preferably having 1 to 4 carbon atoms) and 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 a trifluoromethyl group, a pentafluoropropyl group, a pentafluoroethyl group, a heptafluorobutyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, (2-methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluoroox A perfluoro (trimethyl) hexyl group, a 2,2,3,3-tetrafluorocyclobutyl group, and a perfluorocyclohexyl group. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable , A hexafluoroisopropyl group, and a heptafluoroisopropyl group are more preferable.

Specific examples of the group represented by formula (F4), for example, _{-C (CF 3) 2 OH,} -C (C 2 F 5) 2 OH, -C (CF 3) (CH 3) OH, -CH (CF ₃₎ there may be mentioned, such as OH, -C (CF _{3) 2} OH is preferred.

The fluorine-containing partial structure may be a direct bond or may be a single bond or two bonds 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, May be combined through a combination of the above groups.

As the repeating unit having a fluorine atom, those shown below are suitably exemplified.

In the formulas, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom, an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and an alkyl group having a substituent, particularly a fluorinated alkyl group) .

W _{3 to} W ₆ each independently represent an organic group containing at least one fluorine atom. Specifically, the atomic groups of the above-mentioned (F2) to (F4) can be mentioned.

In addition to these, resins having the units shown below are also applicable.

In the formulas, R ₄ to R ₇ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and an alkyl group having a substituent, particularly a fluorinated alkyl group) . Provided that 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. Specifically, the atomic groups of the above-mentioned (F2) to (F4) can be mentioned.

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) - , R represents a hydrogen atom or an alkyl group), -NHSO ₂ -, or a bivalent linking group obtained by combining a plurality of these groups.

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

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

In the general formulas (CS-1) to (CS-3)

Each of R ₁₂ to R ₂₆ 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 to} L ₅ represent a single bond or a divalent linking group. Examples of the divalent linking group include a single bond or a combination of two or more groups 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.

n represents an integer of 1 to 5;

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

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

The content of the repeating unit (c '') is preferably from 10 to 100 mol%, more preferably from 20 to 100 mol%, still more preferably from 30 to 100 mol% Is from 40 to 100 mol%.

The fluorine atom or the silicon atom in the resin (C) may be contained in the main chain of the resin or may be substituted in the side chain. The resin (C) may further contain a recurring unit (c1) having at least any one of a fluorine atom and a silicon atom different from the recurring units (c ') and (c ").

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

Examples of the partial structure having a fluorine atom in the repeating unit (c1) include those exemplified above, and those represented by the above general formulas (F2) to (F4) are exemplified.

Examples of the partial structure having a silicon atom in the recurring unit (c1) include the same groups as described above, and groups represented by the general formulas (CS-1) to (CS-3) are exemplified.

The repeating unit (c1) is preferably a (meth) acrylate-based repeating unit.

Specific examples of the repeating unit (c1) are illustrated below, but the present invention is not limited thereto. In the specific examples, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ , and X ₂ represents -F or -CF ₃ .

The resin (C) may have at least one group selected from the group of (x) and (z) below.

(x) an alkali-soluble group,

(z) a group which is decomposed by the action of an acid.

Examples of the alkali-soluble group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (Alkylcarbonyl) imide group, a bis (alkylcarbonyl) methylene group, a bis (alkylcarbonyl) imide group, A methylene group, and a tris (alkylsulfonyl) methylene group.

Preferred examples of the alkali-soluble group include a fluorinated alcohol group (preferably, hexafluoroisopropanol), a sulfonimide group and a bis (carbonyl) methylene group.

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 an alkali-soluble group is bonded to the main chain And a polymerization initiator having an alkali-soluble group and a chain transfer agent may be used at the time of polymerization to introduce them to the end of the polymer chain.

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%, and still more preferably from 5 to 30 mol% based on the total repeating units in the resin (C) ㏖%.

Specific examples of the repeating unit having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto. In embodiments, R x represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The repeating unit having a group (z) decomposed by the action of an acid in the resin (C) includes the same repeating unit having an acid-decomposable group exemplified in the resin of the component (A) described later. The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group. More preferably a tertiary alkyl ester group.

The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following 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 and an acyl group having 5 or less carbon atoms, 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 chain or branched chain) 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 of 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 a single bond or -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.

As the alkyl group of Rx _{1 to} Rx ₃ , 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-

As the cycloalkyl group represented by R x _{1 to} R x ₃ , a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group is preferable .

Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group A polycyclic cycloalkyl group is preferred.

Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are combined to form the above-mentioned cycloalkyl group.

Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms) And the number of carbon atoms is preferably 8 or less.

The content of the repeating unit having a group (z) decomposed by the action of an acid in the resin (C) is preferably from 1 to 80 mol%, more preferably from 10 to 80 mol% based on the total repeating units in the resin (C) To 80 mol%, and more preferably 20 to 60 mol%. (z) a group which is decomposed by the action of an acid, whereby the LWR can be improved.

The resin (C) may further contain other repeating units. Preferred examples of other repeating units include the following.

(cy1) a repeating unit which has a fluorine atom and / or a silicon atom, is stable to an acid, and is poorly 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 is poorly 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 (x) and (z).

(cy4) a repeating unit having no fluorine atom or silicon atom and having a polar group other than the above-mentioned (x) and (z).

(cy1) and (cy2) refers to an alkali-soluble group or a group capable of generating an alkali-soluble group by the action of an acid or an alkali developer (for example, (For example, an acid-decomposable group or a polarity-converting group).

It is preferable that the repeating units (cy1) and (cy2) have an alicyclic hydrocarbon structure having no polar group.

Preferred examples of the repeating units (cy1) to (cy4) are shown below.

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

In the general formula (CIII)

R _c31 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. In the formulas, 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.

The alkyl group represented by R _c32 in formula (CIII) is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group is preferably a cycloalkyl group having from 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 from 3 to 20 carbon atoms.

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

The bivalent linking group of L _c3 is preferably an ester group, an alkylene group (preferably having 1 to 5 carbon atoms), 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 the 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. In the formulas, 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 of 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 cyclic hydrocarbon group and a crosslinked 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 crosslinked cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

These alicyclic hydrocarbon groups may have a substituent, and preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group. Preferable examples of the halogen atom include bromine, chlorine and fluorine, and preferable alkyl groups include methyl, ethyl, butyl and t-butyl. The alkyl group may further have a substituent. Examples of the substituent which may be further include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group.

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 examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms, and preferable examples of the substituted methyl group include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl and 2-methoxyethoxymethyl groups. Preferable examples of the substituted ethyl group include 1-ethoxyethyl Methyl-1-methoxyethyl, and preferred examples of the acyl group include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, An alkoxycarbonyl group having 1 to 4 carbon atoms, and the like.

In the general formula (C5), _Rc6 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 of 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 from 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 from 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, a 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, and a trifluoromethyl group and a t-butyl group are particularly preferable.

(cy1) and (cy2) is preferably a repeating unit represented by the following formula (CII-AB).

Of 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 'includes two bonded carbon atoms (C-C) and represents an atomic group for forming an alicyclic structure.

Further, it is more preferable that the above general formula (CII-AB) is the following general formula (CII-AB1) or general formula (CII-AB2).

In the formula (CII-AB1) and formula _{(CII-AB2), Rc 13} '~Rc 16' represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group independently.

At least two of Rc ₁₃ 'to Rc ₁₆ ' may combine to form a ring.

n represents 0 or 1;

Specific examples of (cy1) and (cy2) are set forth below, but the present invention is not limited thereto. In the formula, Ra represents an _{H, CH 3, CH 2 OH} , CF 3 or CN.

(cy3) and (cy4) is preferably a repeating unit having a hydroxyl group or a cyano group as a polar group. This improves the 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, a norbornyl group substituted with a cyano group, etc. .

Examples of the repeating unit having an 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 represent a hydrogen atom, a hydroxyl group or a cyano group. However, R ₂ c~R ₄ c at least one of represents a hydroxyl group or a cyano group. Preferably one or two of hydroxyl groups in R ₂ c~R ₄ c, and the remaining is a hydrogen atom. In the formula (CAIIa), _two of R ₂ c to R ₄ c are more preferably a hydroxyl group and the remainder are hydrogen atoms.

Specific examples of the repeating units represented by (cy3) and (cy4) are illustrated below, but the present invention is not limited thereto.

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

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

When the resin (C) has a fluorine atom, the content of the fluorine atom is preferably 5 to 80 mass%, more preferably 10 to 80 mass%, based on the molecular weight of the resin (C). The repeating unit containing a fluorine atom is preferably from 10 to 100 mass%, more preferably from 30 to 100 mass%, based on the total repeating units in the resin (C).

When the resin (C) has a silicon atom, the content of the silicon atom is preferably 2 to 50 mass%, more preferably 2 to 30 mass%, based on the molecular weight of the resin (C). The repeating unit containing a silicon atom is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total repeating units of the resin (C).

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 active ray or radiation-sensitive resin composition can be appropriately adjusted so that the receding contact angle of the actinic ray or radiation-sensitive resin film falls within the above range. However, Is preferably 0.01 to 10 mass%, more preferably 0.1 to 9 mass%, and still more preferably 0.5 to 8 mass%, based on the solid content.

It is natural that the resin (C) has few impurities such as metal, like the resin of the component (A) described later, and the residual monomer or oligomer component is preferably 0 to 10 mass%, more preferably 0 to 5 mass %, More preferably 0 to 1% by mass. As a result, a resist free from foreign matter in the liquid and a change with time such as sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersion degree) is preferably in the range of from 1 to 3, more preferably from 1 to 2, and still more preferably from 1 to 3, in view of the resolution, the resist shape, the side wall of the resist pattern, , And most preferably in the range of 1 to 1.5.

Resin (C) may be commercially available or may be synthesized according to the conventional method (for example, radical polymerization). Examples of the general synthesis method include a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and heated to effect polymerization, a dropwise polymerization method in which a solution of a monomer species and an initiator is added dropwise over a period of 1 to 10 hours to a heating solvent And a dropwise polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethylformamide, dimethyl Amide solvents such as acetamide, and solvents for dissolving the composition of the present invention such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and cyclohexanone described later. More preferably, the polymerization is carried out by using the same solvent as that used for the active ray or radiation sensitive resin composition of the present invention. This makes it possible to suppress the generation of particles at the time of storage.

The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, polymerization is initiated using a commercially available radical initiator (azo-based initiator, peroxide, etc.). As the radical initiator, an azo-based initiator is preferable, and an azo-based initiator having an ester group, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis (2-methylpropionate). The concentration of the reaction is usually 5 to 50 mass%, preferably 30 to 50 mass%. The reaction temperature is usually from 10 to 150 캜, preferably from 30 to 120 캜, more preferably from 60 to 100 캜.

After completion of the reaction, the reaction mixture is allowed to stand at room temperature, cooled, and purified. Purification can be carried out by a liquid-liquid extraction method in which residual monomer or oligomer component is removed by combining water or an appropriate solvent, a purification method in a solution state such as ultrafiltration in which only a substance having a specific molecular weight or less is extracted and removed, Such as a reprecipitation method in which residual monomer or the like is removed by solidifying it in a poor solvent or a solid state purification method such as washing a resin slurry filtered and sorted with a poor solvent can be applied. For example, the resin is precipitated as a solid by contacting a poorly soluble or insoluble solvent (poor solvent) at a volume of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.

The solvent (precipitation or reprecipitation solvent) to be used in the precipitation or reprecipitation operation from the polymer solution may be any of the poor solvents of the polymer. The solvent may be a hydrocarbon, a halogenated hydrocarbon, a nitro compound, an ether, a ketone, Carbonates, alcohols, carboxylic acids, water, mixed solvents containing these solvents, and the like. Among them, as a solvent for precipitation or reprecipitation, at least an alcohol (particularly, methanol or the like) or a solvent containing water is preferable.

The amount of the precipitation or reprecipitation solvent to be used may be appropriately selected in consideration of the efficiency and the yield. Generally, 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass, 300 to 1000 parts by mass.

The temperature at the time of precipitation or reprecipitation can be suitably selected in consideration of efficiency and operability, and is usually about 0 to 50 캜, preferably about room temperature (for example, about 20 to 35 캜). The precipitation or reprecipitation operation can be carried out by a known method such as a batch method or a continuous method using a mixing vessel such as a stirring vessel.

The precipitated or reprecipitated polymer is usually provided for public solid-liquid separation such as filtration and centrifugation, and is then dried and provided for use. The filtration is carried out using a solvent-resistant filter medium, preferably under pressure. The drying is carried out under normal pressure or reduced pressure (preferably under reduced pressure) at a temperature of about 30 to 100 占 폚, preferably about 30 to 50 占 폚.

Further, after the resin is once separated and separated, it may be dissolved again in a solvent, and the resin may be contacted with a hardly-sparing or insoluble solvent. That is, after completion of the radical polymerization reaction, the polymer is contacted with a poorly soluble or insoluble solvent to precipitate the resin (step a), and the resin is separated from the solution (step b) (Step c). Thereafter, a solvent in which the resin is sparingly soluble or insoluble is brought into contact with the resin solution A at a volume of 10 times or less (preferably 5 times or less the volume) of the resin solution A to precipitate the resin solids (Step d), and separating the precipitated resin (step e).

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

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 1-4]

The resin (C) may be used alone or in combination of two or more.

Further, it is preferable to use it in combination with a resin (CP) having at least any one of a fluorine atom and a silicon atom different from the resin (C).

(CP) a resin having at least any one of a fluorine atom and a silicon atom

The active ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a resin (CP) having at least one of a fluorine atom and a silicon atom, apart from the resin (C). The receding contact angle of the surface of the resist film with respect to water when the resin (C) and the resin (CP) are uniformalized in the surface layer of the film by containing the resin (C) and the resin (CP) It is possible to improve the liquid immersion harvesting property. The receding contact angle of the film is preferably 60 ° to 90 °, more preferably 70 ° or more. The content of the resin (CP) can be appropriately adjusted so that the receding contact angle of the film falls within the above range, but it is preferably 0.01 to 10% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, More preferably 0.01 to 5% by mass, still more preferably 0.01 to 4% by mass, and particularly preferably 0.01 to 3% by mass.

Unlike the surfactant, the resin (CP) is not necessarily required to have a hydrophilic group in the molecule and may not contribute to uniformly mixing the polar / non-polar substance, unlike the surfactant.

The fluorine atom or the silicon atom in the resin (CP) having at least any one of a fluorine atom and a silicon atom may be contained in the main chain of the resin or may be substituted in the 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 straight chain or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another 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 in an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may 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, groups represented by the general formulas (F2) to (F4) in the resin (C) The present invention is not limited to this.

In the present invention, the groups represented by the general formulas (F2) to (F4) are preferably contained in the (meth) acrylate-based repeating unit.

Specific examples of the repeating unit having a fluorine atom are shown below, but the present invention is not limited thereto.

In the 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 cyclic siloxane structure include groups represented by the general formulas (CS-1) to (CS-3) in the resin (C).

The resin (CP) may further have at least one group selected from the group of (x) and (z) below.

(x) an alkali-soluble group,

(z) a group which is decomposed by the action of an acid.

These groups specifically include groups similar to those in the above-mentioned resin (C).

The repeating unit having a group (z) decomposed by the action of an acid in the resin (CP) includes the same repeating unit having an acid-decomposable group exemplified in the resin of the component (A) described later. The content of the repeating unit having a group (z) decomposed by the action of an acid in the resin (CP) is preferably from 1 to 80 mol%, more preferably from 10 to 80 mol% based on the total repeating units in the resin (CP) To 80 mol%, and more preferably 20 to 60 mol%.

The resin (CP) may further have a repeating unit represented by the general formula (CIII) in the resin (C).

When the resin (CP) has a fluorine atom, the content of the fluorine atom is preferably 5 to 80 mass%, more preferably 10 to 80 mass%, based on the molecular weight of the resin (CP). The repeating unit containing a fluorine atom is preferably 10 to 100 mass%, more preferably 30 to 100 mass%, based on all repeating units in the resin (CP).

When the resin (CP) has a silicon atom, the content of the silicon atom is preferably 2 to 50 mass%, more preferably 2 to 30 mass%, based on the molecular weight of the resin (CP). The repeating unit containing a silicon atom is preferably 10 to 100 mass%, more preferably 20 to 100 mass%, based on the total repeating units of the resin (CP).

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.

It is natural that the resin (CP) has few impurities such as metal, like the resin of the component (A), and the residual monomer or oligomer component is preferably 0 to 10 mass%, more preferably 0 to 5 mass% More preferably from 0 to 1% by mass. Thereby, an actinic ray-sensitive or radiation-sensitive resin composition free from foreign matters in the liquid or change with time such as sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersion degree) is preferably in the range of from 1 to 3, more preferably from 1 to 2, and still more preferably from 1 to 3, in view of the resolution, the resist shape, the side wall of the resist pattern, , And most preferably in the range of 1 to 1.5.

Resin (CP) can be commercially available or can be synthesized according to the 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 any one of a fluorine atom and a silicon atom are shown below. In the following table, the molar ratio (corresponding to each repeating unit and the order from the left), the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of the repeating units in each resin are shown.

[Table 2]

(Liquid immersion medium) filled with a liquid (immersion medium) having a refractive index higher than that of air between the film and the lens at the time of irradiating the actinic ray or radiation to the film formed from the active radiation ray or radiation sensitive resin composition of the present invention You can do it. This makes it possible to improve the resolution. As the immersion medium to be used, any liquid having a refractive index higher than that of air can be used, but it is preferably pure water.

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

The liquid immersion liquid is transparent to the exposure wavelength and is preferably a liquid whose temperature coefficient of refractive index is as small as possible so as to minimize the deformation of the optical image projected onto the film. Particularly when the exposure light source is an ArF excimer laser (wavelength: 193 nm) In addition to the above-described point of view, it is preferable to use water in view of easiness of acquisition and ease of handling.

Further, a medium having a refractive index of 1.5 or more may be used in order to further improve the refractive index. The medium may be an aqueous solution or an organic solvent.

In the case of using water as an immersion liquid, an additive (a liquid) which can negatively affect the influence of the surface of the lens element on the optical coat is not dissolved in the resist film on the wafer in order to reduce the surface tension of water and increase the surface activity. ) May be added in a small proportion. As the additive, aliphatic alcohols having a refractive index almost equal to that of water are preferable, and specific examples thereof include methyl alcohol, ethyl alcohol and isopropyl alcohol. It is possible to obtain an advantage that the change in the refractive index as a whole of the liquid can be made very small even if the alcohol content in the water evaporates due to the addition of an alcohol having a refractive index almost equal to that of water. On the other hand, when an opaque material or a refractive index largely different from water is mixed with 193 nm light, distilled water is preferably used as the water to be used because it causes deformation of the optical image projected on the resist film. It is also possible to use pure water obtained by filtration through an ion exchange filter or the like.

The electrical resistance of water is preferably 18.3 MQcm or more, and the TOC (organic matter concentration) is preferably 20 ppb or less, and it is preferable that deaeration treatment is performed.

In addition, it is possible to improve the lithography performance by improving the refractive index of the immersion liquid. From this point of view, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

Between the membrane of the composition of the present invention and the immersion liquid, an immersion liquid refractory film (hereinafter also referred to as " top coat ") may be formed so as not to directly contact the film with the immersion liquid. The functions required for the topcoat are titration of the coating to the upper layer of the film, transparency to radiation, particularly 193 nm, and immersion insolubility. It is preferable that the topcoat is not mixed with the resist and is uniformly applied to the upper layer of the resist.

From the viewpoint of transparency at 193 nm, the topcoat is preferably a polymer that does not contain an aromatic in a large amount. Specifically, the topcoat is preferably a hydrocarbon polymer, an acrylic ester polymer, a polymethacrylic acid, a polyacrylic acid, a polyvinyl ether, Containing polymer. The above-mentioned hydrophobic resin (C) and resin (CP) are also preferable as a top coat. From the viewpoint that the optical lens is contaminated when the impurities are eluted from the topcoat with the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the topcoat is small.

When the top coat is peeled off, a developer may be used, or a separate peeling agent may be used. As the releasing agent, a solvent having less permeation into the film is preferable. From the viewpoint that the peeling step can be performed at the same time as the development processing step of the film, it is preferable that the peeling can be performed with an alkali developing solution. From the viewpoint of peeling with an alkaline developing solution, the topcoat is preferably acidic, but may be neutral or alkaline from the viewpoint of non-intermixing with the film.

When there is no difference in refractive index between the top coat and the immersion liquid, the resolution is improved. When water is used as the immersion liquid in the 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 bringing the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. Further, from the viewpoints of transparency and refractive index, a thin film is preferable.

It is preferred that the topcoat is not mixed with the membrane and does not mix with the immersion liquid. From this viewpoint, when the immersion liquid is water, the solvent used in the topcoat is preferably a medium which is hardly soluble in the solvent used in the composition of the present invention, and is also a water-insoluble medium. When the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

[Basic compound]

The composition of the present invention preferably contains a basic compound in order to reduce the change in performance due to aging from exposure to heating.

The basic compound is preferably a compound having a structure represented by the following formulas (A) to (E).

Among the general formulas (A) and (E)

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represents 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 6 to 20 carbon atoms) Wherein R ²⁰¹ and R ²⁰² may be bonded to 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.

The alkyl group having a substituent for the alkyl group is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.

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

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

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzoimidazole and the like. 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, 1,8- Cyclo [5,4,0] undeca-7-ene, and the like. 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 (T-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, . As the compound having an onium carboxylate structure, the anion portion of the compound having an onium hydroxide structure is a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, perfluoroalkylcarboxylate and the like . Examples of the compound having a trialkylamine structure include tri (n-butyl) amine, tri (n-octyl) amine and the like. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutyl aniline and N, N-dihexyl aniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris (methoxyethoxyethyl) amine and the like. Examples of the aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.

Preferred examples of the basic compound 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 may be a primary, secondary or tertiary amine compound, and is preferably an amine compound in which at least one alkyl group is bonded to a nitrogen atom. More preferably, the amine compound is a tertiary amine compound. (Preferably having from 3 to 20 carbon atoms) or an aryl group (preferably having from 6 to 12 carbon atoms) in addition to the alkyl group when the at least one alkyl group (preferably having from 1 to 20 carbon atoms) is bonded to the nitrogen atom Or may be bonded to a nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and is formed with an oxyalkylene group. The number of oxyalkylene groups in the molecule is at least 1, preferably from 3 to 9, more preferably from 4 to 6. Among oxyalkylene groups, an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group [-CH (CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-] is preferable, Oxyethylene group.

The ammonium salt compound may be a primary, secondary, tertiary or quaternary ammonium salt compound, and is preferably an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom. When the at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom, the ammonium salt compound may contain a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably 6 to 12 carbon atoms) Or may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and is formed with an oxyalkylene group. The number of oxyalkylene groups in the molecule is at least 1, preferably from 3 to 9, more preferably from 4 to 6. Among oxyalkylene groups, an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group [-CH (CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-] is preferable, Oxyethylene group. Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate. Among them, a halogen atom and a sulfonate are preferable. As the halogen atom, chloride, bromide and iodide are particularly preferable, and as the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkylsulfonate may have a substituent. Examples of the substituent include fluorine, chlorine, bromine, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkylsulfonate include methanesulfonate, ethanesulfonate, butanesulfonate, hexanesulfonate, octanesulfonate, benzylsulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutane Sulfonate and the like. The aryl group of the arylsulfonate includes a benzene ring, a naphthalene ring and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the straight chain or branched alkyl group and the cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group and an acyloxy group.

The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal on the opposite side to the nitrogen atom of the alkyl group of the amine compound or the ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic ester group, an aryl group, an aralkyl group, an acyloxy group, . The substitution position of the substituent may be any of 2-6 positions. The number of substituents may be in the range of 1 to 5.

It is preferable that at least one oxyalkylene group is present between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups in the molecule is at least 1, preferably from 3 to 9, more preferably from 4 to 6. Among oxyalkylene groups, an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group [-CH (CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-] is preferable, Oxyethylene group.

The sulfonic acid ester group in the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group may be any of an alkylsulfonic acid ester, a cycloalkyl group sulfonic acid ester and an arylsulfonic acid ester. In the case of an alkylsulfonic acid ester, 20, the cycloalkyl group in the case of the cycloalkyl sulfonic acid ester has 3 to 20 carbon atoms, and in the case of the aryl sulfonic acid ester, the aryl group preferably has 6 to 12 carbon atoms. The alkylsulfonic acid ester, the cycloalkylsulfonic acid ester and the arylsulfonic acid ester may have a substituent, and as the substituent, a halogen atom, cyano group, nitro group, carboxyl group, carboxylic acid ester group or sulfonate ester group is preferable.

And at least one oxyalkylene group is present between the sulfonate ester group and the nitrogen atom. The number of oxyalkylene groups in the molecule is at least 1, preferably from 3 to 9, more preferably from 4 to 6. Among oxyalkylene groups, an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group [-CH (CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-] is preferable, Oxyethylene group.

These basic compounds may be used alone or in combination of two or more.

The amount of the basic compound to be used is usually 0.001 to 10 mass%, preferably 0.01 to 5 mass%, based on the solid content of the composition of the present invention.

The ratio of the acid generator to the basic compound in the composition is preferably from 2.5 to 300 as the acid generator / basic compound (molar ratio). That is, the mole ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and from the viewpoint of suppressing the resolution lowering due to the thickness of the resist pattern with time after the post-exposure heat treatment, it is preferably 300 or less. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

[Surfactants]

The composition of the present invention preferably further contains a surfactant and may be any one of a fluorine-based and / or silicon-based surfactant (a fluorine-based surfactant, a silicon surfactant, and a surfactant having both fluorine and silicon atoms) It is more preferable to contain a paper phase.

When the composition of the present invention contains the above surfactant, it is possible to impart a resist pattern with good adhesion and development defects with good sensitivity and resolution at the time of using an exposure light source of 250 nm or less, particularly 220 nm or less.

Examples of the fluorine-based and / or silicon-based surfactants include those disclosed in Japanese Patent Application Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950 Japanese Patent Application Laid-Open Nos. 63-34540, 7-230165, 8-62834, 9-54432, 9-5988 Japanese Patent Application Laid-Open No. 2002-277862, U.S. Patent Nos. 5,405,720, 5360692, 5529881, 5296330, and 5436098 The surfactants described in JP-A-5576143, JP-A-5294511 and JP-A-5824451, and the following surfactants may be used as they are.

As commercially available surfactants that can be used, for example, there may be mentioned Faft EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Fluorad FC430, 431 and 4430 (manufactured by Sumitomo 3M Ltd.), Megafac F171 and F173 , F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink and Chemicals, Inc.), Surplon S-382, SC101, 102, 103, 104, 105, GF-300 and GF-150 (manufactured by Toagosei Chemical Industry Co., Ltd.) and SURFLON S-393 (manufactured by Seiyi Chemical Co., Ltd.) FGX-204G, FGX-204G, FGX-204G, FGX-204G, FGX220, 218G, 230G, 204D, 208D, 212D, 218D, and 222D (manufactured by Neos Co., Ltd.) and silicon-based surfactants. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

As the surfactant, in addition to the known ones as described above, fluoro (meth) acrylates introduced from a fluoroaliphatic compound produced by a telomerization method (also referred to as a teror method) or an oligomerization method (also referred to as an oligomer method) Surfactants using a polymer having an aliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable, Or may be block-copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group and a poly (oxybutylene) group. In addition, poly (oxyethylene, oxypropylene and oxyethylene blocks Or may be a unit having an alkylene chain having a different chain length in the chain length, such as a poly (oxyethylene / oxypropylene block). Further, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) may be a monomer having two or more different fluoroaliphatic groups, (Poly (oxyalkylene)) acrylate (or methacrylate) or the like may be copolymerized at the same time.

Examples of commercially available surfactants include Megapac F178, F-470, F-473, F-475, F-476 and F-472 [manufactured by Dainippon Ink Kagaku Kogyo Co., Ltd.]. In addition, copolymers of (meth) acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate (or methacrylate) having C ₆ F ₁₃ groups, acrylates having C ₃ F ₇ groups ) And copolymers of (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate).

In the present invention, surfactants other than fluorine-based and / or silicon-based surfactants may also be used. Specific examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonyl Polyoxyethylene alkylaryl ethers such as phenol ether and phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan Sorbitan fatty acid esters such as trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate Oleate, polyoxyethylene sorbitan tristearate Of polyoxyethylene, and the like sorbitan fatty acid non-ionic surfactants such as esters.

These surfactants may be used alone or in combination of several.

The amount of the surfactant to be used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, particularly preferably 0.0005 to 5% by mass, based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent) 1% by mass

[Carboxylic acid onium salt]

The composition of the present invention may contain a carboxylic acid onium salt. Examples of the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt. Particularly, as the carboxylic acid onium salt, iodonium salt and sulfonium salt are preferable. It is also preferable that the carboxylate residue of the onium carboxylate of the present invention does not contain an aromatic group or a carbon-carbon double bond. As a particularly preferable anion moiety, a linear, branched, monocyclic or polycyclic cyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. More preferably, an anion of a carboxylic acid in which a part or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. As a result, the transparency to light of 220 nm or less is ensured, the sensitivity and resolution are improved, the density dependency and the exposure margin are improved.

Examples of the anion of the fluorine-substituted carboxylic acid include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, , Perfluorocyclohexanecarboxylic acid, and an anion of 2,2-bistrifluoromethylpropionic acid.

These onium salts of carboxylic acid can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

The content of the onium carboxylate in the composition is generally 0.1 to 20 mass%, preferably 0.5 to 10 mass%, more preferably 1 to 7 mass%, based on the total solid content of the composition.

[Solubility inhibiting compound]

The composition of the present invention may contain a dissolution inhibiting compound having a molecular weight of 3,000 or less (hereinafter, also referred to as " dissolution inhibiting compound ") which is decomposed by the action of an acid to increase solubility in an alkali developing solution. As the dissolution inhibiting compound, an alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996) is preferable in order not to lower the permeability at 220 nm or less Do. Examples of the acid-decomposable group and the alicyclic structure include those described in the resin portion of the component (B).

When the composition of the present invention is exposed to a KrF excimer laser or irradiated with an electron beam, it is preferable to contain a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid decomposer. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.

The molecular weight of the dissolution inhibiting compound in the present invention is 3,000 or less, preferably 300 to 3,000, and more preferably 500 to 2,500.

The addition amount of the dissolution inhibiting compound is preferably from 3 to 50 mass%, more preferably from 5 to 40 mass%, based on the solid content of the composition of the present invention.

Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

[Other additives]

(For example, a phenol compound having a molecular weight of 1000 or less, an alicyclic group having a carboxyl group, or an aliphatic compound), etc., for accelerating the solubility in a dye, a plasticizer, a photosensitizer, a light absorber, Can be further contained.

Such phenol compounds having a molecular weight of 1,000 or less are described in, for example, Japanese Patent Application Laid-Open Nos. 4-122938, 2-28531, 4,916,210, and European Patent No. 219294 , And can be easily synthesized by those skilled in the art.

Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, dioxycholic acid and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, cyclohexane Carboxylic acid, cyclohexanedicarboxylic acid, and the like, but are not limited thereto.

Pattern formation method

The 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. The film thickness can be made such that the solid content concentration in the actinic ray-sensitive or radiation-sensitive resin composition is set in an appropriate range to have an appropriate viscosity and the coating property and the film formability are improved.

The total solid content concentration in the actinic radiation-sensitive or radiation-sensitive resin composition is generally from 1 to 10 mass%, more preferably from 1 to 8.0 mass%, and still more preferably from 1.0 to 6.0 mass%.

The composition of the present invention is obtained by dissolving the above components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering the solution, and applying the solution on a predetermined support as follows. The pore size of the filter to be used for filter filtration is preferably polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 탆 or less, more preferably 0.05 탆 or less, and even more preferably 0.03 탆 or less.

For example, the active ray-sensitive or radiation-sensitive resin composition is coated on a substrate (for example, silicon / silicon dioxide coating) used for the production of precision integrated circuit devices by a suitable coating method such as a spinner or a coater, Thereby forming a resist film.

The resist film is irradiated with an actinic ray or radiation through a predetermined mask, preferably baked (heated) to develop and rinse. Thus, a good pattern can be obtained.

Examples of the active light or radiation include infrared light, visible light, ultraviolet light, ultraviolet light, extreme ultraviolet light, X-ray, electron beam and the like, but preferably 250 nm or less, more preferably 220 nm or less, A KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray and an electron beam. The ArF excimer laser, the F ₂ excimer laser Laser, EUV (13 nm) and electron beam are preferable.

An antireflection film may be previously coated on the substrate before forming the film.

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

In the development process, an alkaline developer is used as follows. Examples of the alkali developing solution of the active ray-sensitive or radiation-sensitive resin composition include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia water, primary amines such as ethylamine and n- Secondary amines such as ethylamine, di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium Quaternary ammonium salts such as hydroxides, and cyclic amines such as pyrrole and piperidine.

Alcohols and surfactants may be added to the alkali developing solution in an appropriate amount.

The alkali concentration of the alkali developing solution is usually 0.1 to 20 mass%.

The pH of the alkali developing solution is usually from 10.0 to 15.0.

Alcohols and surfactants may be added to the alkaline aqueous solution in an appropriate amount.

As the rinsing liquid, pure water may be used and an appropriate amount of surfactant may be added.

In addition, a treatment for removing the developing solution or the rinsing liquid adhered to the pattern by the developing treatment or the rinsing treatment with the supercritical fluid can be performed.

(Example)

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.

≪ Synthesis of photoacid generator >

The following photoacid generator PAG 15 was synthesized according to the following synthesis route.

[Synthesis of compound 1]

20 g of bromomethylcyclohexane and 12.5 g of 1-naphthol were dissolved in 300 g of NMP in a three-necked flask, 12 g of potassium carbonate and 14 g of potassium iodide were added, and the mixture was heated at 120 DEG C for 8 hours. 300 g of water was added to the reaction solution and extracted three times with 100 g of hexane. The resulting organic layers were combined, washed once with 100 g of a 1N aqueous sodium hydroxide solution, once with 100 g of water and once with 100 g of brine, 13 g.

[Synthesis of Compound 2]

Compound 2 was synthesized with reference to the method described in Japanese Patent Laid-Open No. 2005-266799.

[Synthesis of PAG15]

13.1 g of Compound 1 was dissolved in 65 g of Eaton reagent in a three-necked flask, and 5.7 g of tetramethylene sulfoxide was added dropwise while stirring, followed by stirring for 3 hours. After the reaction solution was poured into 240 g of water, 25 g of the compound 2 and 50 g of chloroform were added. After the organic layer was separated, the aqueous layer was extracted twice more with 50 g of chloroform. The obtained organic layers were combined and washed twice with water and concentrated. The obtained composition was recrystallized using 20 g of ethyl acetate to obtain 22 g of PAG15.

PAG1 to PAG14 and PAG16 to PAG21 were also prepared in the same manner as PAG15.

≪ Synthesis of Resin (A) >

Synthesis Example 1 Synthesis of Resin (1)

Under a nitrogen gas stream, 8.6 g of cyclohexanone was placed in a three-necked flask and heated to 80 캜. 8.0 g of norbornane lactone methacrylate, 4.0 g of dihydroxyadamantyl methacrylate, 9.0 g of 2-adamantyl isopropyl methacrylate, polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 8 mol% in 70 g of cyclohexanone was added dropwise over 6 hours. After completion of dropwise addition, the reaction was further carried out at 80 DEG C for 2 hours. The reaction solution was left to stand to cool, and then added dropwise to a mixed solution of 800 ml of hexane and 200 ml of ethyl acetate over 20 minutes. The precipitated powder was collected by filtration and dried to obtain 17 g of Resin (1). The weight average molecular weight of the obtained resin was 8500 in terms of standard polystyrene and the dispersion degree (Mw / Mn) was 1.8.

(2) to (4) were prepared in the same manner as in Synthesis Example 1, except that the monomers shown in Table 3 were used and the composition ratio, weight average molecular weight and dispersity (Mw / Mn) (12) were synthesized.

≪ Synthesis of Resin (C) >

Synthesis Example 2 Synthesis of Additive Polymer C-7

Monomers corresponding to the following repeating units were respectively charged in a ratio of 90/10 (molar ratio), and dissolved in PGMEA to prepare 450 g of a solution having a solid content concentration of 15% by mass. To this solution was added 1 mol% of Polymerization Initiator V-60 from Wako Pure Chemical Industries, Ltd., and the resulting solution was added dropwise to 50 g of PGMEA heated to 100 占 폚 over 6 hours in a nitrogen atmosphere. After completion of dropwise addition, the reaction solution was stirred for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 5 L of methanol was crystallized. The precipitated white powder was collected by filtration to recover the target resin C-7.

The polymer composition ratio determined from NMR was 90/10. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 8000 and the degree of dispersion was 1.40.

The above-mentioned resin C-3, C-26, C-49, C-63, C-69, C-76, C-88, C-132 and C-146 were prepared in the same manner as in Synthesis Example 2 (Mw / Mn) shown in Table 1 were synthesized with respect to C-165, C-193 and C-211.

[Table 3]

<Preparation of Resist>

The components shown in the following Table 4 were dissolved in a solvent to prepare a solution having a total solid content concentration of 4% by mass for each solution. The solution was filtered with a polyethylene filter having a pore size of 0.05 탆 to prepare a positive resist solution for immersion exposure. The prepared resist compositions were evaluated by the following methods, and the results are shown in the same table. In addition, the ratio when a plurality of components are used in the same table is the mass ratio.

The amount of the resin (C) added is% by mass with respect to the total solid content of the resist composition.

[Table 4]

The symbols in Table 4 are as follows.

[Acid generator and resin (C)]

The acid generator and the resin (C) correspond to those illustrated earlier.

[Basic compound]

N-1: N, N-dibutyl aniline

N-2: 2,6-diisopropylaniline

N-3: 2-phenylbenzoimidazole

N-6: 2,4,5-triphenylimidazole

[Surfactants]

W-1: Megafac F176 (manufactured by Dainippon Ink & Chemicals, Inc., fluorine)

W-2: Troizol S-366 (manufactured by Troy Chemical)

W-3: PF6320 (manufactured by OMNOVA, fluorine)

[solvent]

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)

SL-2: Propylene glycol monomethyl ether (PGME)

SL-3: Ethyl lactate

SL-4: Cyclohexanone

SL-5: 2-heptanone

SL-6: Propylene carbonate

SL-7: N-methylpyrrolidone

SL-8:? -Butyrolactone

&Lt; Evaluation of resist &

[Exposure conditions: ArF liquid immersion exposure]

An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was coated on a silicon wafer and baked at 205 DEG 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 캜 for 60 seconds to form a resist film having a thickness of 120 nm. The resulting wafer was subjected to a 6-percent halftone process in a 65 nm 1: 1 line and space pattern using an ArF excimer laser immersion scanner (XT1700i, NA1.20, C-Quad, outer Sigma 0.981, Inner Sigma 0.895, XY deflection) And exposed through a mask. Ultrapure water was used as the immersion liquid. Thereafter, the resist film was heated at 130 DEG C for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38 mass%) for 30 seconds, rinsed with pure water, and then spin-dried to obtain a resist pattern.

[Defective application]

5 cc of a resist was spin-coated on a 12-inch silicon wafer at 3000 rpm, baking was performed with a hot plate, and the film thickness within 10 mm from the outer peripheral portion of the wafer after coating was measured. A having a film thickness variation of 4 nm or less, B having a thickness of more than 4 nm but less than 20 nm, C having a thickness of more than 20 nm but less than 50 nm, C exceeding 50 nm, precipitation of a solute, Or that the resist is not coated to the outer peripheral portion of the wafer is referred to as D.

[LWR]

The LWR was measured using a measurement SEM (Hitachi Seisakusho S-9260, manufactured by Hitachi Seisakusho Co., Ltd.), and an isolated pattern of 65 nm at the optimum exposure amount was observed to determine the edge in the longitudinal direction of the line pattern, The distance from the baseline to be present was measured at 50 points, and the standard deviation was calculated to calculate 3σ. The smaller the value, the better the performance.

From Table 4, it was found that the pattern formed by using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention suppressed coating defects and was excellent in LWR performance.

Claims (14)

1. A sensitive active ray or radiation-sensitive resin composition comprising the following components (A) to (D):
(A) a resin whose solubility in an alkali developing solution is increased by the action of an acid;
(B) a compound represented by the following general formula (1-1) or (1-2);
(C) a resin comprising a repeating unit having at least one of a fluorine atom and a silicon atom on one side chain, and a polarity-converting group decomposed by the action of an alkali developer to increase the solubility in an alkali developing solution, A resin having at least a carboxylic acid ester group (-COO-) (however, the carboxylic acid ester group does not include -COO- in the lactone group and -COO- directly connected to the main chain of the repeating unit) as a transducer; And
(D) at least one solvent selected from the group consisting of the following formulas (S1) to (S4), wherein the total content of the solvent is 1 to 20 Mass% mixed solvent.

[In the general formula (1-1)
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.
R _14, when present in plural, independently represent an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group or a group having a monocyclic or polycyclic cycloalkyl skeleton.
R ₁₅ independently represent an alkyl group, a cycloalkyl group or a naphthyl group. Two R &lt; ₁₅ &gt; may be bonded to each other to form a ring.
and l represents an integer of 0 to 2.
r represents an integer of 0 to 8;
X ^- represents an acetylenic anion.
In the general formula (1-2)
M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when having a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbon-carbon double bond.
R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.
R _x and R _y may combine to form a ring.
Two or more of M, R _1c and R _2c may be bonded to form a ring or may contain a carbon-carbon double bond in the ring structure.
X ^- represents an acetonucleophilic anion.

[In the formula (S1) ~ (S3), R 1 ~R 7 is an aryl group which may have a cycloalkyl group, or a substituent which may have an alkyl group which may have a substituent, each independently. R ₁ and R ₂ , R ₃ and R ₄ , or R ₆ and R ₇ may be connected to form a ring.
In the general formula (S4), R ₈ and R ₉ each independently represent an alkyl group which may have a substituent, and the two groups may be connected to each other to form a ring. The method according to claim 1,
Wherein the resin (A) contains a repeating unit containing a lactone structure. The method according to claim 1,
The resin (A) comprises a repeating unit having an acid-decomposable group containing a monocyclic or polycyclic alicyclic structure. The method according to claim 1,
Wherein a liquid immersion exposure is applied. The method according to claim 1,
Wherein the content of the compound (B) is 10 to 30 mass% based on the total solid content of the composition. The method according to claim 1,
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. The method according to claim 1,
Wherein the resin (C) comprises a repeating unit having at least two polarity transducers. The method according to claim 1,
The mixed solvent (D) contains at least one kind of solvent selected from the group consisting of the general formulas (S1) to (S4) as γ-butyrolactone. . The method according to claim 1,
Wherein the mixed solvent (D) contains cyclohexanone as at least one solvent selected from the group represented by the general formulas (S1) to (S4). The method according to claim 1,
Wherein the mixed solvent (D) does not contain a protonic solvent. The method according to claim 1,
Wherein the mixed solvent (D) contains propylene glycol monomethyl ether acetate in an amount of 50 mass% or more. A pattern forming method, characterized by comprising a step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, a step of exposing the film, and a step of developing. 13. The method of claim 12,
Wherein the exposure is an immersion exposure. The method according to claim 1,
Wherein the repeating unit having the polarity converting group is a repeating unit represented by the following general formula (K0).

[Wherein R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group or an aryl group,
R _k2 represents a group having at least one of a fluorine atom and a silicon atom and having a polarity converting group]