TWI497211B - Photosensitive ray- or radiation-sensitive resin composition and pattern forming method using same - Google Patents

Description

Photosensitive ray- or radiation-sensitive resin composition and pattern forming method using same

The present invention relates to a sensitizing ray-sensitive or radiation-sensitive resin composition, and a pattern forming method using the same, and more particularly to the manufacture of a circuit board used for semiconductor manufacturing engineering such as IC, liquid crystal, thermal dislocation, etc., and further Other photosensitive ray-sensitive or radiation-sensitive compositions for use in photo-sensitive etching processes, and pattern forming methods using the same. More specifically, the present invention relates to a sensitized ray- or radiation-sensitive resin composition suitable for use as an exposure light source having a far ultraviolet ray of 250 nm or less, preferably 220 nm or less, and a pattern using the same. The method of formation.

Further, the term "actinic ray" or "radiation" as used in the present invention means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray, an X ray, an electron beam, or the like. Further, the term "light" as used in the present invention means actinic rays or radiation.

As a photosensitive composition for a chemically amplified photoresist composition such as a lithography process for a semiconductor, in particular, an ArF excimer laser (wavelength: 193 nm) is used as a light source from the viewpoints of transparency and dry etching resistance. Look, a resin having an alicyclic hydrocarbon group is used.

In the photosensitive composition containing a resin having an alicyclic hydrocarbon group, a stronger acid is required, and a perfluoroalkylsulfonic acid-producing compound such as triphenylsulfonium trifluoromethanesulfonate or the like is used.

However, the perfluoroalkyl sulfonic acid has high hydrophobicity, and the photosensitive composition using the acid generator which generates the above has a low affinity for the aqueous developing solution, and the developability is deteriorated, the sensitivity is lowered, or development defects are generated. The problem.

In this regard, Patent Document 1 describes a photosensitive composition using a specific acid-generating compound, which specifically produces an acid-containing compound fluorine atom.

However, as the pattern is more refined, various properties, particularly the exposure range and line width roughness, need to be improved.

Further, if the liquid immersion exposure is applied to the chemically amplified photoresist, since the photoresist layer contacts the immersion liquid at the time of exposure, the photoresist layer is deteriorated or the immersion liquid is adversely affected from the photoresist layer so that the components bleed out. Patent Document 2 discloses an example in which the photoresist performance is changed by immersion in water before exposure to the photoresist for ArF exposure, and the problem in the immersion exposure is pointed out.

Patent Document 3 describes an example in which an acid generator having a specific sulfilimine structure is used for liquid immersion exposure.

On the other hand, in the case where an ArF excimer laser is applied to a triarylsulfonium salt such as a triphenylsulfonium salt, although it is high in sensitivity and high in quantum yield, it is absorbed by the benzene ring. The transmitted light at the lower portion of the photoresist film is less, and the pattern shape is trapezoidal (tapered). For this reason, many attempts have been made to produce a high-sensitivity photo-acid generator for photoresist having a high transparency at a wavelength of 193 nm.

By way of example, Patent Document 4 proposes an onium salt compound having an alkoxynaphthalene skeleton. Further, Patent Document 5 proposes a phosphonium cation salt having an alkoxynaphthalene skeleton using a sulfilimine as a relative anion. However, although these compounds have high transparency in the far ultraviolet region, the lithographic properties are not satisfactory.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2004-2252

[Patent Document 2] International Publication No. 04/068242

[Patent Document 3] JP-A-2006-84530

[Patent Document 4] Japanese Patent Publication No. Hei 10-232490

[Patent Document 5] JP-A-2004-12554

An object of the present invention is to provide a sensitized ray-sensitive or radiation-sensitive resin composition which can form a pattern having excellent line width roughness (LWR) performance and which suppresses coating defects, and a pattern forming method using the same.

In order to solve the above problems, the inventors of the present invention have achieved the present invention which has been completed as described below.

(1) A photosensitive ray-sensitive or radiation-sensitive resin composition characterized by the following (A) to (D).

(A) a resin which increases the solubility to an alkali developer by the action of an acid,

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

(C) a resin having at least one of a fluorine atom and a ruthenium atom and a polar conversion group which decomposes by an action of an alkali developer and increases solubility in an alkali developer, and

(D) a mixed solvent of two or more kinds of solvents, that is, at least one solvent selected from the group consisting of the following general formulae (S1) to (S4), and the total content of the solvent is the total solvent. 1 to 20% by mass of a mixed solvent.

In the 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 cycloalkane skeleton having a monocyclic or polycyclic ring. base.

Where a plurality of R ₁₄ are present, each independently representing an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a single ring Or the base of a polycyclic naphthenic skeleton.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may also be combined with each other to form a ring.

l is an integer from 0 to 2.

r is an integer from 0 to 8.

The X ^- line represents a non-nucleophilic anion.

In the 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 also contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond, or 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-sided oxyalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

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

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

The X ^- line represents a non-nucleophilic anion.

In the general formulae (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 bonded to each other to form a ring.

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

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

(3) The photosensitive ray-sensitive or radiation-sensitive resin composition according to (1) or (2), wherein the resin (A) contains a repeating unit containing an acid-decomposable group, and the acid-decomposable group has a single ring or Polycyclic alicyclic structure.

(4) The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (3), which is applicable to liquid immersion exposure.

(5) The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (4), wherein the content of the compound (B) based on the total solid content of the composition is 10 Up to 30% by mass.

(6) A pattern forming method comprising the steps of forming a film using the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5), the step of exposing the film, and developing The steps.

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

According to the present invention, it is possible to provide a sensitized ray-sensitive or radiation-sensitive resin composition which can form a pattern which suppresses coating defects and has excellent LWR performance, and a pattern forming method using the same. Further, the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used as a positive-type photoresist composition.

The following description is directed to the best mode for carrying out the invention.

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

In addition, the term "exposure" as used in the present specification is not limited by the exposure of far ultraviolet rays, X-rays, EUV light, etc. represented by a mercury lamp or a quasi-molecular laser, but also by particles such as an electron beam or an ion beam. The exposure of the line is also included.

[1] Compounds which produce acid by irradiation with actinic rays or radiation

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

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

Even if these compounds are in the above-mentioned range of addition amount, the formed film can maintain high transmittance for ArF light having a wavelength of 193 nm, for example, as a film of 100 nm, the transmittance of light having a wavelength of 193 nm can be 60% or more and 85% or less. . The high transmittance of ArF light is due to the good performance in the patterning of ArF light.

The transmittance of light having a wavelength of 193 nm can be applied to a quartz glass substrate by spin coating, for example, by spin coating at 100 ° C to form a film having a thickness of 100 nm. The absorbance at a wavelength of 193 nm of the film was determined by an ellipsometer EPM-222 (manufactured by JA Woollam Co., Ltd.) or the like.

The total amount of the acid generator is preferably from 80% by mass to 100% by mass based on the compound represented by the formula (1-1) or (1-2), more preferably from 90% by mass to 100% by mass. .

In the 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 cycloalkane skeleton having a monocyclic or polycyclic ring. base.

Where a plurality of R ₁₄ are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or has a single ring or It is the base of a polycyclic cycloalkane skeleton.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may also be combined with each other to form a ring.

l is an integer from 0 to 2.

r is an integer from 0 to 8.

The X ^- line represents a non-nucleophilic anion.

In the 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 also contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond, or 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-sided oxyalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

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

The X ^- line represents a non-nucleophilic anion.

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

In the formula (1-1), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is preferably a linear or branched form and has a carbon number of from 1 to 10, and examples thereof include a methyl group and an ethyl group. , n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl , 2-ethylhexyl, n-decyl, n-decyl, and the like. Among these alkyl groups, a methyl group, an ethyl group, a n-butyl group, a tertiary butyl group or the like is preferred.

The cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group or a ring. The heptenyl group, the cyclohexenyl group, the cyclooctadienyl group, the adamantyl group and the like are preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group.

The alkoxy group of R ₁₃ and R ₁₄ is preferably a linear chain, a branched chain or a cyclic group and has a carbon number of 1 to 10, and examples thereof include a methoxy group, an ethoxy group, and a n-propoxy group. , isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, n-glycol Oxyl, n-octyloxy, 2-ethylhexyloxy, n-decyloxy, n-decyloxy, cycloheptyloxy, cyclooctyloxy and the like. Among these alkoxy groups, a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group or the like is preferred.

The alkoxycarbonyl group of R ₁₃ and R ₁₄ is preferably a linear or branched form and has a carbon number of 2 to 11, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a n-propoxy group. Carbonyl, isopropoxycarbonyl, n-butoxycarbonyl, 2-methylpropoxycarbonyl, 1-methylpropoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, neopentyloxy Carbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-decyloxycarbonyl group, n-decyloxycarbonyl group and the like. Among these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, a n-butoxycarbonyl group and the like are preferable.

Examples of the group having a monocyclic or polycyclic cycloalkane skeleton of R ₁₃ and R ₁₄ include a cycloalkyloxy group having a monocyclic or polycyclic ring, and a ring having a single ring or a polycyclic ring. Alkoxy group of alkyl. These base systems may further have a substituent.

The monocyclic or polycyclic cycloalkoxy group of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, a total carbon number of 7 or more and 15 or less, and a monocyclic naphthenic ring. The skeleton is better. The monocyclic cycloalkoxy group having a total carbon number of 7 or more is represented by a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, and a cyclodecene group. The cycloalkoxy group of a dialkoxy group or the like optionally has a methyl 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. , an alkyl group such as a secondary butyl group, a tertiary butyl group or an isopentyl group, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, a decylamino group, a sulfonylamino group, a methoxy group Alkoxycarbonyl group of alkoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, etc., alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, methyl group, and ethyl group a monocyclic cycloalkoxy group having a substituent such as a mercapto group such as a mercapto group or a benzamidine group, a decyloxy group or a butyloxy group, or a carbonyl group, and the like, and a total carbon number on the cycloalkyl group The total number of the substituents is 7 or more.

Further, examples of the polycycloalkyloxy group having a total carbon number of 7 or more include a norbornyloxy group, a tricyclodecyloxy group, a tetracyclodecyloxy group, an adamantyloxy group, and the like. It may also have the above substituents.

The alkoxy group having a monocyclic or polycyclic cycloalkane skeleton of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less. An alkoxy group having a monocyclic naphthenic skeleton is preferred. The alkoxy group having a monocyclic naphthenic skeleton having a total carbon number of 7 or more is represented by a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group or a octyl group. The alkoxy group of an oxy group, a decyloxy group, a 2-ethylhexyloxy group, an isopropoxy group, a secondary butoxy group, a tertiary butoxy group, an isopentyloxy group or the like may have a single substituent as described above. The cycloalkyl group is substituted, and the total carbon number of the substituent is 7 or more. For example, a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, etc. may be mentioned, and a cyclohexylmethoxy group is preferable.

Further, the alkoxy group having a polycyclic cycloalkane skeleton having a total carbon number of 7 or more is preferably a decyloxy group, a decyloxy group, a tricyclodecylmethoxy group. , tricyclodecyl ethoxy, tetracyclodecyl methoxy, tetracyclodecyl ethoxy, adamantyl methoxy, adamantyl ethoxy, etc., wherein thiol methoxy, hydrazine The ethoxy group is preferred. These lines may also have the above substituents.

The alkyl group of the alkylcarbonyl group of R ₁₄ may be the same as the above-mentioned alkyl group as R ₁₃ to R ₁₅ .

The alkylsulfonyl group and the cycloalkylsulfonyl group of R ₁₄ are preferably a linear, branched or cyclic carbon number of 1 to 10, and examples thereof include a methylalkylsulfonyl group. Ethylsulfonyl, n-propanesulfonyl, n-butylsulfonyl, tert-butylbutanesulfonyl, n-pentylsulfonyl, neopentylsulfonyl, n-hexane Sulfonyl, n-heptylsulfonyl, n-octylsulfonyl, 2-ethylhexylsulfonyl, n-decylsulfonyl, n-decylsulfonyl, cyclopentane Alkylsulfonyl, cyclohexanesulfonyl, and the like. Among these alkylsulfonyl and cycloalkylsulfonyl groups are a methyl sulfonyl group, an ethane sulfonyl group, a n-propane sulfonyl group, a n-butyl sulfonyl group, a cyclopentyl group. A sulfonyl group, a cyclohexanesulfonyl group or the like is preferred.

Each of the above-mentioned groups may have a substituent, and examples of the substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, and an alkoxy group. Alkylcarbonyl, alkoxycarbonyloxy and the like.

The alkoxy group may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a 2-methylpropoxy group or a 1-methylpropoxy group. A linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as a tertiary butoxy group, a cyclopentyloxy group or a cyclohexyloxy group.

The alkoxyalkyl group may, for example, be methoxymethyl, ethoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl or 2-ethoxyB. A linear, branched or cyclic alkoxyalkyl group having a carbon number of 2 to 21 or the like.

The alkoxycarbonyl group may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group or a 2-methylpropoxycarbonyl group. a linear, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms such as 1-methylpropoxycarbonyl, tertiary butoxycarbonyl, cyclopentyloxycarbonyl or cyclohexyloxycarbonyl .

The alkoxycarbonyloxy group may, for example, be a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group or a n-butoxycarbonyl group. a linear, branched or cyclic alkoxycarbonyloxy group having 2 to 21 carbon atoms such as an oxy group, a tertiary butoxycarbonyloxy group, a cyclopentyloxycarbonyloxy group or a cyclohexyloxycarbonyloxy group; Wait.

A ring structure formed by combining two R ₁₅ groups with each other may be a 5-member or 6-member ring formed by two divalent R ₁₅ and a sulfur atom in the formula (1-1). It is a 5-membered ring (ie, a tetrahydrothiophene ring), and may also be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ group may have a substituent, and 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 alkoxy group. Alkyloxy group and the like.

In the case of R ₁₅ , a methyl group, an ethyl group, a naphthyl group, and two R ₁₅ groups are bonded to each other to form a divalent group of a tetrahydrothiophene ring structure together with a sulfur atom.

The substituent of R ₁₃ and R ₁₄ is preferably a hydroxyl group, an alkoxy group, or an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

In the case of 1, it is preferably 0 or 1, more preferably 1.

In terms of r, it is preferably 0 to 2.

The salt represented by the formula (1-1) of the present invention includes the following specific examples.

In the following formula, the X ^- line represents a relative anion.

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

In the formula, 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-sided oxyalkyl 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. When having a ring structure, the ring structure may also contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbon-carbon double bond.

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

Any one of the alkyl chain and the branch of M may be, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and may, for example, be a Base, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl.

Examples of the cyclic alkyl group having 3 to 12 carbon atoms of the cycloalkyl group of M include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group.

The aryl group of M, preferably a carbon number of 5 to 15, may, for example, be a phenyl group or a naphthyl group.

Each of the groups of M may have a cycloalkyl group, an alkoxy group, a halogen atom, a phenylthio group or the like as a substituent. The cycloalkyl group and the aryl group of 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, the substituent has at least one straight chain, branched chain, cyclic alkyl group, linear, branched, cyclic alkoxy group or phenylthio group, and more preferably a substituent. The carbon number is between 2 and 15. Thereby, the solubility of the solvent is further enhanced and the generation of particles is suppressed during storage.

The alkyl group of R _1c and R _2c , for example, an alkyl group having 1 to 12 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms may, for example, be a methyl group, an ethyl group, a linear chain or Branched propyl.

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

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 is preferably a carbon number of 5 to 15, and examples thereof include a phenyl group and a naphthyl group.

In terms of at least two bond forming ring structures of M, R _1c and R _2c , it is preferably a 3 to 12 membered ring, more preferably a 3 to 10 membered ring, still more preferably a 3 to 6 membered ring. The ring skeleton system may also have a carbon-carbon double bond.

R _1c and R _2c in bonded form a ring, groups R _1c to R _2c and the bonding is formed, the carbon number of alkyl group of 2 to 10 extend preferably include stretch e.g. ethyl, propyl extension Base, butyl, pentyl, hexyl and the like. Further, the ring system formed by bonding R _1c and R _2c may have a hetero atom such as an oxygen atom in the ring.

The alkyl group of R _x and R _y may be the same as the alkyl group as R _1c and R _2c .

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

The 2-sided oxyalkyl group may be a group having >C=O at the 2-position of the alkyl group as R _1c and R _2c .

The alkoxy group in the alkoxycarbonylalkyl group may be any of a straight chain, a branched chain, and a cyclic group, and examples thereof include an alkoxy group having 1 to 10 carbon atoms, preferably a carbon number of 1 to 10. a straight chain and a branched alkoxy group (for example: methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, linear or branched pentyloxy), carbon A cyclic alkoxy group of 3 to 8 (for example, a cyclopentyloxy group or a cyclohexyloxy group). Further, the alkyl group in the alkoxycarbonylalkyl group, for example, an alkyl group having 1 to 12 carbon atoms, preferably a linear chain having 1 to 5 carbon atoms such as a methyl group or an ethyl group.

In the case of the allyl group, there is no particular restriction, but an allyl group which is unsubstituted or substituted with a monocyclic or polycyclic cycloalkyl group is preferred.

There is no particular restriction on the vinyl group, but a vinyl group which is unsubstituted or substituted with a monocyclic or polycyclic cycloalkyl group is preferred.

Examples of the ring structure in which R _x and R _y may be bonded to each other include divalent R _x and R _y (for example, methylene, exoethyl, propyl, etc.) and formula (1). -2) A ring of 5 or 6 members formed by a sulfur atom in the middle, and a ring of 5 members (ie, a tetrahydrothiophene ring).

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

The cation of the compound represented by the formula (1-2) of the present invention includes the following specific examples.

The relative ion represented by X ^- in the general formulae (1-1) and (1-2) is a structure represented by the following general formula (II).

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

R ₁ represents an organic group having a valence of one fluorine atom, and preferably an organic group having a value of (the mass of all fluorine atoms contained) / (mass of all atoms contained) = 0.13 or less.

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

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

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

R ₁ is an organic group having one valence of a fluorine atom, and is preferably an organic group having a fluorine content of 0.35 or less expressed by (the mass of all fluorine atoms contained) / (mass of all atoms contained). In R ₁ , the fluorine content is more preferably 0.30 or less, and particularly preferably 0.25 or less.

The organic group having one valence of a fluorine atom represented by R ₁ may, for example, be an organic group containing an alkylene group substituted with at least one fluorine atom bonded to a sulfonyl group, and the alkylene group is preferably. It is a perfluoroalkylene group. Further, it is preferred that the terminal end is substituted with a group having a cyclic structure, and may be substituted with a linking group. From the viewpoint of a low fluorine content, the base having a cyclic structure preferably has no fluorine atom. In one R ₁ represents a monovalent organic group of lines may be configured to include in a later corresponding to said patterns of formula (III) R ₁ of the above.

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

In the case of a chain alkyl group, it may be a linear chain or a branched chain, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a dodecane group. Base, 2-ethylhexyl, isopropyl, secondary butyl, tert-butyl, isopentyl, and the like.

The alkyl group may have a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, a decylamino group, a sulfonylamino group, and a methyl group. , ethyl, propyl, n-butyl, secondary butyl, hexyl, 2-ethylhexyl, octyl, etc. alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropyl An alkoxy group such as an oxy group or a butoxy group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; a mercapto group such as a mercapto group, an ethyl fluorenyl group or a benzamidine group; an ethoxy group; a decyloxy group or the like, a methoxy group or a carbonyl group.

The monocyclic alkyl group is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group, a cyclopentenyl group, or a ring. A hexenyl group, a cyclooctyl group or the like is particularly preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group.

The monocyclic alkyl group may have a substituent, and examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, a decylamino group, a sulfonylamino group, and a Base, ethyl, propyl, n-butyl, secondary butyl, hexyl, 2-ethylhexyl, octyl, etc. alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxy An alkoxycarbonyl group such as a propoxy group or a butoxy group, an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, a mercapto group such as a mercapto group, an ethyl fluorenyl group or a benzamidine group, or an ethoxy group. An oxy group or a carbonyl group such as a butyl oxy group.

Examples of the polycyclic hydrocarbon group include bicyclo [4.3.0] fluorenyl, decahydronaphthalene, tricyclo [5.2.1.0 (2,6)] fluorenyl, fluorenyl, isodecyl, norbornyl, Adamantyl, noradamantane, 1,7,7-trimethyltricyclo[2.2.1.0 ^2,6 ]heptyl, 3,7,7-trimethylbicyclo[4.1.0]g Base, etc., particularly preferably a thiol group, an adamantyl group, a norantayl group.

The monocyclic aryl group means a substituted or unsubstituted phenyl group, and examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, a decylamino group, and a sulfonate. Alkyl, methyl, ethyl, propyl, n-butyl, secondary butyl, hexyl, 2-ethylhexyl, octyl, etc. alkyl, methoxy, ethoxy, hydroxyethoxy, An alkoxy group such as a propoxy group, a hydroxypropoxy group or a butoxy group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; a mercapto group such as a methyl group, an ethyl group or a benzyl group; An oxy group or a carbonyl group such as an ethoxy group or a butoxy group.

The R ₂ is preferably an electron withdrawing group from the viewpoint of acid strength. The electron withdrawing group is not particularly limited, and examples thereof include a cyano group, a trifluoromethyl group, a nitro group, a carboxyl group, a ketone group, a decyloxy group, a hydroxyl group, a perfluoroalkyl group, a methoxy group, and an ethoxy group. The alkoxy group such as an isopropoxy group, a tertiary butoxy group or a benzyloxy group, a halogen atom such as a fluorine atom or a chlorine atom, or the like is preferably a fluorine atom. More preferably, the R ₂ is a group having a fluorine atom having a molecular weight of 220 or less, and particularly preferably R ₂ is a trifluoromethyl group.

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

In the formula (III), A, R ₂ , m, and n are synonymous with each of the formula (II).

In the case of a plurality of R ₃ , each of them may independently represent an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group having a substituent, and R ₄ represents a hydrogen atom.

The L system is represented by a single bond or a linking group.

P1 represents an integer from 1 to 8, p2 represents =1 or 2, and p3 represents =0 or 1.

In the case of p2=2, the two R ₃ systems may be bonded to each other to form a ring structure, and when n=2 or more, a plurality of R ₃ systems may be bonded to each other to form a ring structure.

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

Here, from the viewpoint of the low fluorine content of the R ₃ system, it is preferred that no fluorine atom is present.

L is preferably a single bond, an oxygen atom (-O-), a sulfur atom (-S-), a nitrogen atom (>N-), a carboxyl group (-OC=O-, -CO=O-), a guanamine group. (>NC=O-), sulfonamide (>NSO ₂ -). In particular, in the case where p2 = 2, two R _{3 are} bonded to each other to form a ring, and L is preferably a linking group having a nitrogen atom such as a guanamine group or a sulfonylamino group, in which case two R _{3 are} bonded to each other to form a ring. a cyclic amine residue having a nitrogen atom on L.

In terms of the structure of the cyclic amine residue, 吖 (aziridine), azetidine, pyrrolidine, piperidine, hexamethyleneimine, heptamethyleneimine, piperazine , decahydroquinoline, decahydroquinoline, 8-indene bicyclo[3.2.1]octane, anthracene, Oxazole, tetrahydrothiazole, 2-indolyl decane, 7-fluorene decane, Porphyrin A phenyl or the like may also have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, a decylamino group, a sulfonylamino group, a methyl group, an ethyl group, a propyl group, and a n-butyl group. Alkyloxy of alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, butoxy, etc. of secondary butyl, hexyl, 2-ethylhexyl, octyl, etc. An alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, a fluorenyl group, an ethyl fluorenyl group, a benzhydryl group, and a carbonyl group such as a carbonyl group on a ring-forming carbon, an ethoxy group, and a butyl group. A methoxy group or a carbonyl group such as a decyloxy group.

The following specific examples are given to the relative anion structure represented by the general formula (II) of the present invention.

The compound (B) represented by the formula (1-1) which produces an acid is exemplified by the following compounds, but is not limited thereto.

The compound (B) represented by the formula (1-2) which produces an acid is exemplified by the following compounds, but is not limited thereto.

The acid generator (B) represented by the general formulae (1-1) and (1-2) may be used singly or in combination of two or more.

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

Further, the total amount of the photoacid generator preferably contains 80% by mass to 100% by mass of the compound (B), and more preferably 90% by mass to 100% by mass.

[Other photoacid generators]

In the present invention, in addition to the photoacid generator (B), a compound which decomposes to generate an acid by irradiation with actinic rays or radiation may be used. In such a photoacid generator which can be suitably used, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodegrading agent for a dye, a photochromic agent, or It is used as a conventional compound which generates an acid by irradiation of actinic rays or radiation, such as a micro-resistance, and the like.

Examples thereof include a diazonium salt, a phosphonium salt, a phosphonium salt, a phosphonium salt, a phosphonium imidesulfonate, an anthracenesulfonate, an anthraquinone, a diterpene, and an o-nitrobenzylsulfonate.

Further, such a compound which generates an acid group by irradiation with actinic rays or radiation, or a compound which introduces a compound into a main chain or a side chain of a polymer, for example, can be used as described in U.S. Patent No. 3,849,137, German Patent No. Japanese Patent Publication No. 3,914,407, Japanese Laid-Open Patent Publication No. JP-A-63-164824, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 A compound such as JP-A-62-153853 and JP-A-63-146029.

Further, a compound which generates an acid by light, which is described in the specification of U.S. Patent No. 3,779,778, and the specification of European Patent No. 126,712, can also be used.

Preferred compounds in the acid generator include compounds represented by the following formulae (ZI), (ZII), and (ZIII).

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

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

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and may further contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring. The group formed by the two bonds in R ₂₀₁ to R ₂₀₃ may, for example, be an alkyl group (for example, a butyl group or a pentyl group).

The Z ^- line represents a non-nucleophilic anion.

As Z ^- of the non-nucleophilic anion, examples thereof include sulfonic acid anion, for example, a carboxylic acid anion, sulfonic acyl acyl imide anion, bis (alkylsulfonyl yl) imide anion XI, ginseng (alkyl Sulfhydryl) methyl anion and the like.

The non-nucleophilic anion is an anion having a significantly low ability to generate a nucleophilic reaction, and is an anion capable of suppressing the decomposition of the nucleophilic reaction in the molecule. Thereby, the diachronic stability of the sensitizing ray-sensitive or radiation-sensitive resin composition is improved.

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

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

The aliphatic moiety in the aliphatic sulfonic acid anion may be 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, and examples thereof include a methyl group. , ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopropyl, cyclo Pentyl, cyclohexyl, adamantyl, norbornyl, fluorenyl and the like.

The aromatic group in the aromatic sulfonic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, the cycloalkyl group, and the 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, the cycloalkyl group and the aryl group in the aliphatic sulfonic acid anion and the aromatic sulfonic acid anion include a nitro group and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). ), a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), a cycloalkyl group (preferably having a carbon number of 3 to 15), and an aryl group (preferably having a carbon number of 6 to 14) an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), a mercapto group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), and an alkane sulfur a base (preferably having a carbon number of 1 to 15), an alkylsulfonyl group (preferably having a carbon number of 1 to 15), an alkylimidosulfonyl group (preferably having a carbon number of 2 to 15), and an aryloxy group. a sulfonyl group (preferably having a carbon number of 6 to 20), an alkylaryloxysulfonyl group (preferably having a carbon number of 7 to 20), a cycloalkylaryloxysulfonyl group (preferably a carbon number) 10 to 20), an alkoxyalkyloxy group (preferably, a carbon number of 5 to 20), a cycloalkylalkyloxyalkoxy group (preferably having a carbon number of 8 to 20), and the like. The aryl group and the ring structure of each group may further be an alkyl group (preferably having a carbon number of 1 to 15).

The aliphatic moiety in the aliphatic carboxylic acid anion may, for example, be the same alkyl group and cycloalkyl group as the aliphatic sulfonate anion.

The aromatic group in the aromatic carboxylic acid anion may, for example, be the same aryl group as the aromatic sulfonic acid anion.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthalene group. Butyl and the like.

The alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group in the aliphatic carboxylic acid anion, the aromatic carboxylic acid anion, and the aralkyl carboxylate anion may have a substituent. Examples of the substituent of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group in the aliphatic carboxylic acid anion, the aromatic carboxylic acid anion, and the aralkyl carboxylate anion include, for example, an aromatic sulfonate anion. The same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group or the like.

The sulfonyl quinone imine anion may, for example, be a saccharin anion.

The alkyl group in the bis(alkylsulfonyl) quinone imine anion or the exemplified (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group. , propyl, isopropyl, n-butyl, isobutyl, secondary butyl, pentyl, neopentyl, and the like. Examples of the substituent of the alkyl group 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 ring. The alkylaryloxysulfonyl group or the like is preferably an alkyl group substituted with a fluorine atom.

Examples of the other non-nucleophilic anion include phosphorus fluoride, boron fluoride, and cesium fluoride.

To Z ^- substituent of the non-nucleophilic anion, preferable are sulfonic α position by a fluorine atom aliphatic sulfonic acid anion, a fluorine atom or an aromatic sulfonic acid anion substituted with a fluorine atom of the group, an alkyl group A bis(alkylsulfonyl) fluorenylene anion substituted with a fluorine atom, and an alkyl (alkylsulfonyl) methylated anion substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms, an benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion or perfluorooctanesulfonate. Acid anion, pentafluorobenzenesulfonate anion, 3,5-bis(trifluoromethyl)benzenesulfonate anion.

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

In the 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, most preferably from the following formula (XI) Indicates the organic base.

The organic group of R may have one or more carbon atoms, and it is preferred that the atom bonded to the oxygen atom in the ester bond represented by the general formula (Xa) is a carbon atom, for example, having an alkyl group, The group having a cycloalkyl group, an aryl group, an aralkyl group or a lactone structure may have a hetero atom such as an oxygen atom or a sulfur atom in the chain. Further, these may have a substituent as a substituent, and may have a substituent such as a hydroxyl group, a decyl group, a decyloxy group, an oxy group (=O), or a halogen atom.

-(CH ₂ ) _n -Rc-(Y) _m formula (XI)

In the formula (XI), Rc represents a monocyclic or polycyclic ring having a carbon number of 3 to 30 which may also contain a cyclic ether, a cyclic thioether, a cyclic ketone, a cyclic carbonate, a lactone or an indoleamine structure. Cyclic organic group. 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, a mercapto group having 1 to 10 carbon atoms, An alkoxycarbonyl group having 2 to 10 carbon atoms, a decyloxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or a halogenated alkyl group having 1 to 8 carbon atoms. m = 0 to 6, and there are a plurality of Y cases, which may be the same or different. n=0~10.

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 preferably a monocyclic or polycyclic cyclic organic group of 7 to 16.

In the 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. Further, the Rb systems may be different from each other or may be bonded to each other to form a ring. The organic group of Rb may have one or more carbon atoms, and preferably the atom bonded to the nitrogen atom in the indole bond represented by the formula (Xb) is a carbon atom, and for example, an alkane may be mentioned. The group having a structure of a group, a cycloalkyl group, an aryl group, an aralkyl group or a lactone may have a hetero atom such as an oxygen atom or a sulfur atom in the chain. Further, these may have a substituent as a substituent, and may have a substituent such as a hydroxyl group, a decyl group, a decyloxy group, an oxy group (=O), or a halogen atom.

The molecular weight of the non-nucleophilic anion moiety represented by the general formula (Xa) and the general formula (Xb) is usually from 300 to 1,000, preferably from 400 to 800, and further preferably from 500 to 700.

The organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may, for example, be a group corresponding to the compounds (ZI-1), (ZI-2) and (ZI-3) described below.

Further, it may be a compound having a plurality of structures represented by the general formula (ZI). For example, a compound in which at least one of R ₂₀₁ to R ₂₀₃ represented by the formula (ZI) is bonded to at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by the formula (ZI) may be used.

Further preferred as the component (ZI), the compounds (ZI-1), (ZI-2), and (ZI-3) described below are exemplified.

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

The aryl hydrazine compound may also be any of R ₂₀₁ to R ₂₀₃ which may be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group, with an alkyl group or a cycloalkyl group remaining.

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

The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may also be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (which is formed by losing one hydrogen atom from the furan). a thiophene residue (a group formed by the loss of one hydrogen atom from thiophene), a hydrazone residue (a group formed by losing one hydrogen atom from hydrazine), a benzofuran residue (borrowed) a group formed by losing one hydrogen atom from benzofuran, a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), or the like. In the case where the aryl fluorene compound has two or more aryl groups, two or more aryl groups may be the same or different.

The aryl hydrazine compound preferably has an alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include methyl group and ethyl group. Base, propyl, n-butyl, secondary butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclohexyl and the like.

The aryl, alkyl or cycloalkyl group of R ₂₀₁ to R ₂₀₃ may have an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), and an aryl group (for example, a carbon number of 6 to 14), an alkoxy group (for example, a carbon number of 1 to 15), a halogen atom, a hydroxyl group, and a phenylthio group as a substituent. In the preferred substituent, it is 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. The group is more preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The substituent system may be substituted for any of the three R ₂₀₁ to R ₂₀₃ , and may be substituted for all three. Further, in the case where R ₂₀₁ to R ₂₀₃ are an aryl group, the substituent is preferably substituted at the para position of the aryl group.

Next, the compound (ZI-2) will be described.

The compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represent an organic group which does not contain an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.

The organic group which does not contain an aromatic ring as R ₂₀₁ to R ₂₀₃ is usually a carbon number of 1 to 30, preferably a carbon number of 1 to 20.

R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, a vinyl group, more preferably a linear or branched 2-sided oxyalkyl group or a 2-sided oxocycloalkyl group. An alkoxycarbonylmethyl group, particularly preferably a linear or branched 2-sided oxyalkyl group.

The alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ may, for example, be a linear or branched alkyl group having a carbon number of 1 to 10 (for example, methyl group, ethyl group, propyl group, butyl group, or the like). Pentyl), a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl, cyclohexyl, norbornyl). The alkyl group is more preferably a 2-sided oxyalkyl group or an alkoxycarbonylmethyl group. More preferably, the cycloalkyl group is a 2-sided oxocycloalkyl group.

The 2-sided oxyalkyl group may be any of a straight chain or a branch, and preferably has a group of >C=O at the 2-position of the above-mentioned alkyl group.

The 2-oxocycloalkyl group is preferably a group having >C=O at the 2-position of the above 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, pentyloxy group). ).

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

The compound (ZI-3) is a compound represented by the following formula (ZI-3); and is a compound having a benzamidine methyl phosphonium salt structure.

In the 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.

Two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y may each form a ring-bonding structure, and the ring structure may also contain an oxygen atom or a sulfur atom. Ester bond, guanamine bond. _Examples of the group formed by bonding two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butyl group, a pentyl group and the like.

Zc- represents a non-nucleophilic based anion, exemplified by the general formula (ZI) in the Z ^- the same non-nucleophilic anion.

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 linear chain and a branched alkyl group having 1 to 12 carbon atoms. a group (for example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group), and a cycloalkyl group, for example, a carbon number of 3 to a cycloalkyl group of 8 (e.g., cyclopentyl, cyclohexyl).

The alkoxy group of R _1c to R _5c may be any of a straight chain, a branch, and a ring, and may, for example, be an alkoxy group having 1 to 10 carbon atoms, preferably a carbon number of 1 to 5. Chains and branched alkoxy groups (for example: methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, linear or branched pentyloxy), carbon number 3 to a cyclic alkoxy group of 8 (e.g., cyclopentyloxy, cyclohexyloxy).

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

_Examples of the alkyl group and the cycloalkyl group of R _x and R _y include the same alkyl group and cycloalkyl group as in R _1c to R _7c , more preferably a 2-sided oxyalkyl group or a 2-sided oxocycloalkyl group. , alkoxycarbonylmethyl.

The 2-oxo-oxyalkyl group and the 2-oxo-oxocycloalkyl group include an alkyl group as R _1c to R _7c and a group having >C=O at the 2-position of the cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group is the same alkoxy group as in R _1c to 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, still more preferably an alkyl group or a cycloalkyl group of 8 or more.

In the general formulae (ZII) and (ZILI), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl group of R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, and still 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 or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (which is formed by losing one hydrogen atom from the furan). a thiophene residue (a group formed by the loss of one hydrogen atom from thiophene), a hydrazone residue (a group formed by losing one hydrogen atom from hydrazine), a benzofuran residue (borrowed) a group formed by losing one hydrogen atom from benzofuran, a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), or the like.

The alkyl group and the cycloalkyl group in R ₂₀₄ to R ₂₀₇ include a linear or branched alkyl group having preferably 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, and the like). Pentyl), a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl, cyclohexyl, norbornyl).

R ₂₀₄ to R ₂₀₇ of aryl, alkyl, cycloalkyl system may have a substituent. Examples of the substituent which the aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include, for example, an alkyl group (for example, a carbon number of 1 to 15) and a cycloalkyl group (for example, a carbon number of 3 to 15). And an aryl group (for example, a carbon number of 6 to 15), an alkoxy group (for example, a carbon number of 1 to 15), a halogen atom, a hydroxyl group, a phenylthio group or the like.

Z ^- represents a non-nucleophilic based anion, exemplified by the general formula (ZI) in the Z ^- of the same non-nucleophilic anions are.

Further, examples of the acid generator include compounds represented by the following general formulae (ZIV), (ZV), and (ZVI).

In the general formulae (ZIV) to (ZVI), Ar ₃ and Ar ₄ each independently represent an aryl group. R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group.

The A group represents an alkyl group, an alkenyl group or an aryl group.

Among the acid generators, compounds represented by the general formulae (ZI) to (ZIII) are more preferred.

Further, as the acid generator, an acid generating compound having a sulfonic acid group or a quinone imine group is preferred, and an acid generating compound of a monovalent perfluoroalkyl sulfo group or a monovalent product is further preferred. Further, an acid generating compound of an aromatic sulfo group substituted with a fluorine atom or a fluorine atom group, or an acid generating compound of a monovalent sulfonium atom group substituted with a fluorine atom or a fluorine atom group, further preferably, a fluorinated substituted alkylsulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted sulfimine or a fluorinated substituted methylated acid sulfonium salt. The acid generator which can be used is particularly preferably a fluorinated substituted alkylsulfonic acid, a fluorinated substituted benzenesulfonic acid or a fluorinated substituted sulfiliic acid having a pKa of pKa = -1 or less, which enhances sensitivity.

Among the acid generators, a particularly preferred example is given below.

[2] Solvent

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains at least one solvent selected from the group represented by any one of the following general formulae (S1) to (S4) as a mixed solvent (D). ).

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

In the general formulae (S1) to (S3), R ₁ to R ₇ each independently represent an alkyl substituent, may have a cycloalkyl substituent, or may have an aryl substituent. R ₁ and R ₂ , R ₃ and R ₄ , or R ₆ and R ₇ may be bonded to each other to form a ring.

R ₁ to R ₇ in the general formulae (S1) to (S3) are preferably an alkyl group, more preferably R ₁ and R ₂ , R ₃ and R ₄ , or R ₆ and R _{7 are} bonded to each other to form a ring.

The alkyl group of R ₁ to R ₇ may, for example, be an alkyl group having 1 to 4 carbon atoms. Examples of the cycloalkyl group include a cycloalkyl group having a carbon number of 3 to 6 (monocyclic or polycyclic), and examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. The substituent which is contained has a hydroxyl group.

Further, when R ₁ and R ₂ , R ₃ and R ₄ , R ₆ and R _{7 are} bonded to each other to form a ring (heterocyclic ring), R ₁ and R ₂ , R ₃ and R ₄ , R ₆ and R ₇ are used. The divalent base formed is preferably an alkylene group having 2 to 6 carbon atoms.

In the formula (S4), R ₃ and R ₉ each independently may have an alkyl substituent, or two groups may be bonded to each other to form a ring.

The alkyl group of R ₈ and R ₉ may, for example, be an alkyl group having 1 to 5 carbon atoms.

Preferably, R ₃ and R ₉ are bonded to each other to form a ring, preferably a 5- to 8-membered ring. The formula (S4) is more preferably represented by the following formula (s4). Wherein n is an integer from 1 to 4.

The solvent having a structure represented by the general formulae (S1) to (S4) is preferably a boiling point (1 atm) of from 150 to 250 ° C, more preferably from 180 to 250 ° C. For example, a solvent having an ester structure in γ-butyrolactone or the like, a cyclic ketone structure having a cyclopentanone or cyclohexanone, a n-methylpyrrolidone, a propylene carbonate or the like is preferable, and particularly Preferably, γ-butyrolactone or cyclohexanone is γ-butyrolactone.

The solvent which is less preferably used in the present invention is a protic solvent.

The protic solvent may, for example, be ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol or propylene glycol monomethyl ether (PGME, alias 1-methoxy-2-propanol). , propylene glycol monoethyl ether, ethyl lactate and the like.

The solvent (D) of the present invention is preferably an aprotic solvent which is preferably used in the solvent represented by the above formulas (S1) to (S4), and is not particularly limited, but propylene glycol monomethyl ether is exemplified. The acetate (PGMEA) is preferably a mixed solvent containing 50% by mass or more of PGMEA.

Suitable examples of the mixed solvent (D) include at least one solvent selected from the group consisting of the general formulas (S1) to (S4) and propylene glycol monomethyl ether acetate (PGMEA). Mixed solvent.

[3] A resin which increases the solubility to an alkali developer by the action of an acid

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin which increases the solubility to an alkali developer by the action of an acid (hereinafter also referred to as "resin (A)" or "acid-decomposable resin (A) "Wait."

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

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

The acid-decomposable group is preferably one having a structure in which the alkali-soluble group is decomposed and desorbed by the action of an acid.

The alkali-soluble group is not particularly limited as long as it is a group which dissociates to form an ion in an alkali developing solution, and a preferred base of the alkali-soluble group is a carboxyl group or a fluorinated alcohol group (preferably hexafluoroiso). Propyl alcohol), sulfonic acid group.

A group which is preferably an acid-decomposable group is a group in which a hydrogen atom of the alkali-soluble group is substituted with a group which is desorbed with an acid.

Examples of the group which is separated by an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )( R ₀₂ ) (OR ₃₉ ) and so on.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group. R ₃₆ and R ₃₇ may also 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 arylalkyl group or an alkenyl group.

Preferably, in terms of an acid-decomposable group, An ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

The repeating unit having the acid-decomposable group obtained by the resin (A) is preferably a repeating unit represented by the following 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 is a hydroxyl group or a monovalent organic group, and examples of the organic group include an alkyl group having 5 or less carbon atoms, a mercapto group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. . Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The T system represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represent an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).

At least two of Rx ₁ to Rx ₃ may also be combined to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the linking group of the two valencies of T include an alkylene group, a -COO-R tertiary group, and a -O-R tertiary group. In the formula, Rt represents an alkylene group or a cycloalkyl group.

The T system is preferably a single bond or a -COO-R tertiary group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH ₂ - group or a -(CH ₂ ) ₃ - group.

The alkyl group of Rx ₁ to Rx ₃ is preferably a carbon number of 1 to 4 such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a tertiary butyl group.

Cycloalkyl to Rx ₁ to _{Rx. 3} in terms of, preferably cyclopentyl, cyclohexyl, etc. groups of the monocyclic, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl A polycyclic cycloalkyl group.

The cycloalkyl group formed by bonding at least two of Rx ₁ to Rx ₃ is preferably a cycloalkyl group of a cyclopentyl group, a cyclohexyl group or the like, a decyl group, a tetracyclic fluorenyl group or a tetracyclic decene group. A polycyclic cycloalkyl group such as a dialkyl group or an adamantyl group.

Rx ₁ is a methyl group or an ethyl group, preferably a combination of Rx ₂ and Rx ₃ to form the above cycloalkyl group.

Each of the above-mentioned groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, and an alkoxy group. The carbonyl group (carbon number 2 to 6) or the like is preferably 8 or less carbon atoms.

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

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

In a specific example, 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. The Z system represents a substituent containing a polar group, a hydroxyl group, a cyano group, an amine group, an alkanoylamino group or a sulfonylamino group, or an alkyl group or a ring having any of these, a straight chain or a branched chain. alkyl. In the case where there are multiple cases, they are independent. p represents a system 0 or a positive integer.

The resin (A) is a resin represented by the general formula (AI), and preferably has at least one of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2). Further, the resin (A) is in another form, and the repeating unit represented by the general formula (AI) is preferably a resin having at least two kinds of repeating units represented by the general formula (1), and is also preferably a resin. A resin having at least one of a repeating unit represented by the formula (1) and at least one of a repeating unit represented by the formula (2).

In the formulae (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 represents preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The alkyl group in R ₂ may be a linear type or a branched type, and may have a substituent.

The cycloalkyl group in R ₂ may be a single ring or a polycyclic ring or may have a substituent.

R ₂ is preferably an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 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 having a carbon number of 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 a linear type or a branched type, and may have a substituent. The alkyl group is preferably a carbon number of 1 to 4 such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tertiary butyl group.

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be a single ring or a polycyclic ring or may have a substituent. In the case of a cycloalkyl group, a polycyclic ring such as a cyclopentyl group such as a cyclopentyl group or a cyclohexyl group, a decyl group, a tetracyclononyl group, a tetracyclododecyl group or an adamantyl group is preferable. alkyl.

The repeating unit represented by the formula (1) includes a repeating unit represented by the following formula (1-a).

In the formula, R ₁ and R ₂ are synonymous with each of the formula (1).

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

In the formula (2-1), R ₃ to R ₅ are synonymous with each of the formula (2).

R ₁₀ represents a substituent containing a polar group. There are a plurality of R ₁₀ cases, which may be the same or different from each other. The substituent containing a polar group may, for example, be a hydroxyl group, a cyano group, an amine group, an alkanoylamino group or a sulfonylamino group, or a linear or branched group having any of these. The alkyl group or the cycloalkyl group is preferably an alkyl group having a hydroxyl group. More preferably, it is a branched alkyl group having a hydroxyl group. In the case of a branched alkyl group, an isopropyl group is preferred.

p is an integer from 0 to 15. The p-system is preferably from 0 to 2, more preferably 0 or 1.

A preferred combination of the case where the resin (A) is decomposed with an acid by a repeating unit is preferably exemplified below. In the following formula, R each independently represents a hydrogen atom or a methyl group.

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

In the case of a lactone group, any one may be used as long as it has a lactone structure, but it is preferably a 5- to 7-membered ring lactone structure to form a bicyclic structure or a spiro structure in the form of a 5- to 7-membered cyclic lactone. It is better to construct other ring structures. More preferably, it has a repeating unit having a lactone structure represented by any one of the following general formulae (LC1-1) to (LC1-17). Further, the lactone structure may be directly bonded to the main chain. In terms of preferred lactone structure, (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17) The LWR and development defects are improved by the ester structure used in the specific one.

The lactone structural moiety may or may not have a substituent (Rb ₂ ). In ₍₂ Rb) in terms of preferred substituents include an alkyl group of 1 to 8 carbon atoms, a cycloalkyl group having a carbon number of 4 to 7 carbon atoms of an alkoxy group having 1 to 8 carbon atoms of 1 to 8, An alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, or the like. More preferably, it is an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. The n ₂ system represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

In the case of a repeating unit having a lactone structure. A repeating unit represented by the following formula (AII) is preferred.

In the formula (AII), Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Rb ₀ may have an alkyl group, and a preferred substituent is a hydroxyl group or 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. It is preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab is a 2-valent linking group, an ether group, an ester group, a carbonyl group, or a combination of these two-valent linking groups, which has a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure. It is preferably a single bond, a divalent linking group represented by -Ab ₁ -CO ₂ -. Ab ₁ is a linear, branched alkyl, monocyclic or polycyclic cycloalkyl group, preferably a methylene group, an ethyl group, a cyclohexyl group, an adamantyl group, or a decyl group.

V is a group having a lactone structure. Specifically, for example, it means a group having a structure represented by any one of the general formulae (LC1-1) to (LC1-17).

Among the units represented by the general formula (AII), the repeating unit having a lactone group particularly preferably in the case where Ab is a single bond includes the following repeating unit. In a specific example, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ . By selecting the most suitable lactone group, the appearance of the pattern and the density dependence become good.

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

In the formula (3), the A group represents an ester bond (group represented by -COO-) or a group represented by -CONH-.

R ₀ is a plurality of cases, each independently representing an alkylene group, a cycloalkyl group, or a combination thereof.

When there are a plurality of Z systems, each independently represents an ether bond, an ester bond, a guanamine bond, a urethane bond, or a urea bond.

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

n is a repeating number of a 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 alkyl group of R ₀ may have a substituent.

The Z system is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group of 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, and examples of the substituent include a halogen atom or a mercapto group such as a fluorine atom, a chlorine atom or a bromine atom, a hydroxyl group, a methoxy group, an ethoxy group, and an isopropoxy group. And an alkoxy group such as a tertiary butoxy group or a benzyloxy group; an ethoxy group such as an ethyl sulfonyl group or a propyl fluorenyl group; R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The preferred chain alkyl group in R ₀ is preferably a chain alkylene having a carbon number of 1 to 10, more preferably a carbon number of 1 to 5, and examples thereof include a methylene group and a stretching group. Base, propyl and the like. In the case of the preferred cyclic alkylene, the cyclic alkylene having 1 to 20 carbon atoms may, for example, be a cyclohexane, a cyclopentane, a decane, an adamantane or the like. In order to express the effect of the present invention, a chain alkyl group is preferred, and a methylene group is preferred.

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 formulae (LC1-1) to (LC1-17). Among these, the structure represented by (LC1-4) is particularly preferable. Further, it is more preferable that n ₂ is 2 or less in (LC1-1) to (LC1-17).

Further, R ₈ is an unsubstituted organic group having a lactone structure, or preferably a monovalent organic group having a lactone structure with a methyl group, a cyano group or an alkoxycarbonyl group as a substituent, The cyano group as a substituent has a monovalent organic group having a lactone structure (cyanolactone).

Specific examples of the repeating unit having a lactone structural group 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 or a halogen atom which may have a substituent, and preferably represents a hydrogen atom, a methyl group, a methyl group having a substituent, a hydroxymethyl group or an acetoxymethyl group. .

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

In the formula (3-1), R ₇ , A, R ₀ , Z, and n are synonymous with the above formula (3).

When R ₉ is plural, each independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group. In the case of a plurality of R ₉ groups, two R ₉ groups may be bonded and Form a ring.

The X system represents an alkyl group, an oxygen atom or a sulfur atom.

m is the number of substituents and represents an integer of 0 to 5. The m system is preferably 0 or 1.

The alkyl group of 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. The cycloalkyl group may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group. The ester group may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a n-butoxycarbonyl group or a tertiary butoxycarbonyl group. Examples of the substituent include a halogen atom such as an alkoxy group such as a hydroxyl group, a methoxy group or an ethoxy group, a cyano group or a fluorine atom.

The R ₉ system is more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and still more preferably a cyano group.

The alkyl group of X is a methylene group, an ethyl group, and the like. The X system is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

In the case of m = 1, it is preferred that R ₉ is substituted at the α-position or the β-position of the carbonyl group of the lactone, and it is particularly preferred to carry out the substitution at the α-position.

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

The repeating unit having a lactone group usually has an optical isomer, but any optical isomer can also 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%, still more preferably from 30 to 50 mol%, based on all the repeating units in the resin.

In order to enhance the effect of the present invention, two or more lactone repeating units selected from the general formula (3) may be used. In the case of the general formula (3), it is preferred to use two or more kinds of lactone repeating units having n of 1 for use. Further, in the general formula (AII), a repeating unit in which Ab is a single bond and a repeating unit in which a n is 1 in the formula (3) is also preferable.

The resin (A) is preferably a repeating unit having a hydroxyl group or a cyano group (a repeating unit represented by the above formula (3) or (AI) has a hydroxyl group or a cyano group, and is not included.). Thereby, the substrate adhesion and the developer affinity are improved. 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. In the alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group, an adamantyl group, a diamond alkyl group or a norbornyl group is preferable in terms of an alicyclic hydrocarbon structure. Preferred examples of the alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group include a monohydroxyadamantyl group, a dihydroxyadamantyl group, a monohydroxy diamond alkyl group, a dihydroxyadamantyl group, and a cyano group substitution.莰基等.

Examples of the repeating unit having the above atomic group include repeating units represented by the following general formulae (AIIa) to (AIId).

In the general formulae (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, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or both of R ₂ c to R ₄ c are a hydroxyl group, and the balance is a hydrogen atom. In the formula (VIIa), it is more preferred that two of R ₂ c to R ₄ c are a hydroxyl group, and the balance is a hydrogen atom.

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

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

The resin used in the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonylamino group, a sulfonyl fluorenylene group, a bis-sulfonyl fluorenylene group, and an α-position of an aliphatic alcohol substituted with an electron withdrawing group (for example, hexafluorocarbon). Isopropanol group) is more preferably a repeating unit having a carboxyl group. The resolution in the use of the contact hole is increased by containing a repeating unit having an alkali-soluble group. In the case of a repeating unit having an alkali-soluble group, a repeating unit such as acrylic acid or methacrylic acid directly bonds an alkali-soluble repeating unit based on a resin backbone, or an alkali-soluble resin-based backbone via a linking group The repeating unit, when further used for polymerizing a polymerization initiator or a chain shifting agent having an alkali-soluble group, is preferably introduced into the end of the polymer chain, and the linking group may also have a single ring or a polycyclic ring. Cyclic hydrocarbon structure. Particularly preferred is a repeating unit made of 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%, still more preferably 5 to 10 mol% based on all the repeating units in the resin (A). ear%.

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

The resin (A) of the present invention preferably further has an alicyclic hydrocarbon structure having no polar group and a repeating unit which does not exhibit acid decomposition property. Thereby, it is possible to reduce the elution of the low molecular component from the film formed of the photosensitive ray-sensitive or radiation-sensitive resin composition to the liquid immersion liquid during immersion exposure. The repeating unit represented by the general formula (4) is exemplified as such a repeating unit.

In the formula (4), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no hydroxyl group or cyano group.

The Ra system represents a hydrogen atom, an alkyl group or a -CH2-O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. Ra is preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

The cyclic structure of R ₅ has a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. The monocyclic hydrocarbon group may, for example, be a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group having 3 to 12 carbon atoms. In the preferred monocyclic hydrocarbon group, it is a monocyclic hydrocarbon group having 3 to 7 carbon atoms.

In the polycyclic hydrocarbon group, it contains a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a 4-ring hydrocarbon ring. Further, the crosslinked cyclic hydrocarbon ring also contains a condensed cyclic hydrocarbon ring (for example, a condensed ring obtained by shrinking a plurality of 5- to 8-membered cycloalkyl rings). Preferred examples of the crosslinked cyclic hydrocarbon ring include a thiol group and an adamantyl group.

The alicyclic hydrocarbon group may have a substituent. Preferred substituents include a halogen atom, an alkyl group, a protecting group-protected hydroxyl group, a protecting group-protected amine group, and the like. The preferred halogen atom is a bromine, chlorine or fluorine atom, and a preferred alkyl group is a methyl group, an ethyl group, a butyl group or a tertiary butyl group. The above alkyl group may further have a substituent, and examples of the substituent may further include a halogen atom, an alkyl group, a protecting group-protected hydroxyl group, and a protecting group-protected amine group.

The protecting group may, for example, be an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group or an aralkyloxycarbonyl group. The preferred alkyl group is an alkyl group having 1 to 4 carbon atoms, and the preferred substituted methyl group is methoxymethyl, methoxythiomethyl, benzyloxymethyl or the like. a butoxymethyl group, a 2-methoxyethoxymethyl group, and a preferably substituted ethyl group, a 1-ethoxyethyl group, a 1-methyl-1-methoxy group The ethyl group, preferably a mercapto group, may have a carbon number of 1 to 6 such as a mercapto group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl sulfonyl group, an isobutyl fluorenyl group, a pentamidine group or a trimethyl acetyl group. The group is a fluorenyl group, and the alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 4 carbon atoms.

The alicyclic hydrocarbon structure having no polar group, and the content of the repeating unit which does not exhibit acid decomposition property is preferably 0 to 40 mol%, more preferably 0 to 20 mol% based on all the repeating units in the resin (A). ear%.

Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and exhibiting no acid decomposition property are listed below, but the present invention is not limited thereto. In the formula, the Ra system represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The resin used in the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is adjusted for dry etching resistance or standard developer suitability, substrate adhesion, photoresist profile, and further light in addition to the above-described repetitive structure unit. The resolving power, heat resistance, sensitivity, etc., which are generally required for the resistance, may have various repetitive structural units.

In the case of such a repeating structural unit, a repeating structural unit corresponding to the following monomer may be mentioned, but it is not limited thereto.

Thereby, the properties required for the resin used for the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention can be finely adjusted, in particular, (1) solubility in a coating solvent, and (2) film forming property (glass) Transfer point), (3) alkali developability, (4) film thinning (hydrophobicity, alkali-soluble base selection), (5) adhesion to a substrate of an unexposed portion, (6) dry etching resistance, and the like.

Examples of such a monomer include those selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. One compound which adds a polymerizable unsaturated bond, etc.

Other than the addition polymerizable unsaturated compound copolymerizable with the monomer corresponding to the above various repeating structural units, it may be copolymerized.

In the resin (A) used in the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention, each of the repeating structural units contains a molar ratio in order to adjust the dry etching resistance of the photoresist or the standard developer suitability, substrate adhesion The properties, the resist profile, and the resolution, heat resistance, sensitivity, and the like of the performance required for the general resistance of the photoresist are appropriately set.

When the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is used for ArF exposure, it is preferably used for the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention from the viewpoint of transparency to ArF light. The resin (A) does not have an aromatic group.

Further, the resin (A) is preferably a fluorine-free atom or a ruthenium atom from the viewpoint of compatibility with a hydrophobic resin (C) to be described later.

The resin (A) used in the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is preferably one in which all repeating units are composed of (meth)acrylic repeating units. In this case, any of the repeating units may be a methacrylic repeating unit, all of the repeating units may be an acrylic repeating unit, and all of the repeating units may be a methacrylic repeating unit and an acrylic repeating unit. However, it is preferred that the acrylic repeating unit be 50 mol% or less of all repeating units.

Further, it is preferably 20 to 50 mol% of a (meth)acrylic repeating unit having an acid-decomposable group, 20 to 50 mol% of a (meth)acrylic repeating unit having a lactone group, and a hydroxyl group or a cyanide group. A copolymer of 5 to 30 mol% of a (meth)acrylic repeating unit having an alicyclic hydrocarbon structure, further containing 0 to 20 mol% of other (meth)acrylic repeating units.

The resin (A) of the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, in a general synthesis method, a monomer species and an initiator are dissolved in a solvent, and polymerization is carried out by heating, and the monomer species is added dropwise in 1 to 10 hours in a heating solvent. The solution of the initiator is dropped into a polymerization method or the like, and is preferably a dropping polymerization method. The reaction solvent may, for example, be tetrahydrofuran or 1,4-di An ether such as an alkane or a diisopropyl ether; a ketone such as methyl ethyl ketone or methyl isobutyl ketone; an ester solvent such as ethyl acetate; dimethylformamide or dimethylacetonitrile; A solvent for dissolving the composition of the present invention, such as a guanamine solvent such as an amine, further propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or cyclohexanone described later. It is more preferably polymerized by using the same solvent as the solvent used in the composition of the present invention. Thereby, generation of particles during storage can be suppressed.

The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. A polymerization initiator is used to start polymerization by using a commercially available radical initiator (azo initiator, peroxide, etc.). The radical initiator is preferably an azo initiator, and an azo initiator having an ester group, a cyano group or a carboxyl group is preferred. Preferred examples of the initiator include azobisisobutyronitrile group, azobisdimethylvaleronitrile group, dimethyl 2,2'-azobis(2-methylpropionate), and the like. The desired polymer is added as needed, or the starting agent is added in portions, and after completion of the reaction, the solvent is charged in a powder form or solid recovery. The concentration of the reaction is from 5 to 50% by mass, preferably from 10 to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, further preferably from 60 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, even more preferably from 3,000 to 3,000 in terms of polystyrene by the GPC method. To 10,000. When the weight average molecular weight is in the above range, heat resistance can be improved or dry etching resistance can be prevented from deteriorating, deterioration of developability, deterioration of film forming property due to high viscosity, and the like can be prevented.

The degree of dispersion (molecular weight distribution) is usually in the range of from 1 to 3, preferably from 1 to 2.6, still more preferably from 1 to 2, particularly preferably from 1.4 to 2.0. The smaller the molecular weight distribution, the superior the resolution and the shape of the photoresist, and the side walls of the photoresist pattern are smooth and excellent in roughness.

The amount of the composition of the resin (A) of the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is preferably from 50 to 80% by mass, more preferably from 60 to 80% by mass, based on the total solid content.

Further, the resin (A) of the present invention may be used alone or in combination of two or more.

[3] at least one of a fluorine atom and a ruthenium atom and a resin having a polar conversion group which decomposes by an action of an alkali developer and increases solubility in an alkali developer

The photosensitive ray or radiation-sensitive resin composition of the present invention contains a repeating unit (c) having at least one polar group and contains a resin (C) having at least one of a fluorine atom and a ruthenium atom. The resin (C) is hydrophobic, but the addition of the resin (C) is particularly preferable at the point of reducing development defects.

Here, the polar conversion group is a group which decomposes by the action of an alkali developing solution and increases the solubility in the alkali developing solution. For example, a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C(O)OC(O)-), an acid sulfoximine group (-NHCONH-), a carboxylic acid thioester group (- COS-), carbonate group (-OC(O)O-), sulfate group (-OSO ₂ O-), sulfonate group (-SO ₂ O-), and the like.

Further, in the acrylate or the like, the ester group directly bonded to the main chain of the repeating unit is poor in the function of decomposing by the action of the alkali developing solution and increasing the solubility in the alkali developing solution. The invention does not contain a polar transducer.

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

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

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

However, at least one of R _k1 and R _k2 has a polar conversion group.

Further, the ester group which is directly bonded to the main chain of the repeating unit represented by the formula (K0) is not included in the polar group in the present invention as described above.

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

X in the formula (KA-1) or (KB-1) represents a carboxylate group: -COO-, an acid anhydride group: -C(O)OC(O)-, a hydrazide imine group: -NHCONH- Carboxylic acid ester group: -COS-, carbonate group: -OC(O)O-, sulfate group: -OSO ₂ O-, sulfonate group: -SO ₂ O-.

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

Further, since the repeating unit (c) has a group having a partial structure represented by the general formula (KA-1) or (KB-1), it has a preferred polar conversion group, but is represented by the general formula (KA-1). Partial structure, as in the case where Y ¹ and Y ² are part of the structure represented by the case of monovalent (KB-1), the part of the structure generally has no connection bond, and the basis of the structure having the partial structure is removed. A group having a monovalent or higher group of at least one arbitrary hydrogen atom in the partial structure. A partial structure represented by the general formula (KA-1) or (KB-1) is bonded to the main chain of the resin (C) via a substituent at an arbitrary position.

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

X in the general formula (KA-1) is preferably a carboxylate group (that is, a case where KA-1 forms a lactone ring structure), and an acid anhydride group or a carbonate group. More preferably, it is a carboxylate group.

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

There are a plurality of cases of Z _ka1 each independently representing an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, a decylamino group, an aryl group, a lactone ring group, or an electron withdrawing group.

Z _ka1 may also be bonded to each other to form a ring. _Examples of the ring formed by bonding Z _{ka1 to} each other include a cycloalkane ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).

The nka system represents an integer of 0 to 10. It is preferably an integer of 0 to 8, more preferably an integer of 0 to 5, further preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

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

Further, the above electron withdrawing group may be substituted by another electron withdrawing group.

Z _kal 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. Further, in the case of an ether group, those substituted with an alkyl group or a cycloalkyl group, that is, an alkyl ether group or the like are preferred. The electron withdrawing system is synonymous with the foregoing.

The halogen atom of Z _{kal is preferably} a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and the fluorine atom is preferred.

The alkyl group which is Z _kal may have a substituent, and may be either a straight chain or a branch. The linear alkyl group is preferably a carbon number of 1 to 30, more preferably 1 to 20, and examples thereof include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a secondary butyl group, and a tertiary group. Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl and the like. The branched alkyl group is preferably a carbon number of 3 to 30, further preferably 3 to 20, and examples thereof include an isopropyl group, an isobutyl group, a tertiary butyl group, an isopentyl group, and a tertiary pentyl group. , isohexyl, tertiary hexyl, isoheptyl, tertiary heptyl, isooctyl, tertiary octyl, isodecyl, tertiary sulfhydryl, and the like. It is preferably a carbon number of 1 to 4 such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tertiary butyl group.

The cycloalkyl group of Z _kal may have a substituent, and may be a monocyclic type, a polycyclic type, or a bridged type. For example, a cycloalkyl group may have a crosslinked structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group and the like. The polycyclic type may be a group having a bicyclic ring, a tricyclic ring or a tetracyclic structure having a carbon number of 5 or more, and preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include adamantyl group and a lower alkyl group. Indenyl, isodecyl, camphoryl, dicyclopentyl, α-decenyl, tricyclodecyl, tetracyclododecyl, androstanyl or the like. Further, a part of the carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

Preferred examples of the above alicyclic moiety include adamantyl, noradamantyl, decahydronaphthyl, tricyclodecyl, tetracyclododecyl, norbornyl, cedar, and ring. Hexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl. More preferred are adamantyl, decahydronaphthyl, norbornyl, cedarol, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, tricyclodecyl.

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, and more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. The alkoxy group is preferably a carbon number of 1 to 4 such as a methoxy group, an ethoxy group, a propoxy group or 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, a carbon number of 1 to 4).

Further, examples of the further substituent which the above-mentioned group may have include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, and a cyano group, and the above alkyl group may be a methoxy group or a Alkoxy groups such as oxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, ternary butoxy, tert-butoxy, etc., methoxycarbonyl, B Alkoxycarbonyl group such as oxycarbonyl group, benzyl group, phenethyl group, An aryl group, an aralkyloxy group, a decyl group, an ethyl fluorenyl group, a butyl group, a benzyl group, a cyanomyl group, a fluorenyl group such as a pentyl group, a butyl group, etc. The oxy group, the alkenyl group described above may be an alkenyloxy group such as a vinyloxy group, a propyleneoxy group, an allyloxy group or a butenyloxy group, and the aryl group may be an aryloxy group such as a phenoxy group. An aryloxycarbonyl group such as a benzamidine group or the like.

X in the formula (KA-1) is a carboxylate group, and a part of the structure represented by the formula (KA-1) is preferably a lactone ring, preferably a 5- to 7-membered lactone ring.

Further, as in the following (KA-1-1) to (KA-1-17), a 5- to 7-membered ring lactone ring which is a part represented by the formula (KA-1) is preferably used to form a double ring. The structure, the form of the spiral structure shrinks the ring structure.

The ring structure which can be bonded to the ring structure represented by the general formula (KA-1) is, for example, the following (KA-1-1) to (KA-1-17), or Those.

The structure including the lactone ring structure represented by the general formula (KA-1) is more preferably a structure represented by any one of the following (KA-1-1) to (KA-1-17). In addition, the lactone structure can also be directly bonded to the main chain. In a preferred configuration, (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA -1-14), (KA-1-17).

The structure containing the lactone ring structure may or may not have a substituent. The preferred substituent is the same as the substituent which the ring structure represented by the above formula (KA-1) may have.

The lactone structure also has optical isomers, but any optical isomer may also be used. Further, one type of optical isomer may be used alone or a plurality of optical isomers may be used in combination. When one type of optical isomer is mainly used, the optical purity (enantiomeric excess value) (ee) is preferably 90 or more, more preferably 95 or more, and most preferably 98 or more.

The X of the formula (KB-1) is preferably a carboxylate group (-COO-).

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

The electron withdrawing system is constructed by a part represented by the following formula (EW). The * in the formula (EW) indicates a linkage key directly bonded to (KA-1) or a linkage key directly bonded to X in (KB-1).

In the formula (EW), n _ew is a repeating number of a linking group represented by -C(R _ew1 )(R _ew2 )-, and represents an integer of 0 or 1. The case where n _ew is 0 indicates a single bond, indicating a direct bond Y _ew1 .

_Examples of Y _ew1 include a halogen atom, a cyano group, a nitrile group, a nitro group, a halogen (cyclo)alkyl group represented by —C(R _f1 )(R _f2 )—R _f3 , a halogenoaryl group, an oxy group, a carbonyl group, The sulfonyl group, the sulfinyl group, and combinations thereof may be, for example, the following structures. Further, the "halo (cyclo)alkyl group" means at least a part of a halogenated alkyl group and a cycloalkyl group. R _ew3 and R _ew4 each independently represent an arbitrary structure. Regardless of the structure of R _ew3 or R _ew4 , a _part of the structure represented by the formula (EW) has an electron attracting property, and may be bonded to, for example, a main chain of a resin, but is preferably an alkyl group, a cycloalkyl group, or a fluorinated group. alkyl.

When Y _ew1 is a group having two or more valences, the remaining linking bonds form a bond with any atom or substituent. At least several groups of Y _ew1 , R _ew1 , and R _ew2 may be linked to the main chain of the resin (C) via a further substituent.

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

R _ew1 and R _ew2 each independently represent an arbitrary substituent and represent, 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 also be combined with each other to form a ring.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, and even more preferably a fluorine atom. Or trifluoromethyl.

R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and may be bonded to R _f2 and R _f3 to form a ring. The organic group means, for example, an alkyl group, a cycloalkyl group, an alkoxy group or the like. R _f2 represents the same group as R _f1 or more preferably is bonded to R _{f3 to} form a ring.

R _f1 to R _f3 may be bonded to each other to form a ring, and examples of the ring to be formed include a (halo)cycloalkane ring and a (halogen)aryl ring.

The (halo)alkyl group in R _f1 to R _f3 may, for example, be an alkyl group in the above Z _ka1 and a halogenated structure.

The ( _per )halocycloalkyl group and the ( _per )haloaryl group in R _f1 to R _f3 or in the ring formed by linking R _f2 to R _f3 include, for example, the ring in the aforementioned Z _ka1 The structure in which the alkyl group is halogenated is more preferably a fluoroalkyl group represented by -C _(n) F _(2n-2) H and a perfluoroaryl group represented by -C _(n) F _(n-1) . The carbon number n is not particularly limited, but preferably 5 to 13 and 6 is more preferable.

The ring formed by _joining at least two of R _ew1 , R _ew2 and Y _{ew1 to} each other may preferably be a cycloalkyl group or a heterocyclic group, and a heterocyclic group is preferably a lactone ring group. The lactone ring is, for example, a structure represented by the above formulas (KA-1-1) to (KA-1-17).

Further, in the repeating unit (c), a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or a general formula (KA) may be provided. Part of the structure of -1) and the formula (KB-1).

Further, part or all of a part of the structure of the general formula (KA-1) may simultaneously be an electron withdrawing group of Y ¹ or Y ^{2 in} the formula (KB-1). For example, when X of the formula (KA-1) is a carboxylate group, the carboxylate group may also function as an electron withdrawing group of Y ¹ or Y ^{2 in} the formula (KB-1).

The repeating unit (c) may be a repeating unit (c') having at least one of a fluorine atom and a ruthenium atom and a polar conversion group on one side chain, or may have a polar conversion group and no fluorine atom or ruthenium atom. The repeating unit (c*) may also be a repeating unit having at least one of a fluorine atom and a ruthenium atom having a polar group on one side chain and having a different side chain from the side chain in the same repeating unit (c) "), but the resin (C) is preferably a repeating unit (c) having a repeating unit (c').

Further, the resin (C) has a repeating unit (c*), and is preferably a copolymer with a repeating unit (repeating unit (c1) to be described later) having at least one of a fluorine atom and a ruthenium atom. Further, the side chain having a polar conversion group in the repeating unit (c") and the side chain having at least one of a fluorine atom and a ruthenium atom are preferably the same carbon atom bonded to the main chain, that is, A general positional relationship of the following formula (4): wherein B1 represents a partial structure having a polar conversion group, and B2 represents a partial structure having at least one of a fluorine atom and a germanium atom.

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

Since the polar conversion group is decomposed by the action of the alkali developing solution and causes polarity switching, the receding contact angle with the water of the resin composition film after alkali development can be reduced.

The receding contact angle of the resin composition film after alkali development with water is preferably 30±3° C. in a room temperature, 23±3° C. in a room temperature, and 45° or less in a humidity of 45±5%, more preferably 40° or less. It is further preferably 35 or less, and most preferably 30 or less.

The receding contact angle is a contact angle measured when the contact line of the droplet-substrate interface retreats, and is generally useful for simulating the dynamic mobility of droplets. Briefly, it can be defined as the contact angle when the droplets ejected from the needle end are dropped onto the substrate and then the droplets are reabsorbed to the needle when the interface of the droplets retreats. The measurement method of the contact angle is performed.

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

The rate of hydrolysis of the alkali developer to the resin (C) is a film thickness of TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%) at 23 ° C, when the resin (C) is formed into a resin film. Reduced speed.

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

In the case where the repeating unit (c) has at least two polar groups, it is preferred to have a group having a partial structure having two polar groups represented by the following formula (KY-1). Further, the structure represented by the general formula (KY-1) does not have a linking bond, and is a group having a monovalent or higher group in which at least one arbitrary hydrogen atom in the structure is removed.

General formula (KY-1) in _a, R _ky1, R ky4 lines each independently represent a hydrogen atom, a halogen atom, alkyl, cycloalkyl, carbonyl group, carbonyloxy group, oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, Amidino or aryl. Or, _{R ky1,} R ky4 junction may form a double bond to the same atom, for example _{R ky1,} R ky4 junction may also be part of the same oxygen atom of a carbonyl group (= O) is formed.

_{R ky2,} R ky3 lines each independently an electron-withdrawing, or R _ky1 and R _ky2 linked to form a lactone ring, while _R ky3 electron withdrawing group. The lactone ring formed is preferably a structure of the above (KA-1-1) to (KA-1-17). The electron-withdrawing group is the same as Y ¹ and Y ² in the above formula (KB-1), preferably a halogen atom, or represented by -C(R _f1 )(R _f2 )-R _f3 Halogen (cyclo)alkyl or haloaryl. _R ky3 is preferably a halogen atom or a halo (cyclo) _f3 represents an alkyl group or an aryl halide group, R _ky2 and R _ky1 are connected by _{-C (R f1) (R f2} ) -R form a lactone ring, with or without An electron withdrawing group of a halogen atom.

_{R ky1,} R _ky2, R ky4 linked to each other by the respective lines may form a monocyclic or polycyclic structure.

_{R ky1,} R ky4 based particularly include the same group of the (KA-1) in the Z _ka1.

R _ky1 lactone form of the coupling ring and R _ky2, preferable are the (KA-1-1) to (KA-1-17) of the structure. The electron-withdrawing group is the same as Y ¹ and Y ² in the above 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). Further, the structure represented by the general formula (KY-2) has a group having a monovalent or higher group in which at least one of the hydrogen atoms in the structure is removed.

Of formula (KY-2) _in, R ky6 to _R ky10 lines each independently represent 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, acyl Amine, or aryl.

R _ky6 to R _ky10 may be connected to each other in two or more to form a single ring or a polycyclic structure.

R _ky5 represents an electron withdrawing group. The electron withdrawing group is the same as those of the above Y ¹ and Y ² , and is preferably a halogen atom or a halogen (cyclo)alkyl group or a halogen represented by -C(R _f1 )(R _f2 )-R _f3 . Aryl.

R _ky5 to R _ky10 are specifically the same as those of Z _ka1 in the formula (KA-1).

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

In the formula (KY-3), each of Z _ka1 and nka is synonymous with the above formula (KA-1). The R _ky5 system is synonymous with the above formula (KY-2).

L _ky means an alkyl group, an oxygen atom or a sulfur atom. The methylene group, the ethyl group and the like are exemplified by the alkyl group of L _ky . The L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

The repeating unit (c) is not limited as long as it is obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation or the like, but is preferably obtained by addition polymerization of a carbon-carbon double bond. Repeat unit. Examples thereof include acrylic repeating units (including a system having a substituent at the α-position and the β-position), a styrene-based repeating unit (a system also having a substituent at the α-position and the β-position), and a vinyl ether. a repeating unit of a repeating unit, a norbornene-based repeating unit, a maleic acid derivative (maleic anhydride or a derivative thereof, maleimide, etc.), preferably an acrylic repeat a unit, a styrene repeating unit, a vinyl ether repeating unit, a norbornene-based repeating unit, more preferably an acrylic repeating unit, a vinyl ether-based repeating unit, or a norbornene-based repeating unit, and an acrylic repeating unit optimal.

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

In the formula (cc), the Z ₁ groups each independently represent a single bond, an ether bond, an ester bond, a guanamine bond, a urethane bond or a urea bond, and preferably represent an ester bond.

The Z ₂ groups each independently represent a chain or cyclic alkyl group, and preferably represent a C 1 or 2 alkylene group or a C 5 to 10 cycloalkyl group.

The Ta system each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, a decylamino group, an aryl group or an electron withdrawing group (as in the above formula (KB-1) as Y ¹ and Y ² The electron withdrawing group is synonymous), preferably an alkyl group, a cycloalkyl group, an electron withdrawing group, and more preferably an electron withdrawing group. In the case where there are a plurality of Ta, Ta may be bonded to each other to form a ring.

L ₀ represents a single bond or a hydrocarbon group of m+1 (preferably having a carbon number of 20 or less), and preferably represents a single bond. As a single bond of L ₀ , m is 1. The hydrocarbon group which is a m+1 valence of L ₀ represents, for example, an alkyl group, a cycloalkyl group, a phenyl group, or a m+1 valent hydrocarbon group in which m-1 arbitrary hydrogen atoms are removed from the combination. When k is 2, two L ₀ may also be bonded to each other to form a ring.

The L system 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, a decylamino group, an aryl group or an electron withdrawing group (and an electron withdrawing group as Y ¹ and Y ^{2 in} the above formula (KB-1)) Synonymous).

* indicates a bond to the main chain or side chain of the resin. That is, a part of the structure represented by the formula (cc) may be directly bonded to the main chain, or a portion represented by the formula (cc) may be bonded to the side chain of the resin. Further, the connection bond to the main chain is a bond to an atom existing in a bond constituting the main chain, and the bond of the opposite side chain is an atom existing in a bond other than the bond constituting the main chain. Connection key.

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

k is an integer of 0 to 2, preferably 1.

The q system represents an integer of 0 to 5, preferably 0 to 2.

r is an integer from 0 to 5.

Further, instead of -(L)r-Tc, -L0-(Ta)m may be substituted.

In the case where the terminal of the sugar lactone has a fluorine atom, and the side chain having a side chain different from the sugar lactone side in the same repeating unit has a fluorine atom (repeating unit (c")) is also preferable.

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

In the general formulae (ca-2) and (cb-2), Z ₁ , Z ₂ , Tc, Ta, L, q and r are synonymous with each of the formula (cc).

Each of Tb independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, a decylamino group, an aryl group or an electron withdrawing group (as in the above formula (KB-1) as Y ¹ and Y ² The electron-withdrawing base is synonymous).

* indicates a bond to the main chain or side chain of the resin. That is, a part of the structure represented by the formula (ca-2) or (cb-2) may be directly bonded to the main chain, and the side chain of the resin may be bonded by the formula (ca-2) or (cb-2). Indicates the partial construction.

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

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

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

In the formula (2), R ₂ represents a chain or a cyclic alkyl group, and when it is plural, it may be the same or different.

R ₃ is a hydrocarbon group in which a part or all of a hydrogen atom on a carbon is substituted with a fluorine atom, and represents a linear, branched or cyclic hydrocarbon group.

R ₄ represents a halogen atom, a cyano group, a hydroxyl group, a decylamino group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, a fluorenyl group, an alkoxycarbonyl group, or RC(=O)- or RC ( =O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). There are a plurality of cases of R ₄ , which may be the same or different, and two or more R ₄ may be bonded and form a ring.

The X system represents an alkyl group, an oxygen atom or a sulfur atom.

The Z system represents a single bond, an ether bond, an ester bond, a guanamine bond, a urethane bond or a urea bond, and when there are a plurality of them, they may be the same or different.

* indicates the connection key to the main chain of the resin.

The n system represents a repetition number and represents an integer of 0 to 5.

m is the number of substituents and represents an integer of 0 to 7.

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

A specific example of the repeating unit (c) having a polar shift group is shown, but is not limited thereto.

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

Further, the resin (C) contains a repeating unit having at least one of a fluorine atom and a ruthenium atom.

Thereby, the photosensitive ray or the radiation sensitive resin film is on the surface layer, the resin (C) is not uniform, and the liquid immersion medium is water, and the surface of the photoresist film for water when the sensitized ray or the radiation sensitive resin is formed into a film The back contact angle is raised to improve the liquid immersion followability.

The photosensitive ray or the radiation sensitive resin film is subjected to a back contact angle system, and the temperature at the time of exposure is usually 23±3° C. at room temperature and 45±5% at a humidity, preferably 60° to 90°, more preferably 65° or more. More preferably, it is 70 or more, and particularly preferably 75 or more.

The resin (C) is generally not uniform at the interface as described above, but unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule, and it is not advantageous to uniformly mix the polar/nonpolar substance.

In the immersion exposure step, the exposure head is followed by scanning the wafer at a high speed to form an exposure pattern. Since the liquid immersion liquid needs to be active on the wafer, the contact angle of the liquid immersion liquid for the photoresist film becomes important in the dynamic state. The droplets have no residue, and the performance of the high-speed scanning following the exposure head is required by the photoresist system.

As the resin (C), since at least one of a fluorine atom and a ruthenium atom is provided, the hydrophobicity (water followability) of the resist surface is improved, and the development residue (scum) is reduced.

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

The alkyl group having a fluorine atom (preferably having a carbon number of 1 to 10, more preferably 1 to 4 carbon atoms) may have a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further substituted base.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may have further substituents.

The aryl group having a fluorine atom may be one in which a hydrogen atom of at least one of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may have further substituents.

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 formulae (F2) to (F4). The present invention is not limited thereto.

In the general formulae (F2) to (F4), R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight chain or branched). However, 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 represent a fluorine atom, or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably Carbon number 1 to 4).

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

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

Specific examples of the group represented by the formula (F3) include a trifluoromethyl group, a pentafluoropropyl group, a pentafluoroethyl group, a heptafluorobutyl group, a hexafluoroisopropyl group, and a heptafluoroisopropyl group. Hexafluoro(2-methyl)isopropyl, nonafluorobutyl, octafluoroisobutyl, nonafluorohexyl, nonafluoro-tertiary butyl, perfluoroisopentyl, perfluorooctyl, perfluoro(three Methyl)hexyl, 2,2,3,3-tetrafluorocyclobutyl, perfluorocyclohexyl, and the like. More preferably, it is hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro(2-methyl)isopropyl, octafluoroisobutyl, nonafluoro-tertiary butyl, perfluoroisopentyl, and further preferably It is hexafluoroisopropyl or heptafluoroisopropyl.

Specific examples of the group represented by the general formula (F4) include, for example, -C(CF ₃ ) ₂ OH, -C(C ₂ F ₅ ) ₂ OH, and -C(CF ₃ )(CH ₃ ). OH, -CH(CF ₃ )OH or the like is preferably -C(CF ₃ ) ₂ OH.

The fluorine-containing part of the structure may also be directly bonded, or further may be derived from an alkyl group, a phenyl group, an ether group, a thioether group, a carbonyl group, an ester group, a decyl group, an urethane group, or a stretching group. The group consisting of urea groups is selected to be bonded alone or in combination of two or more groups.

The repeating unit having a fluorine atom is preferably a lower one.

In the formula, 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; In particular, fluorinated alkyl groups are mentioned.

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

Further, a resin having a unit as generally shown below may be applied in addition to these.

In the formula, 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; In particular, a fluorinated alkyl group can be mentioned. However, at least one of R ₄ to R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may also form a ring.

W ₂ represents an organic group containing at least one fluorine atom. Specifically, the atomic groups of the above (F2) to (F4) are mentioned.

L ₂ represents a single bond or a divalent linking group. In the case of a divalent linking group, a substituted or unsubstituted extended aryl group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted stretched cycloalkyl group, -O-, -SO ₂ -, -CO- And -N(R)- (wherein R represents a hydrogen atom or an alkyl group), -NHSO ₂ - or a combination of a plurality of such divalent linking groups.

As the partial structure having a ruthenium atom in the repeating unit, a resin having an alkyl fluorenylene structure (preferably a trialkyl decyl group) or a cyclic siloxane structure is preferable.

Specific examples of the alkyl fluorenyl structure and the cyclic siloxane structure include a group represented by the following general formulae (CS-1) to (CS-3).

In the general formulae (CS-1) to (CS-3), R ₁₂ to R ₂₆ each independently represent a straight-chain or branched alkyl group (preferably, a carbon number of 1 to 20) or a cycloalkyl group (preferably). The carbon number is 3 to 20).

L ₃ to L ₅ represent a single bond or a divalent linking group. The divalent linking group may be composed of an alkyl group, a phenyl group, an ether group, a thioether group, a carbonyl group, an ester group, a decyl group, a urethane group or a ureido group. The group selection is either alone or a combination of two or more.

The n system represents an integer of 1 to 5.

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

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

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

The structure having a fluorine atom in the repeating unit (c1) is the same as the above, and is preferably a group represented by the above formulas (F2) to (F4).

The partial structure having a ruthenium atom in the repeating unit (c1) is the same as the above, and is preferably a group represented by the above formula (CS-1) to (CS-3).

The repeating unit (c1) is preferably a (meth)acrylic repeating unit.

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

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

(x) an alkali-soluble group, (z) a group decomposed by the action of an acid.

Examples of the (x) alkali-soluble group include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamino group, a sulfonimide group, or an alkylsulfonyl group. Methyl carbonyl) methylene, (alkyl sulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl) fluorenylene, bis (alkyl sulfonate) Mercapto) methylene, bis(alkylsulfonyl)phosphonium imino group, ginseng (alkylcarbonyl) methylene group, ginseng (alkylsulfonyl) methylene group, and the like.

The preferred alkali-soluble group may, for example, be a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group or a bis(carbonyl)methylene group.

The repeating unit having an alkali-soluble group (x) may be a repeating unit in which a base-soluble group is directly bonded to a main chain of a resin such as a repeating unit of acrylic acid or methacrylic acid, or a link-based resin. The repeating unit of the main chain-bonded alkali-soluble group or the like may be further introduced at the end of the polymer chain by using a polymerization initiator or a chain-moving agent having an alkali-soluble group during polymerization, and any of them is preferred. .

The content of the repeating unit having the alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 30 mol%, based on all the 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 a specific example, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

In the resin (C), the repeating unit having a group (z) which is decomposed by the action of an acid is the same as the repeating unit having an acid-decomposable group exemplified by the resin of the component (A) to be described later. Preferably, in terms of an acid-decomposable group, An ester group, an enol ester group, an acetal ester group, a 3-alkyl ester group or the like. More preferably, it is a 3-stage alkyl ester group.

In the case of a repeating unit having an acid-decomposable group, a repeating unit represented by the following formula (CAI) is preferred.

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 is a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and a mercapto group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa ₁ represents preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The T system represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represent an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).

At least two of Rx ₁ to Rx ₃ may also be combined to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the linking group of the two valencies of T include an alkylene group, a -COO-R tertiary group, and a -O-R tertiary group. In the formula, Rt represents an alkylene group or a cycloalkyl group.

The T system is preferably a single bond or a -COO-R tertiary group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH ₂ - group or a -(CH ₂ ) ₃ - group.

The alkyl group of Rx ₁ to Rx ₃ is preferably a carbon number of 1 to 4 such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a tertiary butyl group.

Cycloalkyl to Rx ₁ to _{Rx. 3} in terms of, preferably cyclopentyl, cyclohexyl, etc. groups of the monocyclic, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl A polycyclic cycloalkyl group.

In the case of a cycloalkyl group formed by bonding at least two of Rx ₁ to Rx ₃ , a cycloalkyl group of a monocyclic group such as a cyclopentyl group or a cyclohexyl group, a decyl group, a tetracyclic fluorenyl group, and a tetracyclic decene are preferable. A polycyclic cycloalkyl group such as a dialkyl group or an adamantyl group.

It is preferred that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the above cycloalkyl group.

Each of the above-mentioned groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, and an alkoxy group. The carbonyl group (carbon number 2 to 6) or the like is preferably 8 or less carbon atoms.

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

The resin (C) may further have other repeating units. The following are the preferred aspects of other repeating units.

(cy1) a repeating unit having a fluorine atom and/or a ruthenium atom and being stable to an acid and insoluble or insoluble to an alkali developer.

(cy2) a repeating unit which does not have a fluorine atom or a ruthenium atom, is stable to an acid, and is insoluble or insoluble to an alkali developer.

(cy3) a repeating unit having a fluorine atom and/or a ruthenium atom and having a polar group other than the above (x) and (z).

(cy4) a repeating unit which does not have a fluorine atom or a ruthenium atom and has a polar group other than the above (x) and (z).

The so-called (cy1), (cy2) repeating unit is sparingly soluble or insoluble in an alkali developing solution, indicating that (cy1), (cy2) is an alkali-soluble group-free or alkali-soluble by the action of an acid or alkali developing solution. a group (for example, an acid-decomposable group or a polar group).

The repeating units (cy1) and (cy2) are preferably those having an alicyclic hydrocarbon structure without a polar group.

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

The repeating unit (cy1) or (cy2) is preferably a repeating unit represented by the following formula (CIII).

In the formula (CIII), R _c31 represents an alkyl group, a cyano group or a -CH ₂ -O-Rac ₂ group which may be substituted by a hydrogen atom or a fluorine atom. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. R _c31 is preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, and 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 also be substituted by fluorine atoms or germanium atoms.

L _c3 represents a single bond or a divalent linking group.

In the formula (CIII), the alkyl group of R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.

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

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

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

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

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

The repeating unit (cy ₁ ) or (cy ₂ ) is preferably a repeating unit represented by the following formula (C4) or (C5).

In the formula (C4), R _c5 represents a hydrocarbon group having at least one cyclic structure and having no hydroxyl group or cyano group.

Rac means an alkyl group, a cyano group or a -CH ₂ -O-Rac ₂ group which may be substituted by a hydrogen atom or a fluorine atom. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. Rac is preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, and 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. The monocyclic hydrocarbon group may, for example, be a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group having 3 to 12 carbon atoms. In the preferred monocyclic hydrocarbon group, it is a monocyclic hydrocarbon group having 3 to 7 carbon atoms.

The polycyclic hydrocarbon group contains a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group. The crosslinked cyclic hydrocarbon ring system is a 2-ring hydrocarbon ring, a 3-ring hydrocarbon ring, a 4-ring hydrocarbon ring or the like. Further, the crosslinked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring (for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkyl rings are condensed). Preferred crosslinked cyclic hydrocarbon ring systems are a thiol group, an adamantyl group.

The alicyclic hydrocarbon group may have a substituent. Preferred substituents include a halogen atom, an alkyl group, a protecting group-protected hydroxyl group, a protecting group-protected amine group, and the like. The preferred halogen atom is a bromine, chlorine or fluorine atom, and a preferred alkyl group is a methyl group, an ethyl group, a butyl group or a tertiary butyl group. The above alkyl group may further have a substituent, and the substituent may further include a halogen atom, an alkyl group, a protecting group-protected hydroxyl group, and a protecting group-protected amine group.

The protecting group may, for example, be an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group or an aralkyloxycarbonyl group. The preferred alkyl group is an alkyl group having 1 to 4 carbon atoms, and a preferably substituted methyl group is methoxymethyl, methoxythiomethyl or benzyloxymethyl. Tertiary butoxymethyl, 2-methoxyethoxymethyl, in the case of a preferred substituted ethyl group, 1-ethoxyethyl, 1-methyl-1-methoxy The ethyl group, preferably a fluorenyl group, may have a carbon number of 1 to 6 such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a amyl group or a trimethyl ethyl group. The aliphatic fluorenyl group, and the alkoxycarbonyl group, is an alkoxycarbonyl group having 1 to 4 carbon atoms.

In the formula (C5), R _c6 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxycarbonyl group or an alkylcarbonyloxy group. These groups may also be substituted by fluorine atoms or germanium atoms.

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 3 to 20 carbon atoms.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

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

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

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

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

R _c6 is preferably an unsubstituted alkyl group or an alkyl group substituted by a fluorine atom, and is particularly preferably a trifluoromethyl group or a tertiary butyl group.

In the case of (cy1) and (cy2), the following repeating unit represented by the formula (CII-AB) is also preferred.

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

Zc' means an atomic group containing a bonded two carbon atoms (C-C) in order to form an alicyclic structure.

Further, the above formula (CII-AB) is more preferably a formula (CII-AB1) or a formula (CII-AB2).

In the formulae (CII-AB1) and (CII-AB2), R _c13 ' to R _c16 ' each independently represent a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group.

Further, at least two of R _c13 ' to R _c16 ' may be combined to form a ring.

The n system represents 0 or 1.

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

In the case of (cy3) or (cy4), the polar group is preferably a repeating unit having a hydroxyl group or a cyano group. Thereby enhancing 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. In the alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group, an adamantyl group, a diamond alkyl group or a ruthenium group is preferable in terms of an alicyclic hydrocarbon structure. Preferred examples of the alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group include a monohydroxyadamantyl group, a dihydroxyadamantyl group, a monohydroxy diamond alkyl group, a dihydroxyadamantyl group, and a cyano group-substituted lowering.莰基等.

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

In the general formulae (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, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or both of R ₂ c to R ₄ c are a hydroxyl group, and the balance is a hydrogen atom. In the formula (CAIIa), it is more preferred that two of R ₂ c to R ₄ c are a hydroxyl group, and the balance is a hydrogen atom.

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

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

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 from 5 to 80% by mass, more preferably from 10 to 80% by mass, based on the molecular weight of the resin (C). Further, the repeating unit of the fluorine atom is preferably from 10 to 100% by mass, more preferably from 30 to 100% by mass, based on all the repeating units in the resin (C).

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

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

The content of the resin (C) in the sensitized ray or the radiation-sensitive resin composition can be appropriately adjusted and used so that the sensitized ray or the radiation-sensitive resin film has a receding contact angle within the above range, but the sensitized ray or the sensitized radiation is used. The total solid content of the resin composition is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 9% by mass, even more preferably from 0.5 to 8% by mass, based on the total solid content.

The resin (C) is similar to the resin of the component (A) to be described later, and of course, the impurities such as metal are small, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably 0 to 5 by mass. %, further preferably from 0 to 1% by mass. By this, a photoresist which does not change over time such as foreign matter or sensitivity in the liquid is obtained. Further, the molecular weight distribution (Mw/Mn, also referred to as the degree of dispersion) is preferably in the range of 1 to 3, more preferably 1 in terms of resolution, photoresist shape, side wall of the resist pattern, roughness, and the like. Further, it is preferably from 1 to 1.8, and most preferably from 1 to 1.5.

The resin (C) can also be used in various commercial products, and can be synthesized according to a conventional method (for example, radical polymerization). For example, in a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent, and polymerization is carried out by heating, and a monomeric species is added dropwise in a heating solvent for 1 to 10 hours. The dropwise addition polymerization method or the like of the solution of the initiator is preferred to the dropwise addition polymerization method. In terms of the reaction solvent, for example, tetrahydrofuran, 1,4-two An ether such as an alkane or a diisopropyl ether; a ketone such as methyl ethyl ketone or methyl isobutyl ketone; an ester solvent such as ethyl acetate; dimethylformamide or dimethylacetonitrile; A solvent such as a guanamine solvent such as an amine or a propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) or cyclohexanone which will be described later, which dissolves the composition of the present invention. More preferably, it is polymerized using the same solvent as the solvent used in the composition of the present invention. Thereby, generation of particles during storage can be suppressed.

The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. A polymerization initiator is used to start polymerization by using a commercially available radical initiator (azo initiator, peroxide, etc.). The radical initiator is preferably an azo initiator, and is preferably an ester group, a cyano group or an azo initiator having a carboxyl group. Preferred examples of the initiator include azobisisobutyronitrile group, azobisdimethylvaleronitrile group, dimethyl 2,2'-azobis(2-methylpropionate), and the like. The concentration of the reaction is usually from 5 to 50% by mass, preferably from 10 to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, further preferably from 60 to 100 ° C.

After the reaction was completed, it was allowed to cool to room temperature and purified. The refining method may be a liquid-liquid extraction method in which a residual monomer or an oligomer component is removed by washing with water or a suitable solvent, or a method of purifying in a solution state by extracting and removing only a specific molecular weight or less, or a resin. Ordinary method in which a solution is dropped into a poor solvent to solidify the resin in a poor solvent, a reprecipitation method for removing a residual monomer or the like, or a method of refining a solid state in which the filtered resin slurry is washed with a poor solvent or the like method. For example, a solvent (lean solvent) which is insoluble or insoluble in the above resin is brought into contact with a volume of 10 times or less, preferably 10 to 5 times the volume of the reaction solution, whereby the resin is precipitated as a solid.

For the solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation of the polymer solution, as long as it is a poor solvent of the polymer, it can be derived from hydrocarbons, halogenated hydrocarbons, and nitrates depending on the type of the polymer. The base compound, an ether, a ketone, an ester, a carbonate, an alcohol, a carboxylic acid, water, a mixed solvent containing a solvent, etc. are suitably used. Among these, the precipitation or reprecipitation solvent is preferably a solvent containing at least an alcohol (especially methanol or the like) or water.

The amount of the precipitating or reprecipitation solvent to be used may be appropriately selected in consideration of efficiency, productivity, etc., but is usually from 100 to 10,000 parts by mass, preferably from 200 to 2,000 parts by mass, more preferably from 100 parts by mass to the polymer solution. 300 to 1000 parts by mass.

The temperature at the time of precipitation or reprecipitation is suitably selected in consideration of efficiency or workability, but is usually about 0 to 50 ° C, preferably about room temperature (for example, about 20 to 35 ° C). The precipitation or reprecipitation operation can be carried out by a conventional method such as batch type, continuous type, or the like using a conventional mixing container such as a stirring tank.

The precipitated or reprecipitated polymer is usually subjected to conventional solid-liquid separation such as filtration, centrifugation, etc., and dried for use. The filtration system uses 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 from about 30 to 100 ° C, preferably from about 30 to 50 ° C.

Further, once the resin is precipitated and separated, it is dissolved in a solvent, and the resin may be brought into contact with a solvent which is poorly soluble or insoluble. That is, it may be a method comprising the steps of: contacting the polymer with a poorly soluble or insoluble solvent after the radical polymerization reaction is completed, and precipitating the resin (step a), separating the resin from the solution (step b) And dissolving it in the solvent to prepare the resin solution A (step c), and thereafter, in the resin solution A, the solvent which is insoluble or insoluble in the resin is less than 10 times the volume of the resin solution A. (preferably, a volume of 5 times or less) is brought into contact to precipitate a resin solid (step d), and the precipitated resin is separated (step e).

A specific example of the resin (C) is shown. Moreover, the molar ratio of the repeating unit in each resin (corresponding to the order of each repeating unit from the left), the weight average molecular weight (Mw), and the degree of dispersion (Mw/Mn) are shown in the following table.

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

Further, it is preferably used in combination with a resin (CP) different from the resin (C) and at least one of a fluorine atom or a ruthenium atom.

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

The sensitizing 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 ruthenium atom other than the above resin (C). When the resin (C) ‧ resin (CP) is contained, the resin (C) ‧ resin (CP) and the liquid immersion medium are water in the surface layer of the film, and the water-resistant film for water formation can be improved. Surface receding contact angle, lifting fluid immersion followability. The film receding contact angle is preferably 60 to 90, and more preferably 70 or more. The content of the resin (CP) is appropriately adjusted so that the film receding contact angle is within the above range, but it is preferably 0.01 to 10 based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition. The mass% is more preferably 0.01 to 5% by mass, still more preferably 0.01 to 4% by mass, particularly preferably 0.01 to 3% by mass.

The resin (CP) is generally not uniform in the interface as described above, but unlike the surfactant, it does not have a hydrophilic group in the molecule, and it does not contribute to the uniform mixing of the polar/nonpolar substance.

In the resin (CP) having at least one of a fluorine atom and a ruthenium atom, the fluorine atom or the ruthenium atom may be contained in the main chain of the resin or may be substituted for the side chain.

The resin (CP) is a resin having a fluorine atom, preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

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

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may further have other substituents.

In the case of the aryl group having a fluorine atom, at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group may be substituted with a fluorine atom, and further may have other substituents.

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 the formulae (F2) to (F4) in the above resin (C). However, the present invention is not limited thereto.

In the present invention, the group represented by the general formulae (F2) to (F4) is preferably contained in a (meth)acrylic repeating unit.

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

In a specific example, 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 a structure of a ruthenium atom, and preferably has a structure of an alkylene group (preferably a trialkane group) or a cyclic siloxane.

Specifically, the alkylene group structure or the cyclic oxime structure is a group represented by the general formulae (CS-1) to (CS-3) in the above resin (C).

Further, the resin (CP) may have at least one selected from the group of (x) and (z) below. (x) an alkali-soluble group, (z) a group decomposed by the action of an acid.

The basis of these is specifically the same as those in the above resin (C).

In the resin (CP), a repeating unit having a group (z) decomposed by an action of an acid is the same as a repeating unit having an acid-decomposable group exemplified by a resin of the component (A) described later. In the resin (CP), the content of the radical (z) repeating unit which is decomposed by the action of an acid is preferably from 1 to 80 mol%, more preferably from 10 to 80 mol, based on all the repeating units in the resin (CP). More preferably, it is 20 to 60 mol%.

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

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

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

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

The resin (CP) is similar to the resin of the component (A). Of course, the impurities such as metal are small, and the residual monomer or oligomer component is preferably from 0 to 10% by mass, more preferably from 0 to 5% by mass. Further preferably, it is 0 to 1% by mass. By this, it is possible to obtain a sensitized ray-sensitive or radiation-sensitive resin composition which does not change over time, such as foreign matter or sensitivity in the liquid. Further, from the viewpoints of the resolution, the shape of the photoresist, the side wall of the photoresist pattern, the roughness, and the like, the molecular weight distribution (Mw/Mn, also in terms of dispersion) is preferably in the range of 1 to 3, more preferably 1 to 2, further preferably 1 to 1.8, most preferably 1 to 1.5.

The resin (CP) can also be used in various commercial products, and can be synthesized according to a conventional method (for example, radical polymerization). Specifically, it can be synthesized in the same manner as the above-mentioned resin (C).

Specific examples of the resin (CP) having at least one of a fluorine atom and a ruthenium atom are shown below. Moreover, the molar ratio of the repeating unit in each resin (corresponding to the order of each repeating unit from the left), the weight average molecular weight (Mw), and the degree of dispersion (Mw/Mn) are shown in the following table.

The film formed of the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention may be filled with a liquid having a higher refractive index than air (liquid immersion medium) between the film and the lens when irradiating actinic rays or radiation. Exposure (liquid immersion exposure). This can improve the resolution. As the liquid immersion medium to be used, any liquid having a higher refractive index than air can be used, but it is preferably pure water.

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

The liquid immersion liquid is transparent to the exposure wavelength, and preferably retains the deformation of the optical image projected on the film to a minimum, and the temperature coefficient of the refractive index is as small as possible, especially for the exposure source. In the case of a molecular laser (wavelength; 193 nm), the above-mentioned viewpoint is added, and in terms of ease of use and ease of operation, it is preferable to use water.

Further, in the case where the refractive index can be further increased, a medium having a refractive index of 1.5 or more can also be used. The medium may be an aqueous solution or an organic solvent.

When water is used as the liquid immersion liquid, the surface tension of the water is reduced, and in order to increase the interfacial activity, the photoresist film on the wafer is not dissolved, and may be added in a slight proportion to ignore the underside of the lens element. An additive (liquid) affected by the optical coating. The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specific examples thereof include methanol, ethanol, and isopropanol. By adding an alcohol having a refractive index almost equal to that of water, it is possible to obtain a concentration in which the change in the refractive index of the entire liquid is extremely small even if the concentration of the alcohol component in the evaporated water is changed. On the other hand, in the case where a substance which is opaque to 193 nm light or an impurity which is different in refractive index from water is mixed, in order to cause deformation of an optical image projected on the photoresist film, distilled water is used in terms of water to be used. good. Further, it may be used by filtering pure water by an ion exchange filter or the like.

The electric resistance of the water is preferably 18.3 Mcm or more, and the TOC (organic matter concentration) is preferably 20 ppb or less, and it is preferable to carry out degassing treatment.

Moreover, by increasing the refractive index of the liquid immersion liquid, the lithography performance can be improved. From such a viewpoint, an additive for increasing the refractive index can also be added to water, and heavy water (D ₂ O) can be used instead of water.

Between the film formed by the composition of the present invention and the liquid immersion liquid, in order to prevent the film from directly contacting the liquid immersion liquid, a liquid immersion liquid poorly soluble film may be provided (hereinafter also referred to as "topcoat"). ). In terms of the function required for the surface coating film, the coating to the upper layer of the film is reasonable, and the transparency to the radiation, especially 193 nm, and the poor solubility of the liquid immersion liquid. The surface coating film is not mixed with the photoresist, and is preferably further uniformly applied to the upper layer of the photoresist.

The surface coating film is preferably a polymer containing no aromatics from the viewpoint of transparency at 193 nm, and specific examples thereof include a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, and polyacrylic acid. Polyvinyl ether, ruthenium containing polymer, fluoropolymer, and the like. The above-mentioned hydrophobic resins (C) and (CP) are also preferable as a surface coating film. From the viewpoint of contaminating the optical lens from the surface coating film to dissolve the impurity to the liquid immersion liquid, the residual monomer component of the polymer contained in the surface coating film is less preferred.

A developer may be used when peeling off the surface coating film, and a release agent may also be used. In the case of the release agent, it is preferred that the film is impregnated with a small solvent. The argument can be carried out simultaneously with the development treatment step of the film in the stripping step, preferably by stripping with an alkali developer. The surface coating film is preferably acidic from the viewpoint of being peeled off by the alkali developing solution, but may be neutral or alkaline from the viewpoint of non-mixing property with the film.

There is no difference in refractive index between the surface coating film and the liquid immersion liquid, and the resolution is improved. In the ArF excimer laser (wavelength: 193 nm), when water is used as the liquid immersion liquid, the surface coating film for ArF immersion exposure is preferably similar to the refractive index of the liquid immersion liquid. From the viewpoint of the refractive index and the liquid immersion liquid phase, it is preferred to have a fluorine atom in the surface coating film. Further, from the viewpoint of transparency and refractive index, it is preferably one of the films.

The surface coating film is not mixed with the film, and is preferably further not mixed with the liquid immersion liquid. From this point of view, in the case where the liquid immersion liquid is water, the solvent used for the surface coating film is preferably a solvent which is hardly soluble in the composition used in the present invention, and is a water-insoluble medium. Further, in the case where the liquid immersion liquid is an organic solvent, the surface coating film may be water-soluble or water-insoluble.

[alkaline compound]

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

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

In the general formulae (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represent a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), or a cycloalkyl group (preferably The carbon number is 3 to 20) or the aryl group (carbon number is 6 to 20), and here, 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.

With respect to the above alkyl group, the alkyl group having a substituent 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 group in these general formulae (A) and (E) is more preferably unsubstituted.

Preferred examples of the compound include anthracene, aminopyrrolidine, pyrazole, pyrazoline, and piperazine. Amino group Porphyrin Examples of a further preferred compound include a compound having an imidazole structure, a dioxonium structure, a cesium hydroxide structure, a carboxylic acid hydrazine structure, a trialkylamine structure, an aniline structure or a pyridine structure, and a hydroxyl group. And/or an alkylamine derivative of an ether bond, an aniline derivative having a hydroxyl group and/or an ether bond, or the like.

Examples of the compound having an imidazole structure include imidazole, 2, 4, 5-tribenzimidazole, benzimidazole, 2-phenylbenzimidazole, and the like. In the case of a compound having a diterpene bicyclic structure, 1, 4-dibicyclo[2,2,2]octane, 1,5-dioxabicyclo[4,3,0]non-5-ene, 1 , 8-diindole bicyclo[5,4,0]undec-7-ene, and the like. Examples of the compound having a ruthenium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, benzamidine methylhydrazine hydroxide, and a phosphonium hydroxide having a 2-sided oxyalkyl group, specifically Illustrative examples include triphenylsulfonium hydroxide, hydrazine hydroxide (tertiary butylbenzene) hydrazine, bis(tributylbenzene) hydrazine hydroxide, benzamidine methyl thiobenzoate, and 2-oxo hydroxide Propanethione and the like. In the case of a compound having a ruthenium carboxylate structure, the anion portion of the compound having a ruthenium hydroxide structure may be a carboxylic acid ester, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylic acid. Ester and the like. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the aniline compound include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, n-phenylenediethanolamine, and methoxy(methoxyethoxyethyl)amine. The aniline derivative having a hydroxyl group and/or an ether bond may, for example, be N,N-bis(hydroxyethyl)aniline or the like.

Further, 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 sulfonate group, and an ammonium salt compound having a sulfonate group.

As the amine compound, an amine compound of a first order, a second order, or a third order may be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. The amine compound is more preferably a tertiary amine compound. The amine compound may be bonded to a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group in addition to the alkyl group if at least one alkyl group (preferably having a carbon number of 1 to 20) is bonded to the nitrogen atom. It is preferably a carbon number of 6 to 12) to a nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and forms an oxygen alkyl group. The number of oxygen alkyl groups is one or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. Among the oxygen alkyl groups, an ethyl group (-CH ₂ CH ₂ O-) or an oxygen-extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) More preferably, it is preferably an oxygen-extended ethyl group.

As the ammonium salt compound, an ammonium salt compound of the first, second, third, and fourth grades may be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. When the ammonium salt compound is bonded to the nitrogen atom by at least one alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group may be bonded in addition to the alkyl group. (preferably from 6 to 12 carbon atoms) to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and forms an oxygen-extended alkyl group. The number of oxygen alkyl groups is more than one in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an ethyl group (-CH ₂ CH ₂ O-) or an oxygen-extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) More preferably, it is preferably an oxygen-extended ethyl group. The anion of the ammonium salt compound may, for example, be a halogen atom, a sulfonate, a borate or a phosphate, but among them, a halogen atom or a sulfonate is preferred. Particularly preferred as the halogen atom is a chloride, a bromide or an iodide, and in the case of a sulfonate, an organic sulfonate having a carbon number of 1 to 20 is particularly preferred. The organic sulfonate may, for example, be an alkanesulfonate or an arylsulfonate having 1 to 20 carbon atoms. The alkyl group of the alkanesulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy, decyl, aryl and the like. Specific examples of the alkanesulfonate include methanesulfonate, ethanesulfonate, butanesulfonate, hexanesulfonate, octanesulfonate, benzylsulfonate, trifluoromethanesulfonate, Pentafluoroethane sulfonate, nonafluorobutane sulfonate, and the like. The aryl group of the aryl sulfonate is a benzene ring, a naphthalene ring or an anthracene ring. The benzene ring, the naphthalene ring, and the anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and the cycloalkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tertiary butyl group, a n-hexyl group, and a cyclohexyl group. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyanogen, a nitrate, a decyl group, a decyloxy group and the like.

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 also 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 carboxylate group, a sulfonate group, an aryl group, an aralkyl group, and an anthracene group. Oxyl, aryloxy, and the like. The substituent of the substituent may be any of the 2 to 6 positions. The number of substituents is in the range of 1 to 5.

Between the phenoxy group and the nitrogen atom, it is preferred to have at least one oxygen alkyl group. The number of oxygen alkyl groups is more than one in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an ethyl group (-CH ₂ CH ₂ O-) or an oxygen-extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) More preferably, it is preferably an oxygen-extended ethyl group.

In the case where the sulfonate group has an amine compound and the sulfonate group has an ammonium salt compound, in the case of a sulfonate group, any of an alkyl sulfonate, a cycloalkyl sulfonate, and an aryl sulfonate The alkyl group is preferably a carbon number of 1 to 20 in the case of an alkyl sulfonate, and preferably a carbon number of 3 to 20 in the case of a naphthenic acid sulfonate. The basis is preferably from 6 to 12 carbon atoms. The alkyl sulfonate, cycloalkyl sulfonate, and aryl sulfonate may further have a substituent. In the case of a substituent, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, and a sulfonate are preferred. Acid ester group.

Preferably, the sulfonate group and the nitrogen atom have at least one oxygen alkyl group. The number of oxygen alkyl groups is more than one in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an ethyl group (-CH ₂ CH ₂ O-) or an oxygen-extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) More preferably, it is preferably an oxygen-extended ethyl group.

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

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

The ratio of use of the acid generator to the composition of the basic compound is preferably an acid generator/basic compound (mole ratio) = 2.5 to 300. In other words, in terms of sensitivity and resolution, it is preferable that the molar ratio is 2.5 or more, and the reduction in resolution due to the thickness of the resist pattern from the time of exposure to the heat treatment is 300. The following is preferred. The acid generator/basic compound (mole ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

[Surfactant]

The composition of the present invention preferably further contains a surfactant, and more preferably contains a fluorine-based and/or a lanthanoid surfactant (a fluorine-based surfactant, a lanthanoid surfactant, and a fluorine atom and a ruthenium atom). Either of the surfactants) or two or more types.

When the composition of the present invention contains the above-mentioned surfactant, when it is used at an exposure light source of 250 nm or less, particularly 220 nm or less, it is possible to impart a resist pattern having excellent sensitivity and resolution and having less adhesion and development defects.

For the fluorine-based and/or lanthanum-based surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-62- Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 5,057, 520, the specification of 5, 560, 692, the same as 5, 527, 988, the same as 5, 296, 730, the same as 5, 546, 998, the same as 5, 576, 143, the same as 5,294,511, the same as the description of the 5,842,451, The following commercially available surfactants can also be used directly.

As for the commercially available surfactants, for example, EFTOPEF301, EF303, (New Akita Chemicals Co., Ltd.), FRORAID FC430, 431, 4430 (Sumitomo 3M (share) system), Megafac F171, F173, F176, F189 , F113, F110, F177, F120, R08 (made by Dainippon Ink Chemical Industry Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (made by Asahi Glass Co., Ltd.), Troysol S-366 (Troychemical) (share) system, GF-300, GF-150 (manufactured by East Asia Synthetic Chemicals Co., Ltd.), Surflon S-393 (SEIMICHEMICAL), EFTOPEF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (made by Jemco), PF636, PF656, PF6320, PF6520 (made by OMNOVA), FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (() Eos A fluorine-based surfactant or a quinone-based surfactant. Further, a decane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as the lanthanide surfactant.

Further, as the surfactant, a surfactant using a compound which is a short-chain polymerization method (also referred to as a short-chain polymer) may be used in addition to the above-mentioned conventional ones. The method is a fluoroaliphatic group-derived polymer derived from a fluoroaliphatic compound produced by a low polymerization method (also referred to as an oligomer method). The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

In the case of a polymer having a fluoroaliphatic group, a monomer having a fluoroaliphatic group and (poly(oxyalkylene))acrylic acid and/or (poly(oxyalkylene))methacrylic acid are preferred. The copolymer, even if it is an irregular distribution, can also be block copolymerized. Further, examples of the poly(oxyalkylene) group include a poly(oxyethylene) group, a poly(oxypropylene) group, a poly(oxygen) group, and the like, and may also be a poly(oxygen extension). a chain linker of an ethyl group with an oxygen-extended propyl group and an oxygen-extended ethyl group) or a poly(alkyl-and-oxygen-extended propyl block link) having the same chain length and the like. The unit of the class. Further, the copolymer having a fluoroaliphatic group and a copolymer of (poly(oxyalkylene))acrylic acid (or methacrylic acid) are not all divalent copolymers, and two or more different types of fluorocarbons may be used. A group-based monomer or a copolymer of a ternary system or more of two or more kinds of (poly(oxyalkylene))acrylic acid (or methacrylic acid) or the like.

For example, megafac F178, F-470, F-473, F-475, F-476, and F-472 (made by Dainippon Ink Chemicals Co., Ltd.) are mentioned as a commercially available surfactant. Further, a copolymer of acrylic acid (or methacrylic acid) having a C ₆ F ₁₃ group and (poly(oxyalkylene))acrylic acid (or methacrylic acid), acrylic acid having a C ₃ F ₇ group (or a a copolymer of (acrylic acid) and (poly(oxyethylidene))acrylic acid (or methacrylic acid) and (poly(oxypropyl))acrylic acid (or methacrylic acid).

Further, in the present invention, a surfactant other than a fluorine-based and/or an anthraquinone-based surfactant may be used. Specific examples thereof include polyoxyalkylene lauryl ether, polyoxyethylidene stearyl ether, polyoxyethylidene cetyl ether, polyoxyethylene oleyl ether, and the like. Polyoxyalkylene aryl ethers, polyoxyethylene ethoxylates, propyl ethers, polyoxyethyl octyl phenol ethers, polyoxyethylidene phenol ethers, etc. Block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan A sorbitan fatty acid ester such as tristearate, polyoxyethyl sorbitan monolaurate, polyoxyethyl sorbitan monopalmitate, polyoxyethyl sorbitan monohard Nonionic interfacial activity of polyoxyalkylene sorbitan fatty acid esters such as fatty acid esters, polyoxyethyl sorbitan trioleate, polyoxyethyl sorbitan tristearate Agents, etc.

These surfactants may also be used singly or in combination of several.

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

[carboxylic acid sulfonium salt]

The composition of the present invention may also contain a cerium carboxylate salt. The carboxylic acid cerium salt may, for example, be a cerium carboxylate salt, a carboxylic acid cerium salt or a carboxylic acid ammonium salt. In particular, in the case of a cerium carboxylate salt, a phosphonium salt or a phosphonium salt is preferred. Further, the carboxylate residue of the cerium carboxylate salt of the present invention preferably contains no aromatic group or carbon-carbon double bond. The particularly preferred anion moiety is preferably a linear, branched, monocyclic or polycyclic alkyl carboxylic acid anion having from 1 to 30 carbon atoms. It is further preferred that one or all of the alkyl groups such as those which are fluorine-substituted carboxylic acids are preferred. An oxygen atom may also be contained in the alkyl chain. This ensures transparency to light below 220 nm, enhances sensitivity and resolution, and improves density and exposure latitude.

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, and perfluorocarbon. An alkanoic acid, perfluorocyclohexanecarboxylic acid, an anion of 2,2-bistrifluoromethylpropionic acid, and the like.

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

The content in the composition of the cerium carboxylate salt is usually from 0.1 to 20% by mass, preferably from 0.5 to 10% by mass, still more preferably from 1 to 7% by mass, based on the total solid content of the composition.

[dissolution blocking compound]

The composition of the present invention may further contain a dissolution preventing compound (hereinafter also referred to as "dissolution preventing compound") which is decomposed by an action of an acid and which increases the solubility in an alkali developing solution and has a molecular weight of 3,000 or less. In order to prevent the permeability of the compound from being dissolved, the acid-decomposable group-containing fat of the acid-decomposable group-containing cholic acid derivative of Proceeding of SPIE, 2724, 355 (1996) is preferably used. A cyclosteroid or an aliphatic compound is preferred. The acid-decomposable group or the alicyclic structure may be the same as those described for the resin of the component (B).

In the case where the composition of the present invention is exposed to a KrF excimer laser or irradiated with an electron beam, it is preferred to contain a structure in which a phenolic hydroxyl group of a phenol compound is substituted with an acid-decomposing group. The phenol compound preferably contains from 1 to 9 phenol skeletons, and more preferably from 2 to 6 members.

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

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

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

[Other additives]

Further, if necessary, the composition of the present invention may further contain a dye, a plasticizer, a photosensitizer, a light absorbing agent, and a compound which promotes solubility in a developing solution (for example, a phenol compound having a molecular weight of 1,000 or less, having a carboxyl group) An alicyclic group, or an aliphatic compound).

Such a phenolic compound having a molecular weight of 1,000 or less is described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent No. 219294. Those of ordinary skill in the art can easily synthesize.

Specific examples of the alicyclic group having a carboxyl group or an aliphatic compound include a quinone structure carboxylic acid derivative having an acid such as cholic acid, deoxycholic acid or tricholic acid, an adamantanecarboxylic acid derivative, and adamantane. Dicarboxylic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, etc., but not limited thereto.

Pattern forming method

From the viewpoint of the resolution of the above, the composition of the present invention is preferably used in a film thickness of 30 to 250 nm, more preferably in a film thickness of 30 to 200 nm. The film thickness can be set by setting the solid content concentration in the sensitized ray-sensitive or radiation-sensitive resin composition to an appropriate range to have an appropriate viscosity, improved coatability, and film formability.

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

The composition of the present invention is prepared by dissolving the above-mentioned components in a predetermined organic solvent, dissolving in the above-mentioned mixed solvent, filtering them with a filter, and applying them to a predetermined support as follows. The filter for filter filtration has a pore size of 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less, and is preferably made of polytetrafluoroethylene, polyethylene or nylon.

For example, a sensitizing ray-sensitive or radiation-sensitive resin composition is used for a substrate (for example, ruthenium/ruthenium dioxide coating) for manufacturing a precision integrated circuit element, and is suitably coated by spin coating, coating, or the like. The coating method is applied, dried, and formed into a photoresist film.

Preferably, the photoresist film is irradiated (heated), developed, and rinsed by irradiating actinic rays or radiation through a predetermined mask. A good pattern can be obtained by this.

Examples of actinic rays or radiation include infrared rays, visible light, ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays, X rays, electron beams, and the like, but are preferably 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm. The far-ultraviolet light of the wavelength is specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, electron beam, etc., preferably ArF excimer laser, F ₂ excimer laser, EUV (13 nm), electron beam.

An anti-reflection film may be preliminarily coated on the substrate before the film is formed.

As the antireflection film, any of an inorganic film type such as titanium, titanium oxide, titanium nitride, chromium oxide, carbon, or amorphous germanium, or an organic film type composed of a light absorbing agent and a polymer material can be used. Further, as the organic anti-reflection film, a commercially available organic anti-reflection film such as DUV30 series manufactured by Brewerscience Co., Ltd., DUV-40 series, AR-2, AR-3, AR-5 manufactured by Shipley Co., Ltd., or the like can be used.

In the developing step, an alkali developing solution was used as follows. For the alkali developer of the sensitizing ray-sensitive or radiation-sensitive resin composition, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium methyl citrate or ammonia can be used. a first amine such as an amine or n-propylamine; a second amine such as diethylamine or di-n-butylamine; a third amine such as triethylamine or methyldiethylamine; dimethylethanolamine or triethanolamine. An alkaline aqueous solution such as a fourth-order ammonium salt such as an alcoholamine, tetramethylammonium hydroxide or tetraethylammonium hydroxide, or a cyclic amine such as pyrrole or piperidine.

Further, an alcohol or a surfactant may be added to the alkali developer in an appropriate amount to be used.

The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.

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

Further, an alcohol or a surfactant may be added to the alkaline aqueous solution in an appropriate amount to be used.

In the case of the rinsing liquid, pure water is used and an appropriate amount of a surfactant is added for use.

Further, after the development treatment or the rinsing treatment, a treatment for removing the developer or the rinsing liquid adhering to the pattern by the supercritical fluid may be performed.

[Examples]

The present invention is described below by way of examples, but the invention is not limited thereto.

<Synthesis of photoacid generator>

The photoacid generator PAG15 described below was synthesized in accordance with the following synthetic 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, and then heated at 120 ° C for 8 hours by adding 12 g of potassium carbonate and 14 g of potassium iodide. 300 g of water was added to the reaction solution, and extraction was carried out three times with 100 g of hexane. The obtained organic layer was combined, washed once with 100 g of 1N aqueous sodium hydroxide solution, once with water (100 g), and once with Brine 100 g, and concentrated to give 13 g. Compound 1.

[Synthesis of Compound 2]

Compound 2 was synthesized by the method described in JP-A-2005-266799.

[Synthesis of PAG15]

After dissolving 13.1 g of the compound 1 in 65 g of Eaton's reagent in a three-necked flask, 5.7 g of tetramethylenefluorene was added dropwise while stirring, and the mixture was further stirred for 3 hours. After 240 g of water was added to the reaction mixture, 25 g of a compound 2 and 50 g of chloroform were added. After separating the organic layer, the extraction was further carried out twice from the aqueous layer using 50 g of chloroform. The obtained organic layer was combined, washed twice with water and concentrated. The obtained composition was recrystallized from 20 g of ethyl acetate to obtain 22 g of PAG15.

For PAG1 to PAG14, PAG16 to PAG21, it was also prepared in the same manner as PAG15.

<Synthesis of Resin (A)>

Synthesis Example 1 Synthesis of Resin (1)

8.6 g of cyclohexanone was placed in a three-necked flask under a nitrogen stream, and this was heated to 80 °C. 8.0 g of norbornactone methacrylic acid, 4.0 g of dihydroxyadamantyl methacrylic acid, 9.0 g of 2-adamantyl isopropyl methacrylic acid, and a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) A solution dissolved in 70 g of cyclohexanone with respect to 8 mol% of the monomer was dropped thereon for 6 hours. After the completion of the dropwise addition, the mixture was further reacted at 80 ° C for 2 hours. The reaction solution was allowed to stand for cooling, and then a mixture of 800 ml of hexane / 200 ml of ethyl acetate was added dropwise thereto over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 17 g of a resin (1). The weight average molecular weight of the obtained resin was 8,500 in terms of standard polystyrene, and the degree of dispersion (Mw/Mn) was 1.8.

In the same manner as in the above-mentioned Synthesis Example 1, an acid-decomposable resin having a composition ratio, a weight average molecular weight, and a degree of dispersion (Mw/Mn) shown in the same table was synthesized using the monomers shown in Table 3 shown below. (2) to (12).

<Synthesis of Resin (C)>

Synthesis Example 2 Addition of Polymer C-7

The monomers corresponding to the following repeating units were charged at a ratio of 90/10 (mole ratio), dissolved in PGMEA, and prepared into a solution of 450 g of a solid content concentration of 15% by mass. To the solution was added 1 mol% of a polymerization initiator V-60 manufactured by Wako Pure Chemical Industries Co., Ltd., and 50 g of PGMEA was added dropwise thereto by heating to 100 ° C for 6 hours under a nitrogen atmosphere. After the completion of the dropwise addition, the reaction solution was stirred for 2 hours. After completion of the reaction, the reaction liquid was cooled to room temperature, and crystallized in 5 L of methanol, and the precipitated white powder was collected by filtration to recover the target compound C-7.

The polymer composition ratio determined from NMR was 90/10. Further, the weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 8,000, and the degree of dispersion was 1.40.

The resin C-3, C-26, C-49, C-63, C-69, C-76, C-88, C-132, C- shown above was carried out in the same manner as in the above Synthesis Example 2. 146, C-165, C-193, and C-211 each had a respective resin having a composition ratio, a weight average molecular weight, and a degree of dispersion (Mw/Mn) shown in Table 1 shown above.

<Photoresist modulation>

The components shown in the following table were dissolved in a solvent, and each of them was prepared into a solution having a total solid content concentration of 4% by mass, and this was filtered with a polyethylene filter having a pore diameter of 0.05 μm to prepare a positive resist for liquid immersion exposure. Solution. The prepared photoresist composition was evaluated in the following manner, and the results were shown in the same table. In addition, the ratio of the ratio of each component in the same table and the use of various components is a mass ratio.

The amount of the resin (C) added is % by mass based on the total solid content of the photoresist composition.

Table 4

The symbols in Table 4 above are as follows.

[Acid generator and resin (C)]

The acid generator and the resin (C) correspond to the previous examples.

[alkaline compound]

N-1: N,N-dibutylaniline

N-2: 2,6-diisopropylaniline

N-3: 2-phenylbenzimidazole

N-6: 2,4,5-triphenylimidazole

[Surfactant]

W-1: megafac F176 (Daily Ink Chemical Industry Co., Ltd., fluorine system)

W-2: Troysol S-366 (made by Troy Chemical)

W-3: PF6320 (made 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: γ-butyrolactone

<Photoresist evaluation> [Exposure conditions: ArF immersion exposure]

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto the wafer, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 98 nm. The prepared positive-type photoresist composition was coated thereon, and baked at 130 ° C for 60 seconds to form a photoresist film having a film thickness of 120 nm. The obtained wafer was subjected to an ArF excimer laser immersion scanner (XT1700i, NA1.20, C-Quad, external standard deviation 0.981, internal standard deviation 0.895, XY deflection) manufactured by ASML, and passed through a 65 nm 1:1 line pattern. The 6% halftone mask is exposed. Ultrapure water is used in the case of liquid immersion liquid. Thereafter, the film was heated at 130 ° C for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38 mass%) for 30 seconds, rinsed with pure water, and then rotary dried to obtain a photoresist pattern.

[coating defect]

A 5 cc photoresist was spin-coated at 3000 rpm on a 12-inch wafer, and then baked with a hot plate, and the film thickness within 10 mm from the outer peripheral portion of the coated wafer was measured. When the film thickness variation is within 4 nm, A is given to B, and when it is larger than 4 nm and 20 nm or less, B is given, and when it is larger than 20 nm and 50 nm or less, C is applied, C is larger than 50 nm, streaks are generated, precipitation of solute, film contamination, or photoresist is not covered. The outside of the wafer is given to D.

[LWR]

The measurement of LWR was carried out using a critical dimension scanning electron microscope (CD-SEM) ((H) Hitachi, Ltd. S-9260), and an isolated pattern of 65 nm in the optimum exposure amount was observed for a range of 5 μm from the edge of the longer direction of the line pattern. The distance from the reference line of the edge is measured at 50 points, and the standard deviation is obtained to calculate 3σ. A smaller value indicates good performance.

From Table 4, it is understood that the pattern formed by using the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention suppresses coating defects and has excellent LWR performance.

Claims (13)

A photosensitive ray-sensitive or radiation-sensitive resin composition characterized by containing the following (A) to (D): (A) a resin which increases the solubility to an alkali developer by an action of an acid, and (B) a compound represented by the formula (1-1) or (1-2), (C) comprising at least one of a fluorine atom and a ruthenium atom in one side chain and decomposed and enlarged by the action of an alkali developer a resin of a repeating unit of a polar conversion group which is soluble in an alkali developing solution, and a resin containing a repeating unit having at least a carboxylate group (-COO-) as the polar converting group (except that the carboxylate group does not contain a mixed solvent of -COO-) in the lactone group and (D) two or more solvents, that is, at least one solvent selected from the group consisting of the following general formulae (S1) to (S4) And the total content of the solvent is a mixed solvent of 1 to 20% by mass of the total solvent; In the 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 cycloalkane skeleton having a monocyclic or polycyclic ring. a group; the case where a plurality of R ₁₄ are present, each independently representing an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a a monocyclic or polycyclic cycloalkane skeleton; R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group; 2 R ₁₅ may be bonded to each other to form a ring; 1 is an integer of 0 to 2; system represents an integer of 0-8; X ^- line represents a non-nucleophilic anion; in formula (1-2), M based an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, having the ring structure, the ring structure system may also contain an oxygen atom, a sulfur atom, an ester bond, acyl amine linkage, or a carbon - carbon double bond; R _1c and R _2c each independently represent a line 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-sided oxyalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group; R _x and R _y may also be combined. Form a ring; M, R _1c and R At least two of _2c may also be combined to form a ring, and the ring structure may also contain a carbon-carbon double bond; the X ^- line represents a non-nucleophilic anion; In the general formulae (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 bonded to each other to form a ring; in the formula (S4), R ₈ and R ₉ each independently represent an alkane which may have a substituent. The two groups may also be combined with each other to form a ring. The photosensitive ray-sensitive or radiation-sensitive resin composition of claim 1, wherein the resin (A) contains a repeating unit having a lactone structure. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin (A) contains a repeating unit having an acid-decomposable group containing a monocyclic or polycyclic ester Ring construction. The photosensitive ray-sensitive or radiation-sensitive resin composition of claim 1 of the patent application is applicable to liquid immersion exposure. The photosensitive ray-sensitive or radiation-sensitive resin composition according to the first aspect of the invention, wherein the content of the compound (B) based on the total solid content of the composition is 10 to 30% by mass. The photosensitive ray-sensitive or radiation-sensitive resin composition according to the first aspect of the invention, wherein the content of the resin (C) based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition is 0.01 to 10% by mass. A photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (C) contains a repeating unit having at least two or more polar converting groups. A photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the mixed solvent (D) contains γ-butyrolactone as a group selected from the group consisting of the general formulae (S1) to (S4). At least one solvent. The photosensitive ray-sensitive or radiation-sensitive resin composition of claim 1, wherein the mixed solvent (D) contains cyclohexanone as the general formula (S1) At least one solvent selected from the group indicated by (S4). The photosensitive ray-sensitive or radiation-sensitive resin composition of claim 1, wherein the mixed solvent (D) does not contain a protic solvent. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the mixed solvent (D) contains propylene glycol monomethyl ether acetate in an amount of 50% by mass or more. A pattern forming method comprising the steps of forming a film using a photosensitive ray- or radiation-sensitive resin composition as in the first aspect of the patent application, the step of exposing the film, and the step of developing. The pattern forming method of claim 12, wherein the exposure is immersion exposure.