KR101810520B1 - Active ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

An object of the present invention is to provide a sensitizing actinic ray or radiation-sensitive resin composition excellent in sensitivity, roughness characteristics and aging stability, and a pattern forming method using the same.
To this end, the active radiation-sensitive or radiation-sensitive resin composition according to the present invention comprises a sulfonic acid-generating compound which decomposes by the action of an acid to generate a sulfonic acid having a volume of 240 Å ³ or more, And the repeating unit is a resin having an acetal structure or a resin having a structure represented by the following general formula (I) and a compound capable of generating an acid upon irradiation with an actinic ray or radiation .

Description

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

The present invention relates to a sensitizing actinic ray or radiation-sensitive resin composition and a pattern forming method using the same. Particularly, the present invention is preferably applied to a super-microlithography process and other photofabrication processes that can be applied to, for example, a process of manufacturing a super LSI and a high-capacity microchip, a process of manufacturing a mold for a nanoimprint and a process of manufacturing a high- And a method for forming a pattern using the same.

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

The term " exposure " as used herein means not only light irradiation by a mercury lamp, deep ultraviolet ray, X-ray and EUV light, but also drawing by a particle beam such as an electron beam and an ion beam.

The chemically amplified resist composition is prepared by changing the solubility of the irradiated portion and the non-irradiated portion of the active radiation to the developing solution by a reaction in which the acid is generated in the exposed portion by irradiation of radiation such as extraneous light, As shown in FIG.

When a KrF excimer laser is used as an exposure light source, a resin mainly composed of poly (hydroxystyrene) having a small absorption in the 248 nm region is used as a main component. Therefore, it has a high sensitivity and a high resolution, forms a good pattern, and is in a better state than the conventional naphthoquinonediazide / novolac resin system.

On the other hand, when a light source of a shorter wavelength, for example, ArF excimer laser (193 nm), is used as an exposure light source, the compound having an aromatic group essentially exhibits a large absorption in the region of 193 nm, Did not do it.

For this reason, resists for ArF excimer lasers containing a resin having an alicyclic hydrocarbon structure have been developed.

A triphenylsulfonium salt is generally known as an acid generator which is a main component of a chemical amplification resistor (see, for example, Patent Document 1). However, since the acid generator is still insufficient, development of a photosensitive composition having improved sensitivity, resolution, pattern shape, roughness, and the like is required to be improved by improving the acid generator.

Particularly, the roughness characteristic and the resolution become larger as the pattern dimension becomes smaller. For this reason, in the lithography using X-rays, electron beams, or EUV, it is desired to form a fine pattern of several tens of nm, and therefore, excellent resolution and roughness characteristics are required.

When an electron beam, an X-ray, or a EUV light source is used, since the exposure is performed under vacuum, there is a problem of outgassing that a low-boiling compound such as a solvent or a resist material decomposed by high energy is volatilized and the exposure apparatus is contaminated . In recent years, various researches have been conducted on the reduction of outgas, and a topcoat layer is formed to suppress the volatilization of a low-molecular compound (see, for example, Patent Document 2) Various attempts have been made such as adding a radical trapping agent (see, for example, Patent Document 3), and design of outgas reduction is also required for the acid generator.

Patent Document 4 discloses a method of dissolving a specific acid-decomposable resin and a compound containing a compound (sulfonic acid-generating compound) which is decomposed by the action of an acid to generate a sulfonic acid, for the purpose of solving problems such as occurrence of development defects and scum A positive photoresist composition for deep ultraviolet exposure has been proposed. In Paragraph 0016 of Patent Document 4, it is described that the strength of the acid as the acid from which the sulfonic acid-generating compound is generated is preferably large. It is also described that a sulfonic acid having an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group as the acid is preferable. In the paragraphs 0017 and 0018 of the same document, the compounds represented by the general formulas (1) to (5) are listed as preferred examples of the acid.

Non-Patent Document 1 describes a photoresist using polymeric acid amplifiers. This polymeric acid-proliferating agent has a repeating unit which is decomposed by the action of an acid to generate a sulfonic acid. As the repeating unit, a structure using 2-hydroxy-3-pinanyl p-styrenesulfonate as a monomer is employed.

Non-Patent Document 2 describes an acid-proliferating agent for EUV photoresist. Specifically, in this document, it has been reported that the use of an acid-proliferator that generates fluorinated sulfonic acid can optimize sensitivity, line edge roughness (LER), and exposure latitude. Further, Non-Patent Document 3 describes a more detailed synthesis method of these acid propagating agents.

In recent years, lithography using an electron beam, X-ray, soft X-ray, or EUV light has been developed in addition to lithography using excimer laser light. In addition, microfabrication using a resist composition has been applied not only directly to the manufacture of integrated circuits but also to the so-called production of so-called mold structures for imprints (see, for example, Patent Documents 5 and 6 and Non-Patent Document 4) .

U.S. Patent No. 6548221 Specification of European Patent No. 1480078 U.S. Patent No. 6680157 Japanese Patent No. 3912761 Specification Japanese Patent Application Laid-Open No. 2004-158287 Japanese Patent Application Laid-Open No. 2008-162101

 Sang-Wook Park et al. &Quot; A Novel Photoresist Based on Polymeric Acid Amplifiers ", Chemistry Letters, 2000, pp. 1036-1037.  Robert Brainard et al. "Kinetics, Chemical Modeling and Lithography of Novel Acid Amplifiers for Use in EUV Photoresists", Journal of Photopolymer Science and Technology, Volume 22, Number 1 (2009) 43-50.  Seth Kruger et al. &Quot; Fluorinated Acid Amplifiers for EUV Lithography ", Journal of the American Chemical Society, 2009, 131 (29), pp.9862-9863.  Hirai Yoshihiko (Editor) "Fundamentals and Technology Development and Application of Nanoimprint - Nanoimprint Technology and Latest Technology Development" - Frontia Publishing (issued in June 2006)

An object of the present invention is to provide a sensitizing actinic ray or radiation-sensitive resin composition excellent in sensitivity, roughness characteristics and aging stability and a pattern forming method using the same.

The present invention is, for example, as follows. In the present invention, the "volume of the acid" means the volume of the region occupied by the van der Waals sphere based on the van der Waals radius of the atoms constituting the acid. Specifically, the "volume of acid" is a volume calculated as follows. That is, first, the most stable steric body of the acid is determined by calculating the molecular force field using the MM3 method. Thereafter, the van der Waals volume is calculated by the molecular orbital calculation using the PM3 method for this most stable three-dimensional fundus. This van der Waals volume is referred to as " volume of the acid ".

According to a first aspect of the present invention, there is provided a method for producing a sulfonic acid-generating compound, which comprises decomposing by action of an acid to form a sulfonic acid-generating compound capable of generating a sulfonic acid having a volume of 240 Å ³ or more and a compound capable of generating an acid upon irradiation with an actinic ray or radiation, A radiation-sensitive resin composition is provided.

According to a second aspect of the present invention, there is provided a resin containing a repeating unit which is decomposed by the action of an acid to generate a sulfonic acid, wherein the repeating unit is a resin having an acetal structure, and an acid A radiation-sensitive or radiation-sensitive resin composition containing a compound capable of generating a radiation-sensitive or radiation-sensitive resin.

According to a third aspect of the present invention, there is provided a resin composition comprising a resin having a structure represented by the following general formula (I) and a sensitizing actinic ray or radiation-sensitive resin containing a compound capable of generating an acid upon irradiation with an actinic ray or radiation A composition is provided.

Wherein,

Each of R ₁ to R ₅ represents a hydrogen atom or a substituent. R ₁ to R ₅ may combine with each other to form a ring.

According to a fourth aspect of the present invention, there is provided a resist film formed using the composition according to any one of the first to third aspects.

According to a fifth aspect of the present invention, there is provided a pattern formation method comprising forming a film using the composition according to any one of the first to third aspects, exposing the film, and developing the exposed film.

(Effects of the Invention)

According to the present invention, it becomes possible to provide a sensitizing actinic ray or radiation-sensitive resin composition excellent in sensitivity, roughness characteristics and aging stability and a pattern forming method using the same.

Hereinafter, embodiments of the present invention will be described in detail.

Herein, the groups or atomic groups which do not specify substitution or non-substitution include both substituents and substituents. For example, the "alkyl group" which does not specify the substitution or the non-substitution includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group (substituted alkyl group) having a substituent.

The composition according to the first embodiment contains a [1-1] sulfonic acid generating compound and [2] a compound which generates an acid upon irradiation with an actinic ray or radiation (hereinafter also referred to as a photoacid generator).

[1-1] Sulfonic acid generating compound

The composition according to the first embodiment contains a compound capable of decomposing by action of an acid or by action of an acid and heating to generate a sulfonic acid having a volume of 240 Å ³ or more.

As described above, the composition according to the first embodiment contains a sulfonic acid-generating compound and a photoacid generator. Therefore, when the composition according to the first embodiment is irradiated with actinic rays or radiation, the photoacid generator generates an acid. At least a part of the sulfonic acid generating compounds contained in the composition is decomposed by the action of an acid generated from the photoacid generator to generate the sulfonic acid. Further, the sulfonic acid-generating compound contained in the composition is decomposed by the action of the generated sulfonic acid. As a result, the other sulfonic acid generating compound generates the sulfonic acid.

Thus, the composition according to the first embodiment has a function as an acid propagating agent capable of generating an acid in a chain. Therefore, when the sulfonic acid generating compound is contained, it becomes possible to improve the sensitivity of the actinic ray-sensitive or radiation-sensitive resin composition.

Also, the sulfonic acid that can be generated by the composition according to the first embodiment has a volume of 240 Å ³ or more. That is, bulky groups are bonded to the sulfur atom of the sulfonic acid.

Due to this, the sulfonic acid generated from the sulfonic acid-generating compound hardly causes excessive diffusion in the composition. That is, when such a sulfonic acid-generating compound is used, diffusion of an acid in the composition is suppressed, and it becomes easy to generate an acid only at a desired site. Therefore, when such a sulfonic acid-generating compound is contained, it becomes possible to improve the resolution and roughness characteristics of the actinic radiation-sensitive or radiation-sensitive resin composition. In addition, the sulfo group possessed by the sulfonic acid-generating compound is less susceptible to attack from nucleophilic species. Therefore, the use of such a sulfonic acid-generating compound makes it possible to improve the stability with time of the composition.

Examples of the sulfonic acid having a volume of 240 Å ³ or more that can be generated by the sulfonic acid-generating compound include the following. In the following, the sulfonic acid is represented by the formula A-SO ₃ H. That is, in the following, the residue of the sulfonic acid is represented by the symbol A.

The residue A is, for example, an alkyl group, a cycloalkyl group or an aromatic group. Each of these alkyl groups, cycloalkyl groups and aromatic groups may have a substituent.

The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, 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, a nonyl group, a decyl group, , Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group and 2-ethylhexyl group.

The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a boronyl group, a camhenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoryl group, a dicyclohexyl group and a pinenyl group .

Examples of the aromatic group include a benzene ring, a naphthalene ring, a pentane ring, an indane ring, an azole ring, a heptylene ring, an indene ring, a perylene ring, a pentacene ring, an acetapthalene ring, a phenanthrene ring, an anthracene ring, A thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, an indole ring A benzofuran ring, a benzofuran ring, a quinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring , Phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chroman ring, xanthane ring, phenoxathiine ring, phenothiazine ring, phenanthrene ring. Among them, a benzene ring, a naphthalene ring or an anthracene ring is preferable from the viewpoint of compatibility between roughness improvement and high sensitivity, and a benzene ring is more preferable.

Examples of the substituent which the alkyl group, the cycloalkyl group and the aromatic group may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; An acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a methoxyl group; An alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; An arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; Aryl groups such as a phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; A hydroxy group; A carboxy group; Formyl group; A sulfonyl group; Cyano; An alkylaminocarbonyl group; An arylaminocarbonyl group; A sulfonamide group; Silyl group; An amino group; A titanium radical; Or a combination thereof.

The residue A preferably has a ring structure. More preferably, the sulfonic acid A-SO ₃ H is a compound represented by the following general formula (6) or (7). More preferably, the sulfonic acid A-SO ₃ H is a compound represented by the following general formula (6).

In formula (6)

Ar represents an aryl group and may further have a substituent other than the - (D-B) group.

n represents an integer of 1 or more. n is preferably 1 to 4, more preferably 2 to 3, and most preferably 3.

D represents a single bond or a divalent linking group. The divalent linking group is an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group or an ester group.

B represents a hydrocarbon group.

In formula (7)

Xf each independently represents an alkyl group substituted by a fluorine atom or at least one fluorine atom.

R ₁ and R ₂ each independently represent a group selected from a hydrogen atom, a fluorine atom, an alkyl group and an alkyl group substituted by at least one fluorine atom, and when a plurality of R ₁ and R ₂ are present, R ₁ and R ₂ may be the same or different.

L represents a single bond or a divalent linking group, and L in the presence of a plurality may be the same or different.

E represents a group having a ring structure.

x represents an integer of 1 to 20, preferably 1 to 4; y represents an integer of 0 to 10, preferably 0 to 3; z represents an integer of 0 to 10, preferably 0 to 3;

First, the sulfonic acid represented by the formula (6) will be described in detail.

In the formula (6), Ar is preferably an aromatic ring having 6 to 30 carbon atoms. Specifically, Ar is, for example, a benzene ring, a naphthalene ring, a pentane ring, an indene ring, an azuren ring, a heptylene ring, an indene ring, a perylene ring, a pentacene ring, an acetapthalene ring, a phenanthrene ring, an anthracene ring, A thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a pyrimidine ring, A benzothiophene ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carboxy ring, A phenanthridine ring, a phenanthridine ring, a phenothiazine ring, a phenanthroline ring, a phenanthroline ring, a thianthrene ring, a chroman ring, a xanthylene ring, a phenoxathiine ring, a phenothiazine ring or a phenazin ring. Among them, a benzene ring, a naphthalene ring or an anthracene ring is preferable from the viewpoint of compatibility between roughness improvement and high sensitivity, and a benzene ring is more preferable.

When Ar has a substituent other than - (D-B) group, examples of the substituent include the following. That is, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; An alkyloxy group such as a methylthio group, an ethylthio group and a tert-butylthio group; Arylthioxy groups such as phenylthio group and p-tolylthioxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acetoxy group; Straight chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; Branched alkyl groups; Alkenyl groups such as a vinyl group, a propenyl group and a hexenyl group; An acetylene group; An alkynyl group such as a propynyl group and a hexynyl group; An aryl group such as a phenyl group and a tolyl group; A hydroxy group; A carboxy group; And a sulfonic acid group. Of these, straight-chain alkyl groups and branched alkyl groups are preferred from the standpoint of improving roughness.

In formula (6), D is preferably a single bond or an ether group or an ester group. More preferably, D is a single bond.

In formula (6), B is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a cycloalkyl group. B is preferably an alkyl group or a cycloalkyl group. The alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B may have a substituent.

The alkyl group as B is preferably a branched alkyl group. Examples of the branched alkyl group include isopropyl, tert-butyl, tert-pentyl, neopentyl, sec-butyl, isobutyl, isohexyl, 3,3-dimethylpentyl and 2- Hexyl group.

The cycloalkyl group as B may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a boronyl group, a camhenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoryl group, a dicyclohexyl group and a pinenyl group .

When the alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B has a substituent, examples of the substituent include the following. That is, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; An alkyloxy group such as a methylthio group, an ethylthio group and a tert-butylthio group; Arylthioxy groups such as phenylthio group and p-tolylthioxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acetoxy group; Straight chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; Branched alkyl groups; A cycloalkyl group such as a cyclohexyl group; Alkenyl groups such as a vinyl group, a propenyl group and a hexenyl group; An acetylene group; An alkynyl group such as a propynyl group and a hexynyl group; An aryl group such as a phenyl group and a tolyl group; A hydroxy group; A carboxy group; Sulfonic acid group; And a carbonyl group. Among these, straight-chain alkyl groups and branched alkyl groups are preferable from the viewpoint of both improvement of roughness and high sensitivity.

Next, the sulfonic acid represented by the formula (7) will be described in detail.

In the formula (7), Xf is a fluorine atom or an alkyl group substituted by at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted by a fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, Xf is preferably a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH _{2 CF 3, CH 2 CH 2} CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 , or CH ₂ CH ₂ C ₄ F ₉ . Among them, a fluorine atom or CF ₃ is preferable, and a fluorine atom is most preferable.

Each of R ₁ and R ₂ in the formula (7) is a group selected from a hydrogen atom, a fluorine atom, an alkyl group and an alkyl group substituted by at least one fluorine atom. The alkyl group which may be substituted by the fluorine atom preferably has 1 to 4 carbon atoms. As the alkyl group substituted by a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms is particularly preferable. Specifically, _{CF 3, C 2 F 5,} C 3 F 7, C 4 F 9, C 5 F 11, C 6 F 13, C 7 F 15, C 8 F 17, CH 2 CF 3, CH 2 CH 2 CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ or CH ₂ CH ₂ C ₄ F ₉ Among them, CF ₃ is preferable.

In the formula (7), x is preferably from 1 to 8, more preferably from 1 to 4. y is preferably 0 to 4, more preferably 0. z is preferably 0 to 8, more preferably 0 to 4.

In formula (7), L represents a single bond or a divalent linking group. Examples of the divalent linking group include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, an alkylene group, a cycloalkylene group and an alkenylene group . Of these, -COO-, -OCO-, -CO-, -O-, -S-, -SO- or -SO ₂ - is preferable, and -COO-, -OCO- or -SO ₂ - is more preferable .

E in the formula (7) represents a group having a ring structure. Examples of E include cyclic aliphatic groups, aryl groups, and groups having a heterocyclic structure.

The cyclic aliphatic group as E may have a monocyclic structure or may have a polycyclic structure. As the cyclic aliphatic group having a monocyclic structure, monocyclic cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cyclooctyl group are preferable. The cyclic aliphatic group having a polycyclic structure is preferably a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. Particularly, when a cyclic aliphatic group having a bulky structure with a 6-member ring or more is employed as E, it is possible to suppress the diffusibility in the film in the PEB (post-exposure heating) process, and to further improve the resolution and EL (exposure latitude) .

The aryl group as E is, for example, a benzene ring, a naphthalene ring, a phenanthrene ring or an anthracene ring.

The group having a heterocyclic structure as E may have aromaticity or may not have aromaticity. The hetero atom contained in this group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic structure include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, piperidine ring and morpholine ring. Among them, furan ring, thiophen ring, pyridine ring, piperidine ring and morpholine ring are preferable.

E may have a substituent. Examples of the substituent include an alkyl group (any of linear, branched and cyclic, preferably having 1 to 12 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, A urethane group, a ureido group, a thioether group, a sulfonamide group and a sulfonic acid ester group.

Examples of sulfonic acid ASO ₃ H having a volume of 240 Å ³ or more are listed below.

In each of these examples, calculation values of the volume are added.

This value was obtained as follows using "WinMOPAC" manufactured by Fujitsu Kabushiki Kaisha. That is, first, the chemical structure of the acid according to each example was input. Then, using this structure as an initial structure, the most stable steric body of each acid was determined by calculating the molecular force field using the MM3 method. Thereafter, the "accessible volume" of each acid was calculated by performing molecular orbital calculation using the PM3 method for these most stable three-dimensional fundus.

In addition, the volume of the acid ASO ₃ H is preferably to, and more preferably from 400Å to 300Å ³ or more ³ or more. In addition, the volume is preferably ³ or less in the 1500Å to 2000Å as ³ or less, more preferably. If the volume is excessively increased, the sensitivity and / or solubility of the coating solvent may be lowered.

The sulfonic acid generating compound capable of generating the sulfonic acid ASO ₃ H is a compound having at least one group represented by ASO ₃ -.

As the sulfonic acid generating compound, for example, a compound represented by one of the following general formulas (1) to (5) is used. Preferably, a compound represented by the following general formula (1) is used as the sulfonic acid generating compound.

Each of R ₁ to R ₄ , R ₇ to R ₁₃ and R ₁₅ to R _{19 in the} formula represents a hydrogen atom or a monovalent substituent. Each of R ₅ , R ₆ and R ₁₄ represents a monovalent substituent. And A represents a residue of a sulfonic acid represented by the formula A-SO ₃ H.

Each of the compounds represented by the general formulas (1) to (5) may have a plurality of groups represented by ASO ₃ -. That is, each of the compounds represented by the general formulas (1) to (5) may have a plurality of structures capable of generating sulfonic acid ASO ₃ H in the same molecule.

The compound represented by the general formula (1) will be described in detail.

First, R ₁ to R ₄ will be described.

Each of R ₁ to R ₄ in the formula (1) represents a hydrogen atom or a monovalent substituent.

Examples of the monovalent substituent include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, halogen atoms, alkoxy groups, aryloxy groups, alkanoyl groups, An arylsulfonyl group, a cyano group, an alkylthioxy group, an arylthioxy group and a heterocyclic group. Among them, the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, alkanoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylsulfonyl group, An arylsulfonyl group, a cyano group, an alkylthioxy group, an arylthioxy group and a heterocyclic group may have a substituent.

The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, butyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a phenacyl group, a 1-naphthoylmethyl group, a 2-naphthoylmethyl group, a 4-methylsulfanylphenacyl group, A 4-dimethylaminophenacyl group, a 4-cyanophenacyl group, a 4-methylphenacyl group, a 2-methylphenacyl group, a 3-fluorophenacyl group, a 3-trifluoromethylphenacyl group, And 3-nitrophenacyl group.

The cycloalkyl group may have a monocyclic structure or may have a polycyclic structure. The cycloalkyl group having a monocyclic structure is preferably a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group. As the cycloalkyl group having a polycyclic structure, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group are preferable. A cycloalkyl group having from 3 to 8 carbon atoms is preferable, and for example, a cyclopentyl group and a cyclohexyl group are more preferable.

The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group and a styryl group.

The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, A naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, a quaterphenyl group, o-, m- and p-tolyl groups, a xylyl group, An acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, A phenanthryl group, a phenanthryl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a phenanthryl group, a phenanthryl group, a pyrenyl group, a pyrenyl group, A naphthacenyl group, a furadenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, A naphthyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a heptenyl group, a heptenyl group, a pyranthrenyl group, and an obarenyl group.

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

Examples of the alkoxy group include methoxy, ethoxy, propoxy, n-butoxy, trifluoromethoxy, hexyloxy, t-butoxy, 2-ethylhexyloxy, Silicate period and dodecyloxy period.

Examples of the aryloxy group include a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a tolyloxy group, a methoxyphenyloxy group, a naphthyloxy group, a chlorophenyloxy group, a trifluoromethylphenyloxy group, A cyanophenyloxy group and a nitrophenyloxy group.

The alkanoyl group is preferably an alkanoyl group having 2 to 20 carbon atoms, and examples thereof include an acetyl group, a propanoyl group, a butanoyl group, a trifluoromethylcarbonyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, A 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 3-methylbenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyano A benzoyl group and a 4-methoxybenzoyl group.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, And a trifluoromethyloxycarbonyl group.

Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, a 4-phenylsulfanylphenyloxycarbonyl group, Butoxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, A 3-nitrophenyloxycarbonyl group, a 4-fluorophenyloxycarbonyl group, a 4-cyanophenyloxycarbonyl group, and a 4-methoxyphenyloxycarbonyl group can be given.

The alkylsulfonyloxy group is preferably an alkylsulfonyloxy group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyloxy group, an ethylsulfonyloxy group, a propylsulfonyloxy group, an isopropylsulfonyloxy group, a butylsulfonyloxy group, Ethylhexylsulfonyloxy group, decanoylsulfonyloxy group, octadecanoylsulfonyloxy group, cyanomethylsulfonyloxy group, cyanomethylsulfonyloxy group, cyanomethylsulfonyloxy group, mercapto sulfonyloxy group, A methoxymethylsulfonyloxy group, and a perfluoroalkylsulfonyloxy group.

The arylsulfonyloxy group is preferably an arylsulfonyloxy group having 6 to 30 carbon atoms, and examples thereof include phenylsulfonyloxy group, 1-naphthylsulfonyloxy group, 2-naphthylsulfonyloxy group, 2-chlorophenylsulfonyloxy group , 2-methylphenylsulfonyloxy group, 2-methoxyphenylsulfonyloxy group, 2-butoxyphenylsulfonyloxy group, 3-chlorophenylsulfonyloxy group, 3-trifluoromethylphenylsulfonyloxy group, 3-cyanophenylsulfo 4-methoxyphenylsulfonyloxy group, 4-methylsulfanylphenylsulfonyloxy group, 4-fluorophenylsulfonyloxy group, 4-fluorophenylsulfonyloxy group, Phenylsulfanylphenylsulfonyloxy group, and 4-dimethylaminophenylsulfonyloxy group.

The alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a cyclohexylsulfonyl group, An octylsulfonyl group, a cyanomethylsulfonyl group, a methoxymethylsulfonyl group, and a perfluoroalkylsulfonyl group can be exemplified .

The arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, , 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4- A 4-methoxyphenylsulfonyl group, a 4-methylsulfanylphenylsulfonyl group, a 4-phenylsulfanylphenylsulfonyl group, and a 4-dimethylaminophenylsulfonyl group, have.

Examples of the alkyloxy group include methylthio group, ethylthio group, propylthio group, n-butylthio group, trifluoromethylthio group, hexylthio group, t-butylthio group, A cyclohexylthio group, a decylthio group, and a dodecylthio group.

Examples of the aryloxy group include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a tolylthioxy group, a methoxyphenylthio group, a naphthylthio group, a chlorophenylthio group, A cyano group, a thio group, a cyanophenylthio group and a nitrophenylthio group.

The heterocyclic group is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples of the heterocyclic group include thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thienyl, furyl, A pyridyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, an indolizinyl group, an isoindolyl group, a pyridazinyl group, a pyridazinyl group, a pyridazinyl group, , 3H-indolyl group, indolyl group, 1H-indazolyl group, fluorenyl group, 4H-quinolizinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, A phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, An isothiazolyl group, a phenothiazinyl group, an isoxazolyl group, a furazanyl group, a phenoxazinyl group, an isochromanyl group, a chromanyl group, a pyrrole An imidazolidinyl group, an imidazolidinyl group, a pyrazolinylidene group, a pyrazolinyl group, a piperidyl group, a piperazinyl group, an indolinyl group, an isoindolinyl group, a quinuclidinyl group, A morpholinyl group and a thioxanthryl group.

Examples of the substituent which may have any one of R ₁ to R ₄ include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; An acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a methoxyl group; An alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; An arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkylamino groups such as methylamino group and cyclohexylamino group; Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group; Arylamino groups such as phenylamino group and p-tolylamino group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; Aryl groups such as a phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; A hydroxy group; A carboxy group; Formyl group; A mercapto group; Sulfo group; A mesyl group; p-toluenesulfonyl group; An amino group; A nitro group; Cyano; A trifluoromethyl group; Trichloromethyl group; A trimethylsilyl group; Phosphino group; Phosphono group; A trimethylammonium group; A dimethylsulfonium group, and a triphenylphenacylphosphonium group.

Two or more of R ₁ to R ₄ may be bonded to each other to form a ring structure. The ring structure may be an aliphatic or aromatic hydrocarbon ring or may be a heterocyclic ring containing a hetero atom. These R ₁ to R ₄ may form a polycyclic fused ring.

Examples of the aliphatic or aromatic hydrocarbon ring include a 6-membered ring, a 5-membered ring or a 7-membered ring structure. The hydrocarbon ring is preferably a 6-membered ring or a 5-membered ring structure, particularly preferably a 5-membered ring structure.

Examples of the heterocyclic ring include those containing a sulfur atom, an oxygen atom or a nitrogen atom as a hetero atom. As the heterocyclic ring, it is more preferable to contain a sulfur atom as a hetero atom.

Examples of polycyclic condensed rings include condensed rings composed of only hydrocarbon rings. Examples of the polycyclic condensed rings include those in which 2 to 4 benzene rings form a condensed ring and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.

The polycyclic fused ring may be a condensed ring containing at least one heterocyclic ring. Examples of the polycyclic condensed rings include those in which a benzene ring and a 5-membered heterocyclic ring form a condensed ring and those in which a benzene ring and a 6-membered heterocyclic ring form a condensed ring.

Examples of the ring structure that R ₁ to R ₄ can form include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, a biphenyl ring, a pyrrole ring, , Thiophene ring, dithiolane ring, oxirane, dioxiran ring, thienyl ring, pyrrolidine ring, piperidine ring, imidazole ring, isoxazole ring, benzodithio ring, oxazole ring, thiazole ring, benzothiazole ring , Benzoimidazole ring, benzoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazin ring, indolizine ring, indole ring, benzofuran ring, benzothiophen ring, benzodithio ring, isobenzofuran ring, A phenanthroline ring, a phenanthroline ring, a thianthrene ring, a croman ring, a xanthylene ring, a thiophene ring, a thiophene ring, a thiophene ring, a thiophene ring, Phenanthridine ring, phenothiazine ring, and phenanthrene ring. Among them, dithiolane ring, benzodithiol ring, benzothiazole ring, benzoimidazole ring and benzoxazole ring are particularly preferable.

Examples of R ₁ to R ₄ in the general formula (1) include those described in the following chemical formulas.

Next, R ₅ and R ₆ will be described.

Each of R ₅ and R ₆ in the formula (1) represents a monovalent substituent. Examples of the monovalent substituent include monovalent organic groups and silyl groups. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkanoyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, alkylthiocarbonyl groups, arylthiocarbonyl groups, And a dialkylaminocarbonyl group. These monovalent organic groups may further have a substituent.

Examples of the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, alkanoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylthiocarbonyl group and arylthiocarbonyl group include R ₁ to R ₄ are the same as those listed above.

Examples of the dialkylaminocarbonyl group which may have a substituent include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dipropylaminocarbonyl group and a dibutylaminocarbonyl group.

R ₅ and R ₆ are preferably bonded to each other to form a cyclic acetal structure. The cyclic acetal structure may have an aliphatic or aromatic hydrocarbon ring or a heterocyclic ring containing a hetero atom as a substituent. These hydrocarbon rings and / or heterocyclic rings may form a condensed ring with the cyclic acetal. Examples of the hydrocarbon ring and the heterocyclic ring include the same as those listed above for R ₁ to R ₄ .

Examples of R ₅ and R ₆ in the general formula (1) include those described in the following chemical formulas.

Examples of R ₁ to R ₆ in the general formula (1) include those described in the following formulas.

The compounds represented by the general formulas (2) to (5) will be described in detail.

First, R ₇ to R ₉ in the formula (2) will be described.

R ₇ to R ₉ are each a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group.

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an octyl group.

The cycloalkyl group is preferably a cycloalkyl group having 4 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a boronyl group, an isoboronyl group, a tricyclodecanyl group , A dicyclopentenyl group, a norbornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group and a tetracyclododecanyl group.

The aryl group is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group and a tolyl group.

Examples of the aralkyl group include an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, and a naphthylethyl group.

These alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups may have substituents. Examples of the substituent include a halogen atom such as Cl, Br and F, a -CN group, an -OH group, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, , An aralkyl group such as a benzyl group and a phenethyl group, an allyloxyalkyl group such as a phenoxyethyl group, an alkoxycarbonyl group having a carbon number of 2 to 5, and an acyloxy group having a carbon number of 2 to 5.

Preferred examples of R ₇ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a naphthyl group, a benzyl group and a phenethyl group .

Preferable examples of R ₈ include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a neopentyl group, a cyclohexyl group, a phenyl group, a benzyl group and a hydrogen atom.

Preferable examples of R ₉ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a naphthyl group, a benzyl group and a phenethyl group .

It is more preferable that R ₇ and R ₉ are bonded to each other to form a ring structure. As the ring structure, a cyclopentyl ring or a cyclohexyl ring is particularly preferable.

Next, R ₁₀ and R ₁₁ in the formula (3) will be described.

R ₁₀ and R ₁₁ are each a hydrogen atom or a monovalent substituent.

Examples of R ₁₀ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyloxy group and a hydrogen atom.

Examples of R ₁₁ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group and a hydrogen atom.

Examples of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group include the same groups as those listed above for the general formula (2).

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a cyclohexyloxy group and a butoxy group.

The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group and a naphthoxy group.

The alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, and examples thereof include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group and a cyclohexenyl group.

The alkenyloxy group is preferably an alkenyloxy group having 2 to 8 carbon atoms, and specific examples thereof include a vinyloxy group and an allyloxy group.

These alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, alkenyl groups and alkenyloxy groups may have substituents. Examples of the substituent include the same ones listed above for the general formula (2).

Preferable examples of R ₁₀ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, A t-butyl group, a benzyl group, a phenoxy group, a naphthoxy group, a vinyloxy group and a methylvinyloxy group.

Preferable examples of R ₁₁ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, A t-butyl group, a benzyl group, a phenoxy group, a naphthoxy group, a vinyl group and an allyl group.

It is more preferable that R ₁₀ and R ₁₁ are bonded to each other to form a ring structure. As the ring structure, a 3-oxocyclohexenyl ring or a 3-oxoindenyl ring is particularly preferable. These 3-oxocyclohexenyl ring and 3-oxoindenyl ring may contain an oxygen atom in the ring.

Next, R ₁₂ to R ₁₄ in the formula (4) will be described.

R ₁₂ and R ₁₃ are each a hydrogen atom or a monovalent substituent. R ₁₄ is a monovalent substituent.

Examples of R ₁₂ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group and a hydrogen atom.

Examples of R ₁₃ include an alkyl group, an alkoxy group, a halogen atom, an aralkyl group and a hydrogen atom.

R ₁₄ is, for example, a group which is eliminated by the action of an acid.

Examples of the group eliminated by the action of an acid include -C (R36) (R37) (R38), -C (= O) -OC (R36) (R37) (OR39), -C (R01) (R02) -C (= O) -OC (R36) (R37) (R38) and -CH (R36) (Ar).

In the formula, R36 to R39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R36 and R37 may be bonded to each other to form a ring.

R01 to R02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

Ar represents an aryl group.

Examples of the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkoxy group and the aryloxy group are the same as those enumerated for the general formulas (2) and (3). These groups may have a substituent. Examples of the substituent include the same ones listed above for the general formula (2).

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

Preferred examples of R ₁₂ include a methyl group, an ethyl group, a propyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, a naphthylmethyl group and a hydrogen atom.

Preferable examples of R ₁₃ include a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group and a hydrogen atom.

Preferable examples of R ₁₄ include a tertiary alkyl group such as a t-butyl group, an alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group and a 1-ethoxyethyl group, and a tetrahydropyranyl group.

Next, R ₁₅ to R ₁₉ in the formula (5) will be described.

R ₁₅ to R ₁₉ are each a hydrogen atom or a monovalent substituent.

Examples of R ₁₅ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyloxy group and a hydrogen atom.

Examples of R ₁₆ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group and a hydrogen atom.

Examples of R ₁₇ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group and a hydrogen atom.

Examples of R ₁₈ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group and a hydrogen atom.

Examples of R ₁₉ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group and a hydrogen atom.

Examples of the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkoxy group, the aryloxy group, the alkenyl group and the alkenyloxy group are the same as those enumerated for the general formulas (2) and (3).

These alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, alkenyl groups and alkenyloxy groups may have substituents. Examples of the substituent include the same ones listed above for the general formula (2).

Preferable examples of R ₁₅ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, A t-butyl group, a benzyl group, a phenoxy group, a naphthoxy group, a vinyloxy group and a methylvinyloxy group.

Preferable examples of R ₁₆ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, A t-butyl group, a benzyl group, a phenoxy group, a naphthoxy group, a vinyl group and an allyl group.

Preferable examples of R ₁₇ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, A t-butyl group, a benzyl group, a phenoxy group, a naphthoxy group, a vinyl group and an allyl group.

Preferable examples of R ₁₈ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, A t-butyl group, a benzyl group, a phenoxy group, a naphthoxy group, a vinyl group and an allyl group.

Preferable examples of R ₁₉ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, A t-butyl group, a benzyl group, a phenoxy group, a naphthoxy group, a vinyl group and an allyl group.

At least two of R ₁₅ to R ₁₉ may be bonded to each other to form a ring structure.

Examples of R ₇ to R _{19 in the} general formulas (2) to (5) include those described in the following chemical formulas.

Among the compounds represented by the general formulas (1) to (5), compounds represented by the general formula (1) are particularly preferable in view of sensitivity, resolution and roughness performance.

Examples of the sulfonic acid-generating compound represented by any one of formulas (1) to (5) include the followings.

The content of the sulfonic acid generating compound is preferably from 0.1 to 50 mass%, more preferably from 0.5 to 40 mass%, and still more preferably from 1.0 to 30 mass%, based on the total solid content of the composition.

As a method for producing the sulfonic acid-generating compound of the present invention, an appropriate solvent such as an inert solvent such as THF, DMF and acetonitrile, or an inert solvent such as pyridine or pyridine in the presence of a base (for example, triethylamine or pyridine) using a corresponding alcohol compound and a sulfonyl halide or a sulfonic anhydride In a basic solvent such as tetrahydrofuran or the like. The reaction temperature is preferably -10 to 60 占 폚.

In addition, various sulfonic acid generating compounds corresponding to the above sulfonyl halide can be synthesized by using an alkylsulfonyl halide and an arylsulfonyl halide.

The composition according to the second and third embodiments contains (i) an acid-proliferating agent-carrying resin, (ii) a compound capable of generating an acid upon irradiation with an actinic ray or radiation (hereinafter also referred to as a photoacid generator) .

[1-2] Acid proliferating agent-bearing resin

The acid-proliferating agent-carrying resin contains an acid-proliferating unit. The acid-proliferating unit is a repeating unit which is decomposed by the action of an acid or by the action of an acid and heating to generate a sulfonic acid.

As described above, the compositions according to the second and third embodiments contain the acid-proliferating agent-carrying resin and the photoacid generator. Therefore, when the compositions according to the second and third embodiments are irradiated with an actinic ray or radiation, the photoacid generator generates an acid. At least a part of the acid-proliferating unit contained in the acid-proliferating agent-carrying resin is decomposed by the action of an acid generated from the photoacid generator or by the action of the acid and heating to generate sulfonic acid. In addition, the other acid-proliferating unit is decomposed by the action of the generated sulfonic acid. Whereby the other acid-proliferating unit further generates sulfonic acid. Each of these acid proliferating units can generate an acid in a chain.

An acid propagation unit having a [P] acetal structure

The acid-proliferant-carrying resin according to the second embodiment contains an acid-proliferating unit having an acetal structure.

The inventors of the present invention have found that an acid-proliferating agent-containing resin containing an acid-proliferating unit having an acetal structure has higher acid-proliferating ability and stability than conventional acid-proliferating agents. The reason for this is not necessarily clear, but the present inventors assume as follows. That is, it is presumed that the excellent acid proliferation ability is attributable to the deprotection reaction of the acetal in the presence of an acid and / or the ease of the β-elimination reaction. Further, it is presumed that the excellent stability is due to the high thermal stability of the acetal structure.

Therefore, when an acid-proliferating agent-carrying resin containing an acid-proliferating unit having an acetal structure is used, it becomes possible to obtain a composition having both excellent sensitivity and long-term stability. That is, this makes it possible to achieve both excellent sensitivity and excellent stability over time.

The acid-propagating agent unit preferably has a structure represented by the following general formula (I).

In the formula, each of R ₁ to R ₄ represents a hydrogen atom or a substituent. R ₁ to R ₄ may combine with each other to form a ring structure.

Each of R ₅ and R ₆ represents a substituent. R ₅ and R ₆ may be bonded to each other to form a cyclic acetal structure.

The structure represented by the general formula (I) can generate a sulfonic acid by the action of an acid. Although the mechanism is not necessarily clear, the present inventors believe that the reaction proceeds according to the following scheme. In the following scheme, the part indicated by " o " means a binding site having a structure represented by general formula (I).

Hereinafter, the structure represented by the general formula (I) will be described in detail.

First, R ₁ to R ₄ will be described.

Each of R ₁ to R ₄ represents a hydrogen atom or a substituent. Examples of the substituent include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, halogen atoms, alkoxy groups, aryloxy groups, alkanoyl groups, An alkylsulfonyl group, an arylsulfonyl group, a cyano group, an alkylthioxy group, an arylthioxy group and a heterocyclic group.

Each of R ₁ to R ₃ is preferably a hydrogen atom, an alkyl group or an alkoxy group.

R ₄ is preferably a hydrogen atom, an alkyl group, an aryl group or a cyano group.

The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, butyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a phenacyl group, a 1-naphthoylmethyl group, a 2-naphthoylmethyl group, a 4-methylsulfanylphenacyl group, A 4-dimethylaminophenacyl group, a 4-cyanophenacyl group, a 4-methylphenacyl group, a 2-methylphenacyl group, a 3-fluorophenacyl group, a 3-trifluoromethylphenacyl group, And 3-nitrophenacyl group.

The cycloalkyl group may have a monocyclic structure or may have a polycyclic structure. The cycloalkyl group having a monocyclic structure is preferably a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group. As the cycloalkyl group having a polycyclic structure, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group are preferable. A cycloalkyl group having from 3 to 8 carbon atoms is preferable, and for example, a cyclopentyl group and a cyclohexyl group are more preferable.

The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group and a styryl group.

The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, A naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, a quaterphenyl group, o-, m- and p-tolyl groups, a xylyl group, An acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, A phenanthryl group, a phenanthryl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a phenanthryl group, a phenanthryl group, a pyrenyl group, a pyrenyl group, A naphthacenyl group, a furadenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, A naphthyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a heptenyl group, a heptenyl group, a pyranthrenyl group, and an obarenyl group.

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

Examples of the alkoxy group include methoxy, ethoxy, propoxy, n-butoxy, trifluoromethoxy, hexyloxy, t-butoxy, 2-ethylhexyloxy, Silicate period and dodecyloxy period.

Examples of the aryloxy group include a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a tolyloxy group, a methoxyphenyloxy group, a naphthyloxy group, a chlorophenyloxy group, a trifluoromethylphenyloxy group, A cyanophenyloxy group and a nitrophenyloxy group.

The alkanoyl group is preferably an alkanoyl group having 2 to 20 carbon atoms, and examples thereof include an acetyl group, a propanoyl group, a butanoyl group, a trifluoromethylcarbonyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, A 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 3-methylbenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyano A benzoyl group and a 4-methoxybenzoyl group.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, And a trifluoromethyloxycarbonyl group.

Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, a 4-phenylsulfanylphenyloxycarbonyl group, Butoxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, A 3-nitrophenyloxycarbonyl group, a 4-fluorophenyloxycarbonyl group, a 4-cyanophenyloxycarbonyl group, and a 4-methoxyphenyloxycarbonyl group can be given.

The alkylsulfonyloxy group is preferably an alkylsulfonyloxy group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyloxy group, an ethylsulfonyloxy group, a propylsulfonyloxy group, an isopropylsulfonyloxy group, a butylsulfonyloxy group, Ethylhexylsulfonyloxy group, decanoylsulfonyloxy group, octadecanoylsulfonyloxy group, cyanomethylsulfonyloxy group, cyanomethylsulfonyloxy group, cyanomethylsulfonyloxy group, mercapto sulfonyloxy group, A methoxymethylsulfonyloxy group, and a perfluoroalkylsulfonyloxy group.

The arylsulfonyloxy group is preferably an arylsulfonyloxy group having 6 to 30 carbon atoms, and examples thereof include phenylsulfonyloxy group, 1-naphthylsulfonyloxy group, 2-naphthylsulfonyloxy group, 2-chlorophenylsulfonyloxy group , 2-methylphenylsulfonyloxy group, 2-methoxyphenylsulfonyloxy group, 2-butoxyphenylsulfonyloxy group, 3-chlorophenylsulfonyloxy group, 3-trifluoromethylphenylsulfonyloxy group, 3-cyanophenylsulfo 4-methoxyphenylsulfonyloxy group, 4-methylsulfanylphenylsulfonyloxy group, 4-fluorophenylsulfonyloxy group, 4-fluorophenylsulfonyloxy group, Phenylsulfanylphenylsulfonyloxy group, and 4-dimethylaminophenylsulfonyloxy group.

The alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a cyclohexylsulfonyl group, An octylsulfonyl group, a cyanomethylsulfonyl group, a methoxymethylsulfonyl group, and a perfluoroalkylsulfonyl group can be exemplified .

The arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, , 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4- A 4-methoxyphenylsulfonyl group, a 4-methylsulfanylphenylsulfonyl group, a 4-phenylsulfanylphenylsulfonyl group, and a 4-dimethylaminophenylsulfonyl group, have.

Examples of the alkyloxy group include methylthio group, ethylthio group, propylthio group, n-butylthio group, trifluoromethylthio group, hexylthio group, t-butylthio group, A cyclohexylthio group, a decylthio group, and a dodecylthio group.

Examples of the aryloxy group include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a tolylthioxy group, a methoxyphenylthio group, a naphthylthio group, a chlorophenylthio group, A cyano group, a thio group, a cyanophenylthio group and a nitrophenylthio group.

The heterocyclic group is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples of the heterocyclic group include thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thienyl, furyl, A pyridyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, an indolizinyl group, an isoindolyl group, a pyridazinyl group, a pyridazinyl group, a pyridazinyl group, , 3H-indolyl group, indolyl group, 1H-indazolyl group, fluorenyl group, 4H-quinolizinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, A phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, An isothiazolyl group, a phenothiazinyl group, an isoxazolyl group, a furazanyl group, a phenoxazinyl group, an isochromanyl group, a chromanyl group, a pyrrole An imidazolidinyl group, an imidazolidinyl group, a pyrazolinylidene group, a pyrazolinyl group, a piperidyl group, a piperazinyl group, an indolinyl group, an isoindolinyl group, a quinuclidinyl group, Morpholinyl and thioxanthryl groups.

Examples of the substituent which may have any one of R ₁ to R ₄ include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; An acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a methoxyl group; An alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; An arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkylamino groups such as methylamino group and cyclohexylamino group; Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group; Arylamino groups such as phenylamino group and p-tolylamino group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; Aryl groups such as a phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; A hydroxy group; A carboxy group; Formyl group; A mercapto group; Sulfo group; A mesyl group; p-toluenesulfonyl group; An amino group; A nitro group; Cyano; A trifluoromethyl group; Trichloromethyl group; A trimethylsilyl group; Phosphino group; Phosphono group; A trimethylammonium group; A dimethylsulfonium group, and a triphenylphenacylphosphonium group.

As described above, two or more of R ₁ to R ₄ may be bonded to each other to form a ring structure. The ring structure may be an aliphatic or aromatic hydrocarbon ring or may be a heterocyclic ring containing a hetero atom. These R ₁ to R ₄ may form a condensed ring.

Examples of the aliphatic or aromatic hydrocarbon ring include a 6-membered ring, a 5-membered ring or a 7-membered ring structure. The hydrocarbon ring is preferably a 6-membered ring or a 5-membered ring structure, particularly preferably a 5-membered ring structure.

Examples of the heterocyclic ring include those containing a sulfur atom, an oxygen atom or a nitrogen atom as a hetero atom. As the heterocyclic ring, it is more preferable to contain a sulfur atom as a hetero atom.

As the condensed ring, for example, condensed rings composed only of hydrocarbon rings can be given. Examples of the polycyclic condensed rings include those in which 2 to 4 benzene rings form a condensed ring and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.

The condensed ring may be a condensed ring containing at least one heterocyclic ring. Examples of the condensed rings include those in which a benzene ring and a 5-membered heterocyclic ring form a condensed ring, and those in which a benzene ring and a 6-membered heterocyclic ring form a condensed ring.

Examples of the ring structure that R ₁ to R ₄ can form include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, a biphenyl ring, a pyrrole ring, , Thiophene ring, dithiolane ring, oxirane, dioxiran ring, thienyl ring, pyrrolidine ring, piperidine ring, imidazole ring, isoxazole ring, benzodithio ring, oxazole ring, thiazole ring, benzothiazole ring , Benzoimidazole ring, benzoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazin ring, indolizine ring, indole ring, benzofuran ring, benzothiophen ring, benzodithio ring, isobenzofuran ring, A phenanthroline ring, a phenanthroline ring, a thianthrene ring, a croman ring, a xanthylene ring, a thiophene ring, a thiophene ring, a thiophene ring, a thiophene ring, Phenanthridine ring, phenothiazine ring, and phenanthrene ring. Among them, dithiolane ring, benzodithiol ring, benzothiazole ring, benzoimidazole ring and benzoxazole ring are particularly preferable.

Examples of R ₁ to R ₄ in the general formula (1) include those described in the following chemical formulas.

Next, R ₅ and R ₆ will be described.

Each of R ₅ and R ₆ in the formula (I) represents a substituent. Examples of the substituent include organic groups and silyl groups. Examples of the organic group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkanoyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, alkylthiocarbonyl groups, arylthiocarbonyl groups, and di And an alkylaminocarbonyl group. These organic groups may further have a substituent.

Each of R ₅ and R ₆ is preferably an alkyl group. As described later, it is more preferable that R ₅ and R ₆ are bonded to each other to form a cyclic acetal structure.

Examples of the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, alkanoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylthiocarbonyl group and arylthiocarbonyl group include R ₁ to R ₄ are the same as those listed above.

Examples of the dialkylaminocarbonyl group which may have a substituent include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dipropylaminocarbonyl group and a dibutylaminocarbonyl group.

R ₅ and R ₆ are preferably bonded to each other to form a cyclic acetal structure. This makes it possible to further improve the outgas performance. The cyclic acetal structure may have an aliphatic or aromatic hydrocarbon ring or a heterocyclic ring containing a hetero atom as a substituent. These hydrocarbon rings and / or heterocyclic rings may form a condensed ring with the cyclic acetal.

Examples of the aliphatic or aromatic hydrocarbon ring include a 6-membered ring, a 5-membered ring or a 7-membered ring structure. The hydrocarbon ring is preferably a 6-membered ring or a 5-membered ring structure, particularly preferably a 5-membered ring structure.

Examples of the heterocyclic ring include those containing a sulfur atom, an oxygen atom or a nitrogen atom as a hetero atom. As the heterocyclic ring, it is more preferable to contain a sulfur atom as a hetero atom.

As the condensed ring, for example, condensed rings composed only of hydrocarbon rings can be given. Examples of the condensed rings include those in which 2 to 4 benzene rings form a condensed ring and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.

The condensed ring may be a condensed ring containing at least one heterocyclic ring. Examples of the condensed rings include those in which a benzene ring and a 5-membered heterocyclic ring form a condensed ring, and those in which a benzene ring and a 6-membered heterocyclic ring form a condensed ring.

Examples of the ring structure that R ₅ and R ₆ can form include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, a biphenyl ring, , Thiophene ring, dithiolane ring, oxirane, dioxiran ring, thienyl ring, pyrrolidine ring, piperidine ring, imidazole ring, isoxazole ring, benzodithio ring, oxazole ring, thiazole ring, benzothiazole ring , Benzoimidazole ring, benzoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazin ring, indolizine ring, indole ring, benzofuran ring, benzothiophen ring, benzodithio ring, isobenzofuran ring, A phenanthroline ring, a phenanthroline ring, a thianthrene ring, a croman ring, a xanthylene ring, a thiophene ring, a thiophene ring, a thiophene ring, a thiophene ring, Phenanthridine ring, phenothiazine ring, and phenanthrene ring. Among them, dithiolane ring, benzodithiol ring, benzothiazole ring, benzoimidazole ring and benzoxazole ring are particularly preferable.

Examples of R ₅ and R ₆ in the general formula (I) include those described in the following chemical formulas.

At least a part of the acid-proliferating unit is preferably a repeating unit represented by the following general formula (II). That is, at least a part of the acid-proliferating unit preferably contains the structure represented by the general formula (I) in the form represented by the following general formula (II).

In the general formula (II), Ra and Rb each independently represent a hydrogen atom, an alkyl group or a cyano group.

Rc represents a hydrogen atom or a substituent. L represents a single bond or a linking group. When Rc is the above substituent and L is the above linking group, Rc and L may be bonded to each other to form a ring structure.

Each of R ₁ to R ₆ is the same as that described above for general formula (I).

When at least a part of the acid-propagating agent unit is a repeating unit represented by the general formula (II), a sulfonic acid can be generated in a form bound to the resin. Therefore, in this case, the generated sulfonic acid is hardly diffused in the composition. Therefore, in this case, the resolution and roughness characteristics of the actinic ray-sensitive or radiation-sensitive resin composition can be further improved.

Each Ra and Rb represents a hydrogen atom, an alkyl group or a cyano group, as described above. The alkyl group may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom and a chlorine atom, and a hydroxy group. Examples of the alkyl group of Ra or Rb include a methyl group, a chloromethyl group, a trifluoromethyl group and a hydroxymethyl group. Each of Ra and Rb is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Rc represents a hydrogen atom or a substituent, as described above. Examples of the substituent include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkanoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthiocarbonyl group, , A heterocyclic group, a (di) alkylaminocarbonyl group and an aminothiocarbonyl group.

L represents a single bond or a linking group, as described above.

This linkage is preferably a single bond, an arylene group, an alkylene group, a cycloalkylene group, -O-, -S-, -SO ₂ -, -CO-, -N (R ₃₃ ) - or a combination thereof. This linking group is more preferably a single bond, an arylene group, an alkylene group, -O-, -SO ₂ -, -CO-, -N (R ₃₃ ) - or a combination thereof. Here, R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.

Rc and L may be bonded to each other to form a ring structure. Examples of the ring structure include monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocyclic rings.

Ra, Rb, Rc and L in the general formula (II) are preferably those represented by the following general formulas (III-1), (III-2), (III- ) Or (V-1). Of these, the structures represented by the general formula (III-1) or (III-2) are particularly preferable.

Wherein,

Ar _1a represents an arylene group.

R ₀₁ represents a hydrogen atom, an alkyl group or a cyano group. The alkyl group may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom and a chlorine atom. Examples of the alkyl group of R < ₀₁ > include a methyl group, a chloromethyl group and a trifluoromethyl group. R ₀₁ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Each of R ₀₂ and R ₀₂₁ represents a single bond or a divalent linking group. This divalent linking group is, for example, an arylene group, an alkylene group, a cycloalkylene group, -O-, -S-, -SO ₂ -, -CO-, -N (R ₃₃ ) - or a combination thereof. Here, R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.

The arylene group as R ₀₂ or R ₀₂₁ preferably has 6 to 14 carbon atoms, and specific examples thereof include a phenylene group, a tolylene group and a naphthylene group. The arylene group may further have a substituent.

The alkylene group as R ₀₂ or R ₀₂₁ is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group. The alkylene group may further have a substituent.

The cycloalkylene group as R ₀₂ or R ₀₂₁ is preferably a cycloalkylene group having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group. The cycloalkylene group may further have a substituent.

R ₀₃ and R ₀₁₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.

The alkyl group as R ₀₃ or R ₀₁₉ preferably has a carbon number such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, More preferably 20 or less, and more preferably 8 or less.

The cycloalkyl group as R ₀₃ or R ₀₁₉ may be monocyclic or polycyclic. Examples of the cycloalkyl group include a cyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The aryl group as R ₀₃ or R ₀₁₉ preferably has 6 to 15 carbon atoms. Examples of such an aryl group include a phenyl group, a tolyl group, a naphthyl group and an anthryl group.

The aralkyl group as R ₀₃ or R ₀₁₉ preferably has 6 to 20 carbon atoms. Examples of such an aralkyl group include a benzyl group and a phenethyl group.

Each of these alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups may have a substituent. Examples of the substituent include a hydroxyl group; Halogen atoms such as fluorine, chlorine, bromine and iodine atoms; A nitro group; Cyano; Amide group; A sulfonamide group; An alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group; An alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group and a butoxy group; An alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; An acyl group such as a formyl group, an acetyl group and a benzoyl group; An acyloxy group such as an acetoxy group and a butyryloxy group, and a carboxy group. These substituents preferably have a carbon number of 8 or less.

The arylene group as Ar _1a preferably has 6 to 14 carbon atoms. Examples of such an arylene group include a phenylene group, a tolylene group and a naphthylene group.

The arylene group may have a substituent. Examples of the substituent include the same groups as those listed above for R ₀₃ and R ₀₁₉ .

Preferred examples of the partial structure of the formula (II) include the following.

Specific examples of the polymerizable compound corresponding to the acid-proliferating unit are listed below, but the scope of the present invention is not limited thereto.

The content of the acid-propagating agent unit in the acid-proliferative agent-carrying resin in the second embodiment is preferably within the range of 3 to 80 mol%, more preferably 5 to 70 mol%, based on the total repeating units , And particularly preferably in the range of 7 to 60 mol%.

As a method for producing the acid-proliferating monomers corresponding to the acid-proliferating unit, there may be mentioned a method of reacting an acid generator with a sulfonyl halide or a sulfonic anhydride having a corresponding alcohol compound and a polymerizable group in the presence of a base (for example, triethylamine or pyridine) In an inert solvent such as DMF and acetonitrile, or in a basic solvent such as pyridine. The reaction temperature is preferably -10 to 60 占 폚.

In addition, various acid proliferator monomers corresponding to the sulfonyl halide can be synthesized by using an alkylsulfonyl halide and an arylsulfonyl halide as the sulfonyl halide.

[Q] An acid generator unit represented by the following general formula (I)

The acid-proliferative agent-carrying resin according to the third embodiment has the structure represented by the following general formula (I).

In the formulas, each of R ₁ to R ₅ represents a hydrogen atom or a substituent. R ₁ to R ₅ may combine with each other to form a ring.

The structure represented by the general formula (I) can generate a sulfonic acid by the action of an acid. Although the mechanism is not necessarily clear, the present inventors believe that the reaction proceeds according to the following scheme. In the following scheme, the part indicated by " o " means a binding site having a structure represented by general formula (I).

As shown in the above scheme, the structure represented by general formula (I) generates a carbon-carbon double bond by dehydration reaction using an acid as a catalyst. This structure then involves the desorption of the carbanion and produces the sulfonic acid anion. Thereafter, an alkene is generated from the carbanion and a sulfonic acid is generated from the sulfonic acid anion. The above reaction can proceed with high efficiency since the carbanion generated by the elimination is conjugated and stabilized.

The present inventors have found that the acid-proliferating agent-carrying resin having the structure represented by the general formula (I) has higher acid-proliferating ability and stability as compared with the conventional acid-proliferating agent. The reason for this is not necessarily clear, but the present inventors assume as follows. That is, it is presumed that the excellent acid propagation ability is attributable to the ease of the above-mentioned elimination reaction. Further, it is presumed that excellent stability is due to a high thermal stability of a structure containing a hydroxyl group.

Therefore, when the acid-proliferating agent-carrying resin is used, it becomes possible to obtain a composition having both excellent sensitivity and long-term stability. That is, this makes it possible to achieve both excellent sensitivity and excellent stability over time.

Further, the structure represented by the general formula (I) is supported on the resin. Therefore, the acid-proliferative agent-carrying resin can generate sulfonic acid in a form bound to the resin. Therefore, when the acid-proliferating agent-carrying resin is used, diffusion of the sulfonic acid in the composition can be suppressed. This makes it possible to achieve excellent resolution and roughness characteristics.

Hereinafter, the structure represented by the general formula (I) will be described in detail.

Each of R ₁ to R ₅ represents a hydrogen atom or a substituent. Examples of the substituent include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, halogen atoms, alkoxy groups, aryloxy groups, alkanoyl groups, An alkylsulfonyl group, an arylsulfonyl group, a cyano group, an alkylthioxy group, an arylthioxy group and a heterocyclic group.

Each of R ₁ to R ₃ is preferably a hydrogen atom, an alkyl group or an alkoxy group.

Each of R ₄ and R ₅ is preferably a hydrogen atom, an alkyl group, an aryl group or a cyano group.

The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, butyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a phenacyl group, a 1-naphthoylmethyl group, a 2-naphthoylmethyl group, a 4-methylsulfanylphenacyl group, A 4-dimethylaminophenacyl group, a 4-cyanophenacyl group, a 4-methylphenacyl group, a 2-methylphenacyl group, a 3-fluorophenacyl group, a 3-trifluoromethylphenacyl group, And 3-nitrophenacyl group.

The cycloalkyl group may have a monocyclic ring or may have a polycyclic ring. As the monocyclic cycloalkyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are preferable. The cycloalkyl group having a polycyclic ring is preferably a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. A cycloalkyl group having from 3 to 8 carbon atoms is preferable, and for example, a cyclopentyl group and a cyclohexyl group are more preferable.

The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group and a styryl group.

The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, A naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, a quaterphenyl group, o-, m- and p-tolyl groups, a xylyl group, An acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, an acenaphthyl group, A phenanthryl group, a phenanthryl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a phenanthryl group, a phenanthryl group, a pyrenyl group, a pyrenyl group, A naphthacenyl group, a furadenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, A naphthyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a norbornyl group, a heptenyl group, a heptenyl group, a pyranthrenyl group, and an obarenyl group.

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

Examples of the alkoxy group include methoxy, ethoxy, propoxy, n-butoxy, trifluoromethoxy, hexyloxy, t-butoxy, 2-ethylhexyloxy, Silicate period and dodecyloxy period.

Examples of the aryloxy group include a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a tolyloxy group, a methoxyphenyloxy group, a naphthyloxy group, a chlorophenyloxy group, a trifluoromethylphenyloxy group, A cyanophenyloxy group and a nitrophenyloxy group.

The alkanoyl group is preferably an alkanoyl group having 2 to 20 carbon atoms, and examples thereof include an acetyl group, a propanoyl group, a butanoyl group, a trifluoromethylcarbonyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, A 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 3-methylbenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyano A benzoyl group and a 4-methoxybenzoyl group.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, And a trifluoromethyloxycarbonyl group.

Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, a 4-phenylsulfanylphenyloxycarbonyl group, Butoxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, A 3-nitrophenyloxycarbonyl group, a 4-fluorophenyloxycarbonyl group, a 4-cyanophenyloxycarbonyl group, and a 4-methoxyphenyloxycarbonyl group can be given.

The alkylsulfonyloxy group is preferably an alkylsulfonyloxy group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyloxy group, an ethylsulfonyloxy group, a propylsulfonyloxy group, an isopropylsulfonyloxy group, a butylsulfonyloxy group, Ethylhexylsulfonyloxy group, decanoylsulfonyloxy group, octadecanoylsulfonyloxy group, cyanomethylsulfonyloxy group, cyanomethylsulfonyloxy group, cyanomethylsulfonyloxy group, mercapto sulfonyloxy group, A methoxymethylsulfonyloxy group, and a perfluoroalkylsulfonyloxy group.

The arylsulfonyloxy group is preferably an arylsulfonyloxy group having 6 to 30 carbon atoms, and examples thereof include phenylsulfonyloxy group, 1-naphthylsulfonyloxy group, 2-naphthylsulfonyloxy group, 2-chlorophenylsulfonyloxy group , 2-methylphenylsulfonyloxy group, 2-methoxyphenylsulfonyloxy group, 2-butoxyphenylsulfonyloxy group, 3-chlorophenylsulfonyloxy group, 3-trifluoromethylphenylsulfonyloxy group, 3-cyanophenylsulfo 4-methoxyphenylsulfonyloxy group, 4-methylsulfanylphenylsulfonyloxy group, 4-fluorophenylsulfonyloxy group, 4-fluorophenylsulfonyloxy group, Phenylsulfanylphenylsulfonyloxy group, and 4-dimethylaminophenylsulfonyloxy group.

The alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a cyclohexylsulfonyl group, An octylsulfonyl group, a cyanomethylsulfonyl group, a methoxymethylsulfonyl group, and a perfluoroalkylsulfonyl group can be exemplified .

The arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, , 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4- A 4-methoxyphenylsulfonyl group, a 4-methylsulfanylphenylsulfonyl group, a 4-phenylsulfanylphenylsulfonyl group, and a 4-dimethylaminophenylsulfonyl group, have.

Examples of the alkyloxy group include methylthio group, ethylthio group, propylthio group, n-butylthio group, trifluoromethylthio group, hexylthio group, t-butylthio group, A cyclohexylthio group, a decylthio group, and a dodecylthio group.

Examples of the aryloxy group include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a tolylthioxy group, a methoxyphenylthio group, a naphthylthio group, a chlorophenylthio group, A cyano group, a thio group, a cyanophenylthio group and a nitrophenylthio group.

The heterocyclic group is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples of the heterocyclic group include thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thienyl, furyl, A pyridyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, an indolizinyl group, an isoindolyl group, a pyridazinyl group, a pyridazinyl group, a pyridazinyl group, , 3H-indolyl group, indolyl group, 1H-indazolyl group, fluorenyl group, 4H-quinolizinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, A phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, An isothiazolyl group, a phenothiazinyl group, an isoxazolyl group, a furazanyl group, a phenoxazinyl group, an isochromanyl group, a chromanyl group, a pyrrole An imidazolidinyl group, an imidazolidinyl group, a pyrazolinylidene group, a pyrazolinyl group, a piperidyl group, a piperazinyl group, an indolinyl group, an isoindolinyl group, a quinuclidinyl group, Morpholinyl and thioxanthryl groups.

Examples of the substituent which may have any one of R ₁ to R ₅ include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; An acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a methoxyl group; An alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; An arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkylamino groups such as methylamino group and cyclohexylamino group; Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group; Arylamino groups such as phenylamino group and p-tolylamino group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; Aryl groups such as a phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; A hydroxy group; A carboxy group; Formyl group; A mercapto group; Sulfo group; A mesyl group; p-toluenesulfonyl group; An amino group; A nitro group; Cyano; A trifluoromethyl group; Trichloromethyl group; A trimethylsilyl group; Phosphino group; Phosphono group; A trimethylammonium group; A dimethylsulfonium group, and a triphenylphenacylphosphonium group.

As described above, two or more of R ₁ to R ₅ may be bonded to each other to form a ring. The ring may be an aliphatic or aromatic hydrocarbon ring or a heterocyclic ring containing a hetero atom. These R ₁ to R ₅ may form a condensed ring.

Examples of the aliphatic or aromatic hydrocarbon ring include 6-membered rings, 5-membered rings and 7-membered rings. The hydrocarbon ring is preferably a 6-membered ring or a 5-membered ring, particularly preferably a 5-membered ring.

Examples of the heterocyclic ring include those containing a sulfur atom, an oxygen atom or a nitrogen atom as a hetero atom. As the heterocyclic ring, it is more preferable to contain a sulfur atom as a hetero atom.

As the condensed ring, for example, condensed rings composed only of hydrocarbon rings can be given. Examples of the polycyclic condensed rings include those in which 2 to 4 benzene rings form a condensed ring and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.

The condensed ring may be a condensed ring containing at least one heterocyclic ring. Examples of the condensed rings include those in which a benzene ring and a 5-membered heterocyclic ring form a condensed ring, and those in which a benzene ring and a 6-membered heterocyclic ring form a condensed ring.

Examples of the ring formed by R ₁ to R ₅ include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, a biphenyl ring, a pyrrole ring, A thiophene ring, a dithiolane ring, oxirane, dioxirane ring, thienyl ring, pyrrolidine ring, piperidine ring, imidazole ring, isoxazole ring, benzodithio ring, oxazole ring, thiazole ring, benzothiazole ring, Benzoimidazole, benzoimidazole, benzoxazole, pyridine, pyrazine, pyrimidine, pyridazin, indolizin, indole, benzofuran, benzothiophene, benzodithio, isobenzofuran, quinoline A quinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, , Phenoxathiine ring, phenothiazine ring, and phenanthrene ring. Among them, dithiolane ring, benzodithiol ring, benzothiazole ring, benzoimidazole ring and benzoxazole ring are particularly preferable.

Examples of R ₁ to R ₅ in the general formula (I) include those described in the following formulas.

At least a part of the acid-proliferating unit is preferably a repeating unit represented by the following general formula (II). That is, at least a part of the acid-proliferating unit preferably contains the structure represented by the general formula (I) in the form represented by the following general formula (II).

In the general formula (II), Ra and Rb each independently represent a hydrogen atom, an alkyl group or a cyano group.

Rc represents a hydrogen atom or a substituent. L represents a single bond or a linking group. When Rc is the substituent and L is the connecting group, Rc and L may be bonded to each other to form a ring.

Each of R ₁ to R ₅ is the same as that described above with respect to general formula (I).

Each Ra and Rb represents a hydrogen atom, an alkyl group or a cyano group, as described above. The alkyl group may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom and a chlorine atom, and a hydroxy group. Examples of the alkyl group of Ra or Rb include a methyl group, a chloromethyl group, a trifluoromethyl group and a hydroxymethyl group. Each of Ra and Rb is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Rc represents a hydrogen atom or a substituent, as described above. Examples of the substituent include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkanoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthiocarbonyl group, , A heterocyclic group, a (di) alkylaminocarbonyl group and an aminothiocarbonyl group.

L represents a single bond or a linking group, as described above.

This linkage is preferably a single bond, an arylene group, an alkylene group, a cycloalkylene group, -O-, -S-, -SO ₂ -, -CO-, -N (R ₃₃ ) - or a combination thereof. This linking group is more preferably a single bond, an arylene group, an alkylene group, -O-, -SO ₂ -, -CO-, -N (R ₃₃ ) - or a combination thereof. Here, R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.

Rc and L may be bonded to each other to form a ring. Examples of the ring include monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocyclic rings.

Ra, Rb, Rc and L in the general formula (II) are preferably those represented by the following general formulas (III-1), (III-2), (III- ) Or (V-1). Of these, the structures represented by the general formula (III-1) or (III-2) are particularly preferable.

Wherein,

Ar _1a represents an arylene group.

R ₀₁ represents a hydrogen atom, an alkyl group or a cyano group. The alkyl group may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom and a chlorine atom. Examples of the alkyl group of R < ₀₁ > include a methyl group, a chloromethyl group and a trifluoromethyl group. R ₀₁ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Each of R ₀₂ and R ₀₂₁ represents a single bond or a divalent linking group. This divalent linking group is, for example, an arylene group, an alkylene group, a cycloalkylene group, -O-, -S-, -SO ₂ -, -CO-, -N (R ₃₃ ) - or a combination thereof. Here, R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.

The arylene group as R ₀₂ or R ₀₂₁ preferably has 6 to 14 carbon atoms, and specific examples thereof include a phenylene group, a tolylene group and a naphthylene group. The arylene group may further have a substituent.

The alkylene group as R ₀₂ or R ₀₂₁ is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group. The alkylene group may further have a substituent.

The cycloalkylene group as R ₀₂ or R ₀₂₁ is preferably a cycloalkylene group having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group. The cycloalkylene group may further have a substituent.

R ₀₃ and R ₀₁₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.

The alkyl group as R ₀₃ or R ₀₁₉ preferably has a carbon number such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, More preferably 20 or less, and more preferably 8 or less.

The cycloalkyl group as R ₀₃ or R ₀₁₉ may be monocyclic or polycyclic. Examples of the cycloalkyl group include a cyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The aryl group as R ₀₃ or R ₀₁₉ preferably has 6 to 15 carbon atoms. Examples of such an aryl group include a phenyl group, a tolyl group, a naphthyl group and an anthryl group.

The aralkyl group as R ₀₃ or R ₀₁₉ preferably has 6 to 20 carbon atoms. Examples of such an aralkyl group include a benzyl group and a phenethyl group.

Each of these alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups may have a substituent. Examples of the substituent include a hydroxyl group; Halogen atoms such as fluorine, chlorine, bromine and iodine atoms; A nitro group; Cyano; Amide group; A sulfonamide group; An alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group; An alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group and a butoxy group; An alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; An acyl group such as a formyl group, an acetyl group and a benzoyl group; An acyloxy group such as an acetoxy group and a butyryloxy group, and a carboxy group. These substituents preferably have a carbon number of 8 or less.

The arylene group as Ar _1a preferably has 6 to 14 carbon atoms. Examples of such an arylene group include a phenylene group, a tolylene group and a naphthylene group.

The arylene group may have a substituent. Examples of the substituent include the same ones as described for R ₀₃ and R ₀₁₉ above.

Preferred examples of the partial structure of the formula (II) include the following.

Specific examples of the polymerizable compound corresponding to the acid-proliferating unit are listed below, but the scope of the present invention is not limited thereto.

The content of the acid-propagating agent unit in the acid-proliferative agent-carrying resin in the third embodiment is preferably within the range of 3 to 80 mol%, more preferably 5 to 70 mol%, based on the total repeating units , And particularly preferably in the range of 7 to 60 mol%.

The acid-proliferating monomers corresponding to the acid-proliferating unit can be prepared, for example, in the presence of a base (for example, triethylamine or pyridine) using a sulfonyl halide or sulfonic anhydride having a corresponding alcohol compound and a polymerizable group in THF , An inert solvent such as DMF and acetonitrile, or a basic solvent such as pyridine. The reaction temperature is preferably -10 to 60 占 폚.

In addition, various acid proliferator monomers corresponding to the sulfonyl halide can be synthesized by using an alkylsulfonyl halide and an arylsulfonyl halide as the sulfonyl halide.

[R] Other repeating units

It is preferable that the acid-proliferative agent-carrying resin according to the second and third embodiments further contains the following repeating units in addition to the above-mentioned acid-proliferating unit. That is, the acid-proliferative agent-carrying resin is a repeating unit having (A) an acid-decomposable unit, (B) an alkali-soluble unit, (C) a repeating unit having an alicyclic hydrocarbon structure substituted by a polar group and / or (D) Unit is more preferable. Hereinafter, these repeating units will be sequentially described.

(A) an acid-decomposable unit

The acid-decomposable unit is a repeating unit containing a group which is decomposed by the action of an acid to generate an alkali-soluble group (hereinafter referred to as an acid-decomposable group).

Examples of the acid decomposable group include those in which a hydrogen atom of an alkali-soluble group such as -COOH group and -OH group is replaced by a group which is eliminated by the action of an acid.

The group is eliminated by the action of an acid, for _{example, -C (R 36) (R} 37) (R 38), -C (= O) -OC (R 36) (R 37) (R 38), - _{C (R 01) (R 02} ) (OR 39), -C (R 01) (R 02) -C (= O) -OC (R 36) (R 37) (R 38) , and -CH (R ₃₆ ) (Ar).

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ to R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

Ar represents an aryl group.

The alkyl group as R ₃₆ to R ₃₉ , R ₀₁ or R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, ethyl group, propyl group, n-butyl group, .

The cycloalkyl group as R ₃₆ to R ₃₉ , R ₀₁ or R ₀₂ may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having from 6 to 20 carbon atoms, and examples thereof include an adamantyl group, a norbornyl group, an isoboronyl group, a camphanyl group, a dicyclopentyl group, an a-pyne group, a tricyclodecanyl group , A tetracyclododecyl group and an androstanyl group. A part of the carbon atoms in the cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.

The aryl group as R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ or Ar is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group and an anthryl group.

The aralkyl group as R ₃₆ to R ₃₉ , R ₀₁ or R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and for example, a benzyl group, a phenethyl group and a naphthylmethyl group are preferable.

The alkenyl group as R ₃₆ to R ₃₉ , R ₀₁ or R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group and a cyclohexenyl group.

The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. The cyclic structure is preferably a cycloalkane structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure and a cyclooctane structure. The polycyclic structure is preferably a cycloalkane structure having 6 to 20 carbon atoms, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure and a tetracyclododecane structure. In addition, some of the carbon atoms in the ring structure may be substituted by a hetero atom such as an oxygen atom.

Each of the groups may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, an ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, A carbonyl group, a cyano group and a nitro group. These substituents preferably have a carbon number of 8 or less.

Examples of the acid-decomposable unit include repeating units represented by the following general formula (IA).

In the formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Ar ₁ represents, for example, aromatic ring. Further, R ₀₃ is an alkylene group, and may form a ring together with Lp or a -CC- chain by being bonded to Ar ₁ as an aromatic ring group. Further, R ₀₃ and Ar ₁ may be an alkylene group, and they may be bonded to each other to form, for example, a 5-membered or 6-membered ring together with the -CC- chain.

n Y each independently represents a hydrogen atom or a group which is eliminated by the action of an acid. Provided that at least one of Y represents a group which is eliminated by the action of an acid.

n represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 2, and most preferably 1.

Lp represents a single bond or a divalent linking group.

The alkyl group as R ₀₁ to R ₀₃ is, for example, an alkyl group having 20 or less carbon atoms, and is preferably an alkyl group having a carbon number of 20 or less and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, An acyl group, an octyl group or a dodecyl group. More preferably, these alkyl groups are alkyl groups having 8 or less carbon atoms. These alkyl groups may have a substituent.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R ₀₁ to R ₀₃ .

The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. And preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group. These cycloalkyl groups may have a substituent.

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

When R ₀₃ represents an alkylene group, the alkylene group preferably has 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.

The aromatic ring as Ar ₁ preferably has 6 to 14 carbon atoms, and examples thereof include a benzene ring, a toluene ring and a naphthalene ring. These aromatic rings may have a substituent.

Examples of the divalent linking group of Lp include an alkylene group, a cycloalkylene group, an arylene group, -COO-, -OCO-, -CO-, -O-, -S-, -S (= O) ₂ -, -OS (= O) ₂ -, -NH-, or a combination of two or more thereof.

The alkylene group represented by Lp may be straight-chain or branched. The number of carbon atoms of the alkylene group is preferably 1 to 20, more preferably 1 to 10. Examples of such an alkylene group include a methylene group, an ethylene group and a propylene group.

The cycloalkylene group represented by Lp may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkylene group is preferably from 3 to 20, more preferably from 3 to 10. Examples of such cycloalkylene group include a 1,4-cyclohexylene group.

The number of carbon atoms of the arylene group represented by Lp is preferably 6 to 20, more preferably 6 to 10. Examples of the arylene group include a phenylene group and a naphthylene group.

The alkylene group, cycloalkylene group and arylene group may have a substituent. Examples of such a substituent include the same ones as described for R in the general formula (I).

The group Y to be eliminated by the action of an acid, for _{example, -C (R 36) (R} 37) (R 38), -C (= O) -OC (R 36) (R 37) (R 38), _{-C (R 01) (R 02} ) (OR 39), -C (R 01) (R 02) -C (= O) -OC (R 36) (R 37) (R 38) , and -CH (R ₃₆ ) (Ar). Wherein R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ and Ar are the same as those described above.

As the group which is eliminated by the action of an acid, the structure represented by the following general formula (IIA) is more preferable.

In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group, a pericyclic group, an aromatic group, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. These perspiration and aromatic ring may contain a hetero atom.

At least two of Q, M and L ₁ may be bonded to each other to form a 5-membered or 6-membered ring.

The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group and an octyl group.

The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

The aryl group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group and an anthryl group.

The aralkyl group as L ₁ and L ₂ is, for example, an aralkyl group having 6 to 20 carbon atoms, specifically, benzyl group and phenethyl group.

The divalent linking group as M may be, for example, an alkylene group (e.g., a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group), a cycloalkylene group (such as a cyclopentylene group or a cyclo (E.g., a phenylene group, a tolylene group or a naphthylene group), -S-, -O-, or -O-alkylene groups (for example, , -CO-, -SO ₂ -, -N (R ₀ ) -, or a combination of two or more thereof. Wherein R < ₀ > is a hydrogen atom or an alkyl group. The alkyl group as R ₀ is, for example, an alkyl group having 1 to 8 carbon atoms, and specific examples thereof include a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group and octyl group.

The alkyl group and the cycloalkyl group as Q are the same as the respective groups as L ₁ and L ₂ described above.

Examples of the vicinal group or aromatic group as Q include a cycloalkyl group and an aryl group as L ₁ and L ₂ described above. These cycloalkyl groups and aryl groups are preferably groups having 3 to 15 carbon atoms.

Examples of the heterocyclic group or aromatic ring containing the hetero atom as Q include, for example, thiiran, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, Triazole, thiadiazole, thiazole, and pyrrolidone. However, the ring formed by the carbon and the hetero atom or the ring formed only by the hetero atom is not limited thereto.

Examples of the ring formed by bonding at least two of Q, M and L ₁ to each other include a 5-membered or 6-membered ring formed by forming a propylene group or a butylene group. The 5-membered or 6-membered ring contains an oxygen atom.

Each group represented by L ₁ , L ₂ , M and Q in the general formula (IIA) may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, an ureido group, a urethane group, a hydroxy group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, A cyano group and a nitro group. These substituents preferably have a carbon number of 8 or less.

- (M-Q) is preferably a group of 1 to 30 carbon atoms, more preferably a group of 5 to 20 carbon atoms.

Specific examples of the repeating unit represented by formula (IA) are listed below, but are not limited thereto.

As the acid-decomposable unit, it is also possible to employ a repeating unit represented by the following general formula (X).

Wherein,

Xa ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represents a linear or branched alkyl group or a monocyclic or polycyclic cycloalkyl group. At least two of Rx ₁ to Rx ₃ may be bonded to each other to form a monocyclic or polycyclic cycloalkyl group.

Examples of the divalent linking group as T include an alkylene group, a - (COO-Rt) - group and a - (O-Rt) - group. Here, Rt represents an alkylene group or a cycloalkylene group.

T is a single bond or a - (COO-Rt) - group. Here, 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 as Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-

The cycloalkyl group as Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group to be.

Examples of the cycloalkyl group which may be formed by bonding at least two of Rx ₁ to Rx ₃ to each other include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, or norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, And a cycloalkyl group such as a t-butyl group.

In particular, it is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to each other to form the above-mentioned cycloalkyl group.

Specific examples of the repeating unit represented by formula (X) are shown below, but the scope of the present invention is not limited thereto.

The content of acid-decomposable units in the acid-proliferative agent-carrying resin is preferably within a range of 3 to 90 mol%, more preferably within a range of 5 to 80 mol%, and more preferably within a range of 7 to 70 mol% Mol%.

The molar ratio of the acid-proliferating unit and the acid-decomposable unit (the number of moles of the acid-proliferating unit / the number of moles of the acid-decomposable unit) is preferably 0.04 to 1.0, more preferably 0.05 to 0.9, and particularly preferably 0.06 to 0.8.

(B) an alkali-soluble unit

The alkali-soluble unit is preferably a repeating unit represented by the following general formula (VI).

Wherein,

R ₀₁ , R ₀₂ and R ₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₀₃ represents an alkylene group and may be bonded to Lp or Ar ₁ to form a ring.

Ar ₁ represents aromatic ring.

n represents an integer of 1 or more.

Lp represents a single bond or a divalent linking group.

Specific examples of R ₀₁ , R ₀₂ , R ₀₃ , Lp and Ar _{1 in} the general formula (VI) include the same ones as in the general formula (IA).

Specific examples of the repeating unit represented by formula (VI) are listed below, but the scope of the present invention is not limited thereto.

The content of the alkali-soluble unit in the acid-proliferative agent-carrying resin is preferably within a range of 3 to 90 mol%, more preferably within a range of 5 to 80 mol%, more preferably within a range of 7 to 70 mol% Mol%.

The molar ratio of the acid-proliferating unit and the alkali-soluble unit (the number of moles of acid-proliferating unit / number of moles of alkali-soluble unit) is preferably 0.04 to 1.0, more preferably 0.05 to 0.9, and particularly preferably 0.06 to 0.8.

(C) a repeating unit having an alicyclic hydrocarbon structure substituted by a polar group

It is preferable that the acid-proliferative agent-carrying resin further contains a repeating unit having an alicyclic hydrocarbon structure substituted by a polar group. When the repeating unit is contained in the acid-proliferating agent-carrying resin, substrate adhesion and developer affinity can be further improved.

The polar group contained in the repeating unit is preferably a hydroxyl group or a cyano group. The hydroxyl group as the polar group forms an alcoholic hydroxyl group.

Examples of the alicyclic hydrocarbon structure substituted by a polar group include a structure represented by the following general formula (VIIa) or (VIIb).

In formula (VIIa), R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. However, R ₂ at least one of c ~ R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c is a hydroxyl group, and the remainder is a hydrogen atom. More preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the remaining one is a hydrogen atom.

The group represented by the general formula (VIIa) is preferably a dihydroxyl or monohydroxy, more preferably a dihydroxyl.

General formula (VIIa) or as the repeating units having a group represented by (VIIb) wherein the general formula (II-AB1) or (II-AB2) of the R ₁₃ '~ R _16', at least one is the above-mentioned general formula (VIIa) Or (VIIb), and a repeating unit represented by the following general formula (AIIa) or (AIIb). An example of the former is a structure in which R ₅ of -COOR ₅ is a group represented by the general formula (VIIa) or (VIIb).

Among the general formulas (AIIa) and (AIIb)

R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c ~ R ₄ c is R ₂ c ~ R ₄ c and agreement in the formula (VIIa).

Specific examples of the repeating unit represented by formula (AIIa) or (AIIb) are listed below, but the present invention is not limited thereto.

The content of the repeating unit having an alicyclic hydrocarbon structure substituted by a polar group in the acid-repellent-agent-carrying resin is preferably in the range of 3 to 90 mol%, more preferably in the range of 5 to 80 mol% , More preferably in the range of 7 to 70 mol%.

The molar ratio of the acid proliferating unit to the repeating unit (the number of moles of acid repelling agent unit / repeating unit having an alicyclic hydrocarbon structure substituted by a polar group) is preferably 0.04 to 1.0, more preferably 0.05 to 0.9, 0.06 to 0.8 is particularly preferable.

(D) a repeating unit having a developing aid

It is preferable that the acid-proliferative agent-carrying resin further contains a repeating unit having a group which is decomposed by the action of a developing aid, that is, an alkaline developing solution, to increase the dissolution rate in the developing solution. As a result, the developing aid is decomposed at the time of alkali development to increase the dissolution rate in the alkali developing solution.

The developing aid is, for example, a group which is decomposed by an alkali developer to generate a hydrophilic functional group. Examples of the hydrophilic functional group include an alkali-soluble group such as a carboxyl group and a hydroxyl group.

Examples of the developing aid include a group having a lactone structure, a carboxylic acid ester group substituted by a polar group such as a halogen atom, a group having an acid anhydride structure, a group having a cyclic amide structure, an acid amide group, An ester group, a carbonate ester group, a sulfuric acid ester group, and a sulfonic acid ester group. Preferably a group having at least one partial structure of a lactone structure, a cyclic amide structure and a cyclic acid anhydride structure. Particularly preferred is a lactone group.

Further, a carboxylic acid ester group which is not substituted by a polar group such as a halogen atom (for example, an ester group directly bonded to the main chain of the (meth) acrylate repeating unit and not substituted by a polar group such as a halogen atom Is slow in the decomposition reaction by the alkali developing solution. For this reason, these carboxylic acid ester groups are not included in the developing aid.

The group having a lactone structure is preferably a 5- to 7-membered ring lactone structure, and more preferably another ring is formed in a form that forms a bicyclo structure or spiro structure in a 5- to 7-membered ring lactone structure.

The repeating unit having the developing aid preferably has a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17). The group having a lactone structure may be directly bonded to the main chain. Preferred examples of the lactone structure include (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17) . The use of a particular lactone structure can further reduce line edge roughness and development defects.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Examples of the preferable substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, And an acid-decomposable group.

n ₂ represents an integer of 0 to 4; When n ₂ is an integer of 2 or more, a plurality of existing Rb _{2 s} may be the same or different. In this case also, the plurality of Rb ₂ to each other there may be bonded to each other to form a ring.

Examples of the repeating unit having a lactone structure represented by any one of formulas (LC1-1) to (LC1-17) include repeating units represented by the following formula (AII).

Among the general formula (AII)

Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

As the preferable substituent which the alkyl group of Rb ₀ may have, a hydroxyl group and a halogen atom can be exemplified. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group. Of these, a hydrogen atom and a methyl group are particularly preferable.

Ab represents an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination thereof. Ab is preferably a linking group represented by a single bond or -Ab ₁ -CO ₂ -.

Ab ₁ is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

V is a group represented by any one of formulas (LC1-1) to (LC1-17).

The repeating unit having a lactone structure usually contains an optical isomer, but any of the optical isomers may be used. In addition, one kind of optical isomer may be used singly or a plurality of optical isomers may be used in combination. When one kind of optical isomer is mainly used, the optical purity is preferably 90% ee or more, more preferably 95% ee or more.

As the repeating unit having a particularly preferable lactone group, the following repeating unit can be exemplified. By selecting the optimum lactone group, it becomes possible to make the pattern profile and the coarse-dense dependence better. Rx and R wherein R represents a H, CH _3, CH ₂ OH or CF _3.

The repeating unit provided with the developing aid is, for example, a repeating unit in which a developing aid is bonded to the main chain of the resin such as a repeating unit of an acrylate ester and a methacrylate ester. Alternatively, the repeating unit may be introduced at the end of the resin by using a polymerization initiator or a chain transfer agent having a developing aid.

The content of the repeating unit having the phenomenon or auxiliary agent in the acid-proliferating agent-carrying resin is preferably within a range of 1 to 40 mol%, more preferably within a range of 3 to 30 mol% based on the total repeating units , And particularly preferably from 5 to 15 mol%.

The shape of the acid-proliferating agent-carrying resin may be any of random, block, comb, star and the like.

The acid-proliferating unit and the resin containing other repeating unit can be synthesized, for example, by radical, cationic or anionic polymerization of the unsaturated monomer corresponding to each structure. It is also possible to perform polymerization by using an unsaturated monomer corresponding to the precursor of each structure, followed by polymer reaction.

The molecular weight of the acid-proliferative agent-carrying resin is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100000, more preferably in the range of 1500 to 70000, and particularly preferably in the range of 2000 to 50000. Here, the weight-average molecular weight of the resin was determined by GPC (solvent; N-methyl-2-pyrrolidone (NMP)] in terms of polystyrene.

The dispersion degree (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and further preferably 1.05 to 2.50.

[2] Photo acid generators

The composition according to the present invention contains a photoacid generator as described above.

The photoacid generator is a compound that generates an acid upon irradiation with an actinic ray or radiation. Examples of the photoacid generator include known compounds that generate an acid upon irradiation with an actinic ray or radiation used for photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photochromic agents for colorants, photochromic agents, And a mixture thereof can be appropriately selected and used. Examples thereof include an onium salt such as a sulfonium salt and an iodonium salt, and a diazodisulfone compound such as bis (alkylsulfonyldiazomethane).

Preferable examples of the photoacid generator include compounds represented by the following formulas (ZI), (ZII) and (ZIII).

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The number of carbon atoms of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is, for example, 1 to 30, preferably 1 to 20.

R ₂₀₁ ~ R 2 out of ₂₀₃ are coupled to each other through a single bond or a linking group may be bonded to form a ring. Examples of the linking group in this case include an ether bond, a thioether bond, an ester bond, an amide bond, a carbonyl group, a methylene group and an ethylene group. R ~ ₂₀₁ As the group forming R in combination of two dogs ₂₀₃ may be, for example, a butylene group and a pentylene group such as alkylene group of.

Specific examples of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compounds (ZI-1), (ZI-2) or (ZI-3) described later.

X ^- represents an acetylenic anion. Examples of X ^- include a sulfonic acid anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ^- , PF ₆ ^- and SbF ₆ ^- . X < ^{- &} gt ^; is preferably an organic anion containing a carbon atom. Preferable organic anions include, for example, organic anions shown in the following AN1 to AN3.

Expression of the AN3 AN1 ~ ₁ ~ Rc Rc ₃ represents an organic group independently. The organic group is, for example, 1 to 30 carbon atoms, preferably an alkyl group, an aryl group or a group in which a plurality of these groups are connected through a linking group. Examples of the linking group include a single bond, -O-, -CO ₂ -, -S-, -SO ₃ - and -SO ₂ N (Rd ₁ ) -. Here, Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring with an alkyl group or an aryl group bonded thereto.

The organic group of Rc ₁ to Rc ₃ may be an alkyl group whose 1-position is substituted by a fluorine atom or a fluoroalkyl group, or a phenyl group which is substituted by a fluorine atom or a fluoroalkyl group. By containing a fluorine atom or a fluoroalkyl group, it becomes possible to raise the acidity of an acid generated by light irradiation. This makes it possible to improve the sensitivity of the actinic ray-sensitive or radiation-sensitive resin composition. Also, Rc Rc ₁ ~ ₃ are combined with other alkyl and aryl groups may optionally form a ring.

Further, as a preferable X ^- , a sulfonic acid anion represented by the following general formula (SA1) or (SA2) can be exemplified.

In the formula (SA1)

Ar represents an aryl group and may further have a substituent other than the - (D-B) group.

n represents an integer of 1 or more. n is preferably 1 to 4, more preferably 2 to 3, and most preferably 3.

D represents a single bond or a divalent linking group. The divalent linking group is an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group or an ester group.

B represents a hydrocarbon group.

In the formula (SA2)

Xf each independently represents an alkyl group substituted by a fluorine atom or at least one fluorine atom.

R ₁ and R ₂ each independently represent a group selected from a hydrogen atom, a fluorine atom, an alkyl group and an alkyl group substituted by at least one fluorine atom, and when a plurality of R ₁ and R ₂ are present, R ₁ and R ₂ may be the same or different, They may be different.

L represents a single bond or a divalent linking group, and when there are a plurality of Ls, L may be the same or different.

E represents a group having a cyclic structure.

x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

First, the sulfonic acid anion represented by the formula (SA1) will be described in detail.

In the formula (SA1), Ar is preferably an aromatic ring having 6 to 30 carbon atoms. Specifically, Ar is, for example, a benzene ring, a naphthalene ring, a pentane ring, an indene ring, an azene ring, a heptylene ring, an indene ring, a perylene ring, a pentacene ring, an acetapthalene ring, a phenanthrene ring, A thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, , Indole ring, indole ring, benzofuran ring, benzothiophen ring, isobenzofuran ring, quinolin ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, Phenanthridine ring, phenanthridine ring, phenanthroline ring, phenanthroline ring, thianthrene ring, chroman ring, xanthane ring, phenoxathiine ring, phenothiazine ring or phenazin ring. Among them, a benzene ring, a naphthalene ring or an anthracene ring is preferable from the viewpoint of compatibility between roughness improvement and high sensitivity, and a benzene ring is more preferable.

When Ar has a substituent other than - (D-B) group, examples of the substituent include the following. That is, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; An alkyloxy group such as a methylthio group, an ethylthio group and a tert-butylthio group; Arylthioxy groups such as phenylthio group and p-tolylthioxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acetoxy group; Straight chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; A branched alkyl group; Alkenyl groups such as a vinyl group, a propenyl group and a hexenyl group; An acetylene group; An alkynyl group such as a propynyl group and a hexynyl group; An aryl group such as a phenyl group and a tolyl group; A hydroxy group; A carboxy group; And sulfonic acid groups. Of these, straight-chain alkyl groups and branched-chain alkyl groups are preferable from the standpoint of roughness improvement.

In formula (SA1), D is preferably a single bond or an ether group or an ester group. More preferably, D is a single bond.

In the formula (SA1), B is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a cycloalkyl group. B is preferably an alkyl group or a cycloalkyl group. The alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B may have a substituent.

The alkyl group as B is preferably a branched chain alkyl group. Examples of the branched alkyl group include isopropyl, tert-butyl, tert-pentyl, neopentyl, sec-butyl, isobutyl, isohexyl, 3,3-dimethylpentyl and 2- Ethylhexyl group.

The cycloalkyl group as B may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a boronyl group, a camhenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoryl group, a dicyclohexyl group and a pinenyl group .

When the alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B has a substituent, examples of the substituent include the following. That is, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; An alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; An alkyloxy group such as a methylthio group, an ethylthio group and a tert-butylthio group; Arylthioxy groups such as phenylthio group and p-tolylthioxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acetoxy group; Straight chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; A branched alkyl group; A cycloalkyl group such as a cyclohexyl group; Alkenyl groups such as a vinyl group, a propenyl group and a hexenyl group; An acetylene group; An alkynyl group such as a propynyl group and a hexynyl group; An aryl group such as a phenyl group and a tolyl group; A hydroxy group; A carboxy group; Sulfonic acid group; And a carbonyl group. Among them, straight-chain alkyl groups and branched-chain alkyl groups are preferable from the viewpoint of both improvement of roughness and high sensitivity.

Next, the sulfonic acid anion represented by the formula (SA2) will be described in detail.

In the formula (SA2), Xf is a fluorine atom or an alkyl group substituted by at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted by a fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, Xf is preferably a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH _{2 CF 3, CH 2 CH 2} CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 , or CH ₂ CH ₂ C ₄ F ₉ . Among them, a fluorine atom or CF ₃ is preferable, and a fluorine atom is most preferable.

Each of R ₁ and R ₂ in the formula (SA2) is a group selected from a hydrogen atom, a fluorine atom, an alkyl group and an alkyl group substituted by at least one fluorine atom. The alkyl group which may be substituted by the fluorine atom preferably has 1 to 4 carbon atoms. As the alkyl group substituted by a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms is particularly preferable. Specifically, _{CF 3, C 2 F 5,} C 3 F 7, C 4 F 9, C 5 F 11, C 6 F 13, C 7 F 15, C 8 F 17, CH 2 CF 3, CH 2 CH 2 CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ and a can be mentioned. Among them, a CF ₃ being preferred.

In the formula (SA2), x is preferably 1 to 8, more preferably 1 to 4. y is preferably 0 to 4, more preferably 0. z is preferably 0 to 8, more preferably 0 to 4.

In formula (SA2), L represents a single bond or a divalent linking group. Examples of the divalent linking group include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, an alkylene group, a cycloalkylene group and an alkenylene group . Of these, -COO-, -OCO-, -CO-, -O-, -S-, -SO- or -SO ₂ - is preferable, and -COO-, -OCO- or -SO ₂ - is more preferable .

E in the formula (SA2) represents a group having a ring. Examples of E include cyclic aliphatic groups, aryl groups, and groups having a heterocyclic ring.

The cyclic aliphatic group as E may have a monocyclic ring or may have a polycyclic ring. As the cyclic aliphatic group having a monocyclic ring, monocyclic cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cyclooctyl group are preferable. The polycyclic aliphatic group having a polycyclic ring is preferably a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Particularly, when a cyclic aliphatic group having a bulky structure with a 6-member ring or more is employed as E, it is possible to suppress the diffusibility in the film in the PEB (post-exposure heating) process, and to further improve the resolution and EL (exposure latitude) .

The aryl group as E is, for example, a benzene ring, a naphthalene ring, a phenanthrene ring or an anthracene ring.

The group having a heterocyclic ring as E may have aromaticity or may not have aromaticity. The hetero atom contained in this group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic ring include furan ring, thiophen ring, benzofuran ring, benzothiophen ring, dibenzofuran ring, dibenzothiophen ring, pyridine ring, piperidine ring and morpholine ring. Among them, furan ring, thiophen ring, pyridine ring, piperidine ring and morpholine ring are preferable.

E may have a substituent. Examples of the substituent include an alkyl group (any of linear, branched and cyclic, preferably having 1 to 12 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, An amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group and a sulfonic acid ester group.

As the photoacid generator, a compound having a plurality of structures represented by the general formula (ZI) may be used. For example, the formula of the compound represented by (ZI) R ₂₀₁ ~ R ₂₀₃ of at least one is the general formula (ZI) the addition R ₂₀₁ ~ R a structure combining at least one of ₂₀₃ and one of the other compounds represented by .

As the more preferable component (ZI), the following compounds (ZI-1) to (ZI-4) can be exemplified.

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

Compound (ZI-1) is R ₂₀₁ to R ₂₀₃ may be a whole is an aryl group, R is ₂₀₁ to some of the aryl groups of R _203, may be those other than the alkyl group. When the compound (ZI-1) has a plurality of aryl groups, these aryl groups may be the same or different.

Examples of the compound (ZI-1) include triarylsulfonium compounds, diarylalkylsulfonium compounds and aryldialkylsulfonium compounds.

As the aryl group in the compound (ZI-1), a heteroaryl group such as a phenyl group, a naphthyl group or an indole residue and a pyrrole residue is preferable, and a phenyl group, a naphthyl group or an indole residue is particularly preferable.

The alkyl group optionally possessed by the compound (ZI-1) is preferably a straight chain, branched chain or cycloalkyl group having 1 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, , a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

These aryl group and alkyl group may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group .

Preferred examples of the substituent include a straight chain, branched chain or cyclic alkyl group having 1 to 12 carbon atoms and a straight chain, branched chain or cyclic alkoxy group having 1 to 12 carbon atoms. Particularly preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. The substituent may be substituted with any one of three R ₂₀₁ to R ₂₀₃ , or may be substituted with all three of R ₂₀₁ to R ₂₀₃ . When R ₂₀₁ to R ₂₀₃ are phenyl groups, the substituent is preferably substituted at the p-position of the aryl group.

It is also preferable that one or two of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is an aryl group which may have a substituent and the remaining group is a linear, branched or cyclic alkyl group. As a specific example of this structure, there is a structure described in paragraphs 0141 to 0153 of Japanese Patent Application Laid-Open No. 2004-210670.

In this case, the aryl group is specifically the same as the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , and a phenyl group or a naphthyl group is preferable. The aryl group preferably has any one of a hydroxyl group, an alkoxy group and an alkyl group as a substituent. The substituent is more preferably an alkoxy group having 1 to 12 carbon atoms, and still more preferably an alkoxy group having 1 to 6 carbon atoms.

The straight-chain, branched-chain or cyclic alkyl group as the remaining group is preferably an alkyl group having 1 to 6 carbon atoms. These groups may further have a substituent. When two of the remaining groups are present, these two groups may be bonded to each other to form a ring.

The compound (ZI-1) is, for example, a compound represented by the following general formula (ZI-1A).

Of the general formula (ZI-1A)

R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group or an alkoxycarbonyl group.

When there are a plurality of R _{14 s} , each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group or a cycloalkylsulfonyl group.

And each R ₁₅ independently represents an alkyl group or a cycloalkyl group. The two R < ₁₅ > may be bonded to each other to form a ring.

and l represents an integer of 0 to 2.

r represents an integer of 0 to 8;

X ^- represents an unconjugated anion, and examples thereof include the same as X < ^- > in general formula (ZI).

The alkyl group of R ₁₃ , R ₁₄ or R ₁₅ may be a straight chain alkyl group or a branched chain alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2- methylpropyl group, N-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group. Of these, a methyl group, an ethyl group, an n-butyl group and a t-butyl group are particularly preferable.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ or R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclobentenyl, cyclohexenyl and cyclooctadiene Nyl group. Of these, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl groups are particularly preferred.

Examples of the alkyl group portion of the alkoxy group of R ₁₃ or R ₁₄ include those listed above as alkyl groups of R ₁₃ , R ₁₄ or R ₁₅ . As the alkoxy group, a methoxy group, ethoxy group, n-propoxy group and n-butoxy group are particularly preferable.

As the cycloalkyl part of the cycloalkyl group of R ₁₃ alkyloxy group, for example, those listed as R ₁₃ above, R1 ₄ or a cycloalkyl group of R _15. As the cycloalkyloxy group, a cyclopentyloxy group and a cyclohexyloxy group are particularly preferable.

As the alkoxy group portion of the alkoxycarbonyl group R _13, for example, those listed above as the alkoxy group of R ₁₃ or R _14. The alkoxycarbonyl group is particularly preferably a methoxycarbonyl group, an ethoxycarbonyl group or an n-butoxycarbonyl group.

As the alkyl moiety of the alkylsulfonyl group of R _14, for example, those listed above as the alkyl group of R _13, R ₁₄ or R _15. In addition, as part of a cycloalkyl cycloalkyl group alkylsulfonyl group of R _14, for example, those listed above as R _13, a cycloalkyl group of R ₁₄ or R _15. As the alkylsulfonyl or cycloalkylsulfonyl group, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group and a cyclohexanesulfonyl group are particularly preferable.

1 is preferably 0 or 1, and more preferably 1. r is preferably 0 to 2.

Each group of R ₁₃ , R ₁₄ and R ₁₅ may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, a cycloalkyloxy group, an alkoxyalkyl group, a cycloalkyloxyalkyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, A vinylsulfonyloxy group, a vinylsulfonyloxy group, a vinylsulfonyloxy group and a cycloalkyloxycarbonyloxy group.

The alkoxy group may be straight-chain or branched. Examples of the alkoxy group include a methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, Having 1 to 20 carbon atoms.

Examples of the cycloalkyloxy group include those having 3 to 20 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group.

The alkoxyalkyl group may be straight-chain or branched. Examples of the alkoxyalkyl group include those having 2 to 21 carbon atoms such as methoxymethyl, ethoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl and 2-ethoxyethyl groups .

Examples of the cycloalkyloxyalkyl group include those having 4 to 21 carbon atoms such as a cyclohexyloxymethyl group, a cyclopentyloxymethyl group, and a cyclohexyloxyethyl group.

The alkoxycarbonyl group may be straight chain or branched chain. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, Butoxycarbonyl group and the like having 2 to 21 carbon atoms.

Examples of the cycloalkyloxycarbonyl group include those having 4 to 21 carbon atoms such as a cyclopentyloxycarbonyl group and a cyclohexyloxycarbonyl group.

The alkoxycarbonyloxy group may be straight-chain or branched. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, And a t-butoxycarbonyloxy group, and the like.

Examples of the cycloalkyloxycarbonyloxy group include those having 4 to 21 carbon atoms such as a cyclopentyloxycarbonyloxy group and a cyclohexyloxycarbonyloxy group.

The ring formed by bonding two R < ₁₅ > together may form a 5-membered or 6-membered ring, particularly preferably a 5-membered ring (i.e., a tetrahydrothiophene ring) together with the S atom in the formula (ZI- Is preferable.

The ring may further have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group and an alkoxycarbonyloxy group.

As R ₁₅ , a methyl group, an ethyl group and a bivalent group formed by bonding two R _{15 s} to form a tetrahydrothiophene ring together with a sulfur atom are particularly preferable.

Alkyl group of R _13, cycloalkyl group, alkoxy group and alkoxycarbonyl group, alkyl group of R _14, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group and cycloalkyl sulfonyl group may further have a substituent. As the substituent, a hydroxy group, an alkoxy group, an alkoxycarbonyl group and a halogen atom (especially a fluorine atom) are preferable.

Specific preferred examples of the cation in the compound represented by the general formula (ZI-1A) are shown below.

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

The compound (ZI-2) is a compound in which each of R ₂₀₁ to R ₂₀₃ in the formula (ZI) independently represents an organic group not containing an aromatic ring. Wherein the aromatic ring also includes an aromatic ring containing a heteroatom.

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

It is preferable that each of R ₂₀₁ to R ₂₀₃ independently represents an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group or a vinyl group. More preferably a straight chain, branched chain or cyclic 2-oxoalkyl group or alkoxycarbonylmethyl group, and particularly preferably a straight chain or branched chain 2-oxoalkyl group.

R alkyl group as ₂₀₁ ~ R ₂₀₃ is a straight-chain, branched-chain and may be any one of cyclic to, preferred examples a linear or branched chain alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group) And a cycloalkyl group having from 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group or norbornyl group).

R ₂₀₁ R ₂₀₃ ~ as 2- oxo group may be mentioned a group having a> C = O on the 2-position of the alkyl group is, preferably, may be one straight chain, any one of a branched chain, and cyclic.

As preferable examples of the alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ ~ R ₂₀₃ may be an alkoxy group having a carbon number of 1 to 5 (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, pentoxy group).

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

Two of R ₂₀₁ ~ R ₂₀₃ may be bonded to each other to form a ring. The ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond and / or a carbonyl group in the ring. Examples of the group formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butylene group or a pentylene group).

Next, the compound (ZI-3) is described.

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

In the formula, R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. The alkyl group and the alkoxy group preferably have 1 to 6 carbon atoms.

R _6c and R _7c represent a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 6 carbon atoms.

R _x and R _y each independently represent an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group or a vinyl group. The number of carbon atoms of these atoms is preferably 1 to 6.

Two or more of R _1c to R _7c may be bonded to each other to form a ring. R _x and R _y may be combined to form a ring. These rings may contain an oxygen atom, a sulfur atom, an ester bond and / or an amide bond.

In the formula (ZI-3) X ^- X is in formula (ZI) ^- is synonymous with.

Specific examples of the compound (ZI-3) include compounds described in the compounds exemplified in paragraphs 0046 and 0047 of Japanese Patent Application Laid-Open No. 2004-233661 or in paragraphs 0040 to 0046 of JP-A No. 2003-35948 have.

Next, the compound (ZI-4) is described.

The compound (ZI-4) is a compound having a cation represented by the following general formula (ZI-4). This compound (ZI-4) is effective for inhibiting outgas.

Among the general formula (ZI-4)

Each of R ¹ to R ¹³ independently represents a hydrogen atom or a substituent. At least one of R ¹ to R ¹³ is preferably a substituent containing an alcoholic hydroxyl group. Here, the "alcoholic hydroxyl group" means a hydroxyl group bonded to the carbon atom of the alkyl group.

Z is a single bond or a divalent linking group.

When R ¹ to R ¹³ are substituents containing an alcoholic hydroxyl group, it is preferable that R ¹ to R ¹³ are groups represented by - (WY). Here, Y is an alkyl group substituted by a hydroxyl group, and W is a single bond or a divalent linking group.

Preferable examples of the alkyl group represented by Y include an ethyl group, a propyl group and an isopropyl group. Y particularly preferably contains a structure represented by -CH ₂ CH ₂ OH.

The divalent linking group represented by W is not particularly limited but is preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl or arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, an alkoxycarbonyl group or An arbitrary hydrogen atom in a single bond, an acyloxy group, an alkylsulfonyl group, an acyl group or an alkoxycarbonyl group is preferably a divalent group obtained by substituting any hydrogen atom in a carbamoyl group by a single bond, Is a divalent group substituted by a single bond.

When R ¹ to R ¹³ are substituents containing an alcoholic hydroxyl group, the number of carbon atoms contained is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.

The substituent containing an alcoholic hydroxyl group as R ¹ to R ¹³ may have two or more alcoholic hydroxyl groups. The number of alcoholic hydroxyl groups contained in the substituent containing an alcoholic hydroxyl group as R ¹ to R ¹³ is 1 to 6, preferably 1 to 3, and more preferably 1.

The number of alcoholic hydroxyl groups contained in the compound represented by formula (ZI-4) is 1 to 10, preferably 1 to 6, more preferably 1 to 3, in total for all of R ¹ to R ¹³ .

When R ¹ to R ¹³ do not contain an alcoholic hydroxyl group, examples of the substituent as R ¹ to R ¹³ include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, An alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group An alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an amino group, an amino group, an amino group, an amino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkylsulfonylamino group, A heterocyclic group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl and arylsulfinyl group, an alkyl and arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, Early, an imide group, phosphino group, a phosphine group P, Phosphinicosuccinic group, a phosphinylmethyl group, a phosphono group, a silyl group, a hydrazino group, a ureido group, boronic acid group [-B (OH) _2], [phosphate group -OPO (OH) ₂ ], a sulfate group (-OSO ₃ H), and other known substituents.

R ¹ ~ R ¹³ If this does not contain an alcoholic hydroxyl group, R ¹ ~ R ¹³ is preferably a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a cyano group, A carboxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkylsulfonylamino group, An arylthio group, a sulfamoyl group, an alkyl and arylsulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, a silyl group or an ureido group.

When R ¹ to R ¹³ do not contain an alcoholic hydroxyl group, R ¹ to R ¹³ are more preferably a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a cyano group, an alkoxy group, an acyloxy group, An alkoxycarbonylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, a sulfamoyl group, an alkylsulfonyl group, an alkoxycarbonylamino group, or a carbamoyl group.

When R ¹ to R ¹³ do not contain an alcoholic hydroxyl group, R ¹ to R ¹³ are particularly preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or an alkoxy group.

Two adjacent ^ones of R ¹ to R ¹³ may be bonded to each other to form a ring. The rings include aromatic and non-aromatic hydrocarbon rings and heterocyclic rings. These rings may be combined to further form a condensed ring.

The compound (ZI-4) preferably has a structure in which at least one of R ¹ to R ¹³ contains an alcoholic hydroxyl group, and more preferably at least one of R ⁹ to R ¹³ contains an alcoholic hydroxyl group have.

Z represents a single bond or a divalent linking group, as described above. Examples of the divalent connecting group include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, a thioether group, an amino group, a disulfide group, An alkylsulfonyl group, -CH = CH-, an aminocarbonylamino group and an aminosulfonylamino group.

This divalent linking group may have a substituent. Examples of the substituent include the same ones as those enumerated above for R ¹ to R ¹³ .

Z is preferably a bond or a group having no electron-attracting property such as a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, -CH = CH-, an aminocarbonylamino group and an aminosulfonylamino group . Z is more preferably a single bond, an ether group or a thioether group, and particularly preferably a single bond.

Hereinafter, general formulas (ZII) and (ZIII) will be described.

In formulas (ZII) and (ZIII), each of R ₂₀₄ to R ₂₀₇ independently represents an aryl group, an alkyl group or a cycloalkyl group. These aryl group, alkyl group and cycloalkyl group may have a substituent.

Preferable examples of the aryl group as R ₂₀₄ to R ₂₀₇ include the same groups as those enumerated above for R ₂₀₁ to R ₂₀₃ in the compound (ZI-1).

R ₂₀₄ ~ R ₂₀₇ of the preferred alkyl groups and cycloalkyl groups as examples there may be mentioned the numbered straight-chain, branched chain or cycloalkyl group for R ₂₀₁ ~ R ₂₀₃ in the above compound (ZI-2).

Further, in the general formula (ZII) and (ZIII) X ^- X is in formula (ZI) ^- is synonymous with.

Another preferred example of the photoacid generator is a compound represented by the following general formula (ZIV), (ZV) or (ZVI).

Among the general formulas (ZIV) to (ZVI)

Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.

R ₂₀₈ independently represents an alkyl group, a cycloalkyl group or an aryl group in the formulas (ZV) and (ZVI). These alkyl groups, cycloalkyl groups and aryl groups may be substituted or unsubstituted.

These groups are preferably substituted by fluorine atoms. This makes it possible to increase the strength of the acid from which the photoacid generator is generated.

R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group, an aryl group or an electron-withdrawing group. These alkyl groups, cycloalkyl groups, aryl groups and electron-withdrawing groups may be substituted or unsubstituted.

As the preferable R _{209, a} substituted or unsubstituted aryl group can be exemplified.

As preferable R ₂₁₀ , an electron-withdrawing group can be exemplified. The electron-withdrawing group is preferably a cyano group or a fluoroalkyl group.

A represents an alkylene group, an alkenylene group or an arylene group. These alkylene, alkenylene and arylene groups may have a substituent.

Further, a compound having a plurality of structures represented by formula (ZVI) as a photoacid generator is also preferable. Such compounds include, for example, formula (ZVI) to the indicated compounds of the R ₂₀₉ or that by the R ₂₁₀ and the general formula (ZVI) having a further R ₂₀₉ or R ₂₁₀ structure in which the coupling of different compounds represented by Compounds.

(ZI-1) to (ZI-3) are more preferable as the photoacid generator, and the compound represented by the general formula (ZI) Is particularly preferable.

Specific examples of the photoacid generator are shown below, but the scope of the present invention is not limited thereto.

The photoacid generators may be used singly or in combination of two or more. When two or more kinds are used in combination, it is preferable to combine compounds which generate two kinds of organic acids different in total number of atoms except hydrogen atom.

The content of the photoacid generator is preferably 0.1 to 40 mass%, more preferably 0.5 to 30 mass%, and still more preferably 1 to 20 mass%, based on the total solid content of the composition. When the composition is used for EB or EUV applications, the content is particularly preferably 5 to 20% by mass.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may be used as a positive composition or as a negative composition.

In the case of the former, the composition according to the present invention may further contain a resin [3] which is decomposed by the action of an acid to increase its solubility in an alkali developing solution. In this case, the composition according to the present invention may further contain [5] a compound having a molecular weight of 3000 or less (hereinafter also referred to as a dissolution inhibiting compound) which is decomposed by the action of an acid to increase solubility in an alkali developing solution.

In the latter case, the composition according to the present invention is a resin which is soluble in an alkali developing solution (hereinafter also referred to as " alkali-soluble resin ") and [6] an acid crosslinking agent which is crosslinked with an alkali- . ≪ / RTI >

[3] Resin which is decomposed by the action of an acid and increases in solubility in an alkali developer

The resin decomposed by the action of an acid to increase its solubility in an alkali developing solution typically has a group which is decomposed by the action of an acid to generate an alkali-soluble group (hereinafter also referred to as an acid-decomposable group). The resin may have an acid-decomposable group on one of the main chain and the side chain of the resin, or may be provided on both sides thereof. This resin preferably has an acid-decomposable group in its side chain.

As the acid decomposable group, a group in which the hydrogen atom of an alkali-soluble group such as a -COOH group and -OH group is substituted by a group which is eliminated by the action of an acid is preferable. As the group which is cleaved by the action of an acid, an acetal group or a tertiary ester group is particularly preferable.

When the acid-decomposable group is bonded as a side chain, the base resin may include, for example, an alkali-soluble resin having -OH or -COOH group in the side chain. Examples of such an alkali-soluble resin include those described later.

The alkali dissolution rate of these alkali-soluble resins is preferably measured at 23 DEG C by 0.261N tetramethylammonium hydroxide (TMAH), and is preferably at least 17 nm / sec. This rate is particularly preferably at least 33 nm / second.

Particularly preferred alkali-soluble resins in this respect include o-, m- and p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl substituted poly (hydroxystyrene) Styrene-hydroxystyrene copolymers, hydrogenated novolac resins, etc., partially hydrolyzed styrene block copolymers such as styrene-butadiene styrene block copolymers, styrene-butadiene styrene block copolymers, ; And a resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid and norbornenecarboxylic acid.

Preferred examples of the repeating unit having an acid-decomposable group include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, and (meth) acrylic acid tertiary alkyl esters. As the repeating unit, 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate is more preferable.

Resins which are decomposed by the action of an acid and increase in solubility in an alkali developing solution are disclosed in European Patent No. 254853, Japanese Patent Application Laid-Open Nos. 2-25850, 3-223860 and 4-251259 For example, by reacting a precursor of a group cleaved by the action of an acid on the resin, or by copolymerizing an alkali-soluble resin monomer bonded with a group which is eliminated by the action of an acid, with various monomers.

When the composition of the present invention is irradiated with a KrF excimer laser beam, an electron beam, an X-ray, or a high-energy beam having a wavelength of 50 nm or less (for example, EUV), the resin preferably has a hydroxystyrene repeat unit. More preferably, the resin is a copolymer of hydroxystyrene protected by hydroxystyrene and a group cleaved by the action of an acid, or a copolymer of hydroxystyrene and a (meth) acrylic acid tertiary alkyl ester.

Specific examples of such a resin include a resin having a repeating unit represented by the general formula (IA).

Another preferred resin is a resin having a repeating unit represented by the above general formula (X). The content of the repeating unit represented by the general formula (X) in the resin is preferably within a range of 3 to 90 mol%, more preferably within a range of 5 to 80 mol% based on the total repeating units, And preferably in the range of 7 to 70 mol%.

The content of the repeating unit having an acid-decomposable group is preferably 3 to 95 mol%, more preferably 5 to 90 mol%, and particularly preferably 10 to 85 mol% in the total repeating units constituting the acid-decomposable resin.

Specific examples of the resins described above are shown below, but the present invention is not limited thereto.

In the above embodiment, tBu represents a t-butyl group.

The content of groups capable of being decomposed by an acid is determined by the number of groups (B) capable of being decomposed by an acid in the resin and the number (S) of alkali-soluble groups which are not protected by groups cleaved by an acid, / (B + S). This content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

When the composition of the present invention is irradiated with ArF excimer laser light, the resin preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure. In the following, these resins are referred to as " alicyclic hydrocarbon-based acid-decomposable resins ".

Examples of the alicyclic hydrocarbon-based acid-decomposable resin include repeating units having a partial structure containing an alicyclic hydrocarbon represented by the following formulas (pI) to (pV) and repeating units represented by the following formula (II-AB) Is preferably a resin containing at least one member selected from the group consisting of

Among the general formulas (pI) to (pV)

R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group and Z represents an atomic group necessary for forming a cycloalkyl group together with a carbon atom.

R ₁₂ to R ₁₆ each independently represent a straight-chain or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group. Provided that at least one of R ₁₂ to R ₁₄ represents a cycloalkyl group. Any one of R ₁₅ and R ₁₆ represents a cycloalkyl group.

R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. Provided that at least one of R ₁₇ to R ₂₁ represents a cycloalkyl group. Any one of R ₁₉ and R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group.

R ₂₂ to R ₂₅ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. Provided that at least one of R ₂₂ to R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring structure.

Among the general formula (II-AB)

R ₁₁ 'and R ₁₂ ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Z 'represents an atomic group necessary for forming an alicyclic structure together with two bonded carbon atoms (C-C).

It is more preferable that the formula (II-AB) is represented by the following formula (II-AB1) or (II-AB2)

Of the general formulas (II-AB1) and (II-AB2)

R ₁₃ 'to R ₁₆ ' each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, -COOH, -COOR ₅ , a group which is decomposed by the action of an acid, -C (═O) R ₁₇ ', an alkyl group or a cycloalkyl group. Here, R ₅ represents an alkyl group, a cycloalkyl group or a group having a lactone structure. X represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ - or -NHSO ₂ NH-. A 'represents a single bond or a divalent linking group. R ₁₇ 'represents a group having -COOH, -COOR ₅ , -CN, a hydroxyl group, an alkoxy group, -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ or a lactone structure. Here, R ₆ represents an alkyl group or a cycloalkyl group. At least two of R ₁₃ 'to R ₁₆ ' may be bonded to each other to form a ring structure.

n represents 0 or 1;

In the general formulas (pI) to (pV), the alkyl group in R ₁₂ to R ₂₅ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, Butyl group, sec-butyl group and t-butyl group.

The cycloalkyl group in R ₁₂ to R ₂₅ or the cycloalkyl group formed by Z and the carbon atom may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Specifically, a group having a monocyclo, bicyclo, tricyclo and tetracyclo structure having 5 or more carbon atoms can be exemplified. The carbon number thereof is preferably from 6 to 30, and particularly preferably from 7 to 25.

Preferred examples of the cycloalkyl group include an adamantyl group, a noradamantyl group, a decalin group, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a siderol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, A cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group. More preferably an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group and a tricyclodecanyl group.

These alkyl groups and cycloalkyl groups may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group and an alkoxycarbonyl group (having 2 to 6 carbon atoms). These substituents may have a better substituent. Examples of the better substituent include a hydroxyl group, a halogen atom and an alkoxy group.

The structure represented by the general formulas (pI) to (pV) can be used for protecting an alkali-soluble group. As the alkali-soluble group, various groups well-known in the technical field can be mentioned.

Specifically, there can be mentioned, for example, a structure in which a hydrogen atom such as a carboxylic acid group, a sulfonic acid group, a phenol group or a thiol group is substituted by a structure represented by the general formulas (pI) to (pV). Preferably a structure in which a hydrogen atom of a carboxylic acid group or a sulfonic acid group is substituted by a structure represented by any one of formulas (pI) to (pV).

The repeating unit having an alkali-soluble group protected by the structure represented by any one of formulas (pI) to (pV) is preferably a repeating unit represented by the following formula (pA).

Among the general formula (pA)

R represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Each of the plurality of Rs may be the same or different.

A is selected from the group consisting of a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, a urea group and a combination of two or more thereof, to be.

Rp ₁ is a group represented by any one of formulas (pI) to (pV).

The repeating unit represented by the general formula (pA) is most preferably a repeating unit of 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate .

Specific examples of the repeating unit represented by formula (pA) are shown below.

Wherein, in each formula Rx is H, CH _3, represents a CF ₃ or CH ₂ OH, Rxa and Rxb represents an alkyl group having from 1 to 4 carbon atoms independently of each other.

The halogen atom as R ₁₁ 'or R ₁₂ ' in the formula (II-AB) is, for example, a chlorine atom, a bromine atom, a fluorine atom or an iodine atom.

The alkyl group as R ₁₁ 'or R ₁₂ ' is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, , Hexyl group and heptyl group.

The atomic group represented by Z 'is an atomic group that forms a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin. The atomic group is preferably a repeating unit of a bridged alicyclic hydrocarbon.

The skeleton of the formed alicyclic hydrocarbon may be the same as the cycloalkyl group of R ₁₂ to R ₂₅ in formulas (pI) to (pVI).

The skeleton of the alicyclic hydrocarbon may have a substituent. Examples of such a substituent include R ₁₃ 'to R ₁₆ ' in the above general formulas (II-AB1) and (II-AB2).

The group decomposed by the action of an acid in the alicyclic hydrocarbon-based acid-decomposable resin is a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pV), a repeating unit represented by the general formula (II-AB ) And repeating units of a copolymerization component to be described later.

Each of the substituents of R ₁₃ 'to R ₁₆ ' in the general formulas (II-AB1) and (II-AB2) forms an alicyclic structure or a bridged alicyclic structure in the general formula (II-AB) May also be a substituent of the atomic group Z 'to be used.

The following specific examples are listed as the repeating units represented by the general formula (II-AB1) or the general formula (II-AB2), but the present invention is not limited to these examples.

The alicyclic hydrocarbon-based acid-decomposable resin preferably has a repeating unit containing a lactone group. The lactone group is preferably a group having a 5- to 7-membered cyclic lactone structure, and particularly preferably has a cyclic structure of another cyclic structure in a form of forming a bicyclo structure or spiro structure in a 5- to 7-membered ring lactone structure.

More preferably, the alicyclic hydrocarbon-based acid-decomposable resin contains a repeating unit having a group containing a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17). The group having a lactone structure may be directly bonded to the main chain. Preferred examples of the lactone structure include (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17) . By using a specific lactone structure, line edge roughness and development defects can be further reduced.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Examples of the preferable substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, And an acid-decomposable group.

n ₂ represents an integer of 0 to 4; When n ₂ is an integer of 2 or more, a plurality of existing Rb _{2 s} may be the same or different. In this case also, the plurality of Rb ₂ to each other there may be bonded to each other to form a ring structure.

R ₁₃ in the general formula (LC1-1) ~ Examples of any one repeating unit having a group containing a lactone structure represented, for example, the general formula (II-AB1) and (II-AB2) of (LC1-17) ' To R ₁₆ 'have a group represented by the general formulas (LC1-1) to (LC1-17) and a repeating unit represented by the following general formula (AI). Examples of the former include a structure in which R ₅ of -COOR ₅ is a group represented by formulas (LC1-1) to (LC1-17).

In the general formula (AI) Rb ₀ represents an alkyl group of a hydrogen atom, a halogen atom or a group having from 1 to 4 carbon atoms.

The alkyl group as Rb ₀ is, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group or a t-butyl group. These alkyl groups may have a substituent. Examples of the substituent include a hydroxyl group and a halogen atom.

As the halogen atom of Rb ₀ , a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be exemplified.

Rb ₀ is preferably a hydrogen atom or a methyl group.

Ab represents an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination thereof. Ab is preferably a single bond or a linking group represented by -Ab ₁ -CO ₂ -.

Ab ₁ is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

V is a group represented by any one of formulas (LC1-1) to (LC1-17).

The repeating unit having a lactone structure usually contains an optical isomer, but any of the optical isomers may be used. In addition, one kind of optical isomer may be used singly or a plurality of optical isomers may be used in combination. When one kind of optical isomer is mainly used, the optical purity is preferably 90% ee or more, more preferably 95% ee or more.

As the repeating unit having a particularly preferable lactone group, the following repeating unit can be exemplified. By selecting the optimum lactone group, the pattern profile and the density dependency are improved. Rx and R wherein R represents a H, CH _3, CH ₂ OH or CF _3.

The alicyclic hydrocarbon-based acid-decomposable resin preferably has a repeating unit containing an alicyclic hydrocarbon structure substituted by a polar group. This makes it possible to improve substrate adhesion and developer affinity. The polar group is preferably a hydroxyl group or a cyano group. The hydroxyl group as the polar group forms an alcoholic hydroxyl group.

Examples of the alicyclic hydrocarbon structure substituted by a polar group include a structure represented by the following general formula (VIIa) or (VIIb).

In formula (VIIa), R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. However, R ₂ at least one of c ~ R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c is a hydroxyl group, and the remainder is a hydrogen atom. More preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the remaining one is a hydrogen atom.

The group represented by the general formula (VIIa) is preferably a dihydroxyl or monohydroxy, more preferably a dihydroxyl.

General formula (VIIa) or as the repeating unit having a group represented by (VIIb) wherein the general formula (II-AB1) or (II-AB2) of the R ₁₃ '~ R _16', at least one is the above-mentioned general formula (VIIa) or (VIIb), and repeating units represented by the following general formula (AIIa) or (AIIb). An example of the former is a structure in which R ₅ of -COOR ₅ is a group represented by the general formula (VIIa) or (VIIb).

Among the general formulas (AIIa) and (AIIb)

R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c ~ R ₄ c is R ₂ c ~ R ₄ c and agreement in the formula (VIIa).

Specific examples of the repeating unit represented by formula (AIIa) or (AIIb) are set forth below, but the present invention is not limited thereto.

The alicyclic hydrocarbon-based acid-decomposable resin may have a repeating unit represented by the following general formula (VIII).

Z ₂ in the general formula (VIII) represents -O- or -N (R ₄₁ ) -. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group or -OSO ₂ -R ₄₂ . Here, R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group as R ₄₁ or R ₄₂ may be substituted with a halogen atom or the like. In this case, the halogen atom is preferably a fluorine atom.

As the repeating unit represented by the general formula (VIII), the following specific examples may be mentioned, but the present invention is not limited thereto.

The alicyclic hydrocarbon-based acid-decomposable resin preferably has a repeating unit containing an alkali-soluble group, more preferably a repeating unit containing a carboxyl group. This makes it possible to improve the resolution in the use of the contact hole.

As the repeating unit containing a carboxyl group, both a repeating unit in which a carboxyl group is directly bonded to the main chain of the resin and a repeating unit in which a carboxyl group is bonded to the main chain of the resin through a connecting group are all preferable.

Examples of the former include repeating units derived from acrylic acid or methacrylic acid. The linking group in the latter may have a monocyclic or polycyclic cycloalkyl structure.

The repeating unit containing a carboxyl group is most preferably a repeating unit derived from acrylic acid or methacrylic acid.

The weight average molecular weight of the resin which is decomposed by the action of an acid and increases in solubility in an alkali developing solution is preferably in the range of 2,000 to 200,000 in terms of polystyrene calculated by the GPC method. When the weight average molecular weight is 2,000 or more, heat resistance and dry etching resistance can be particularly improved. When the weight average molecular weight is 200,000 or less, the developability can be particularly improved and the film formability can be improved due to the decrease in the viscosity of the composition.

A more preferred molecular weight is within the range of 2,500 to 50,000, more preferably within the range of 3,000 to 20,000. In the formation of fine patterns using electron beams, X-rays, and high-energy radiation having a wavelength of 50 nm or less (for example, EUV), it is most preferable to set the weight average molecular weight within the range of 3,000 to 10,000. By adjusting the molecular weight, improvement of the heat resistance and resolution of the composition and reduction of development defects can be achieved at the same time.

The degree of dispersion (Mw / Mn) of the resin which is decomposed by the action of an acid and increases in solubility in an alkali developer is preferably 1.0 to 3.0, more preferably 1.2 to 2.5, and further preferably 1.2 to 1.6. By adjusting this degree of dispersion, for example, line edge roughness performance can be improved.

In the first embodiment, the compounding ratio of the acid-decomposable resin is preferably from 0 to 99.9% by mass, more preferably from 50 to 95% by mass, and still more preferably from 60 to 93% by mass based on the total solid content.

In the second and third embodiments, the compounding ratio of the acid-decomposable resin excluding the acid-proliferating agent-containing resin in the composition is preferably from 1.0 to 70 mass%, more preferably from 3.0 to 50 mass%, based on the total solid content of the composition , More preferably from 5.0 to 30 mass%.

[4] A resin soluble in an alkali developer (hereinafter also referred to as " alkali-soluble resin "),

The alkali dissolution rate of the alkali-soluble resin is preferably 2 nm / sec or more (measured at 23 占 폚) using 0.261N tetramethylammonium hydroxide (TMAH). Particularly preferably, this speed is 20 nm / sec or more.

Examples of the alkali-soluble resin include novolac resins, hydrogenated novolak resins, acetone-pyrogallol resins, o-polyhydroxystyrene, m-polyhydroxystyrene, p- Halogenated or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymers, o / p- and m / p-hydroxystyrene copolymers, some O-alkylated products of hydroxyl groups of polyhydroxystyrene For example, it is possible to use 5 to 30 mol% of O-methylated product, O- (1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product or O- (for example, 5 to 30 mol% of O-acetylated or O- (t-butoxy) carbonyl), styrene-maleic anhydride copolymer , Styrene-hydroxystyrene copolymer,? -Methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and There can be a conductor, and a polyvinyl alcohol derivative is not limited to these.

Preferable examples of the alkali-soluble resin include novolak resins, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl substituted polyhydroxystyrene, Alkylated or O-acylated, styrene-hydroxystyrene copolymers and? -Methylstyrene-hydroxystyrene copolymers.

In particular, a resin having a hydroxystyrene structure is preferable in the present invention. Among the hydroxystyrene structures, an m-hydroxystyrene structure is particularly preferable.

The novolac resin is obtained by subjecting a predetermined monomer as a main component to an addition condensation with an aldehyde in the presence of an acidic catalyst.

The weight average molecular weight of the alkali-soluble resin is 2000 or more, preferably 5000 to 200000, and more preferably 5000 to 100000. Here, the weight average molecular weight is defined as a polystyrene reduced value obtained by GPC (gel permeation chromatography).

Two or more of these alkali-soluble resins in the present invention may be used in combination.

The amount of the alkali-soluble resin to be used is, for example, 40 to 97 mass%, preferably 60 to 90 mass%, based on the total solid content in the composition.

[5] A compound having a molecular weight of 3,000 or less (hereinafter also referred to as " dissolution inhibiting compound ") which is decomposed by the action of an acid to increase its solubility in an alkali developer,

As the dissolution inhibiting compound, an alicyclic or aliphatic compound containing an acid-decomposable group is preferable because it does not lower the permeability at 220 nm or less. Examples of such a compound include a cholic acid derivative containing an acid-decomposable group as described in Proceeding of SPIE, 2724, 355 (1996). Examples of the alicyclic structure and the acid decomposable group are the same as those described for the alicyclic hydrocarbon-based acid-decomposable resin.

When the composition according to the present invention is exposed by a KrF excimer laser or irradiated with electron beams, the dissolution inhibiting compound preferably contains a structure in which the phenolic hydroxyl group in the phenol compound is substituted by an acid decomposer. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.

The molecular weight of the dissolution inhibiting compound is 3000 or less, preferably 300 to 3000, more preferably 500 to 2500.

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

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

[6] An acid crosslinking agent for crosslinking with an alkali-soluble resin by the action of an acid

As the acid crosslinking agent, any compound can be used as long as it is capable of crosslinking a resin soluble in an alkali developing solution by the action of an acid. The following (1) to (3) are preferable.

(1) Hydroxymethyl, alkoxymethyl or acyloxymethyl derivatives of phenol derivatives.

(2) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group.

(3) a compound having an epoxy group.

As the alkoxymethyl group, those having 6 or less carbon atoms are preferable. The acyloxymethyl group preferably has 6 or less carbon atoms.

Particularly preferred among these acid crosslinking agents are listed below.

In the formula, L ₁ to L ₈ may be mutually the same or different. Each of L ₁ to L ₈ independently represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group or an alkyl group having 1 to 6 carbon atoms.

The addition amount of the acid crosslinking agent is, for example, 3 to 70 mass%, preferably 5 to 50 mass%, based on the total solid content of the composition.

<Other ingredients>

The composition according to the present invention further contains a basic compound, an organic solvent, a surfactant, an acid decomposable dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a dissolution promoting compound for a developer, and a compound having a proton acceptor functional group There may be.

(Basic compound)

The composition according to the present invention may further contain a basic compound. By further containing a basic compound, it is possible to further reduce the change in performance over time between exposure and heating (post-baking). In addition, this makes it possible to control the diffusing property of the acid generated in the exposure by the exposure.

The basic compound is preferably a nitrogen-containing organic compound. The compound which can be used is not particularly limited, but for example, the following compounds (1) to (4) can be used.

(1) a compound represented by the following general formula (BS-1)

In the general formula (BS-1)

Each R independently represents a hydrogen atom or an organic group. Provided that at least one of the three Rs is an organic group. The organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.

The number of carbon atoms of the alkyl group as R is not particularly limited, but is usually 1 to 20, preferably 1 to 12.

The number of carbon atoms of the cycloalkyl group as R is not particularly limited, but is usually 3 to 20, preferably 5 to 15.

The number of carbon atoms of the aryl group as R is not particularly limited, but is usually 6 to 20, preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

The number of carbon atoms of the aralkyl group as R is not particularly limited, but is usually 7 to 20, preferably 7 to 11. Specifically, benzyl group and the like can be exemplified.

The alkyl group, cycloalkyl group, aryl group and aralkyl group as R may be a hydrogen atom substituted by a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group and an alkyloxycarbonyl group.

In the compound represented by the general formula (BS-1), it is preferable that at least two Rs are organic groups.

Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, But are not limited to, hexyl methyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine, octadecyl amine, didecyl amine, methyl octadecyl amine, dimethyl undecyl amine, N, N-dimethyldodecyl amine, methyl dioctadecyl amine, N , N-dibutylaniline, N, N-dihexyl aniline, 2,6-diisopropylaniline and 2,4,6-tri (t-butyl) aniline.

Further, as a preferable basic compound represented by the general formula (BS-1), at least one R may be an alkyl group substituted by a hydroxyl group. Specific examples thereof include triethanolamine and N, N-dihydroxyethylaniline.

The alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed. The oxyalkylene chain is preferably -CH ₂ CH ₂ O-. Specific examples thereof include tris (methoxyethoxyethyl) amine and compounds exemplified after line 60 of column 3 of US 6040112.

(2) a compound having a nitrogen-containing heterocycle

The nitrogen-containing heterocycle may or may not have aromatics. In addition, a plurality of nitrogen atoms may be contained. It may contain a hetero atom other than nitrogen. Specific examples thereof include compounds having an imidazole structure (2-phenylbenzoimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N- hydroxyethylpiperidine Compounds having a pyridine structure (such as 4-dimethylaminopyridine) and compounds having an antipyrine structure (such as antipyrine and Hydroxy antipyrine, etc.).

A compound having two or more rings is also preferably used. Specific examples thereof include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] undeca-7-ene.

(3) An amine compound having a phenoxy group

The amine compound having a phenoxy group is a compound having an phenoxy group at the terminal on the opposite side to the N atom of an alkyl group containing an amine compound. The phenoxy group may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonate ester group, an aryl group, an aralkyl group, You can have it.

This compound more preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3 to 9, more preferably 4 to 6. Of the oxyalkylene chains, -CH ₂ CH ₂ O- is particularly preferred.

As specific examples, mention may be made of 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)] -amine and US2007 / 0224539A1 The exemplified compounds (C1-1) to (C3-3) are exemplified.

(4) Ammonium salt

Ammonium salts may also be suitably used. The ammonium salt is preferably a hydroxide or a carboxylate. More specifically, tetraalkylammonium hydroxides such as tetrabutylammonium hydroxide are preferable.

Other compounds which can be used in the composition according to the present invention include compounds synthesized in the examples of JP-A-2002-363146 and compounds described in paragraph 0108 of JP-A 2007-298569.

Further, as the basic compound, a photosensitive basic compound may be used. Examples of the photosensitive basic compound are described in Japanese Patent Publication No. 2003-524799 and J. Photopolym. Sci. Tech. Vol. 8, pp. 543-553 (1995) and the like can be used.

The molecular weight of the basic compound is preferably 250 to 2000, more preferably 400 to 1000.

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

The content of the basic compound is preferably 0.01 to 8.0% by mass, more preferably 0.1 to 5.0% by mass, and particularly preferably 0.2 to 4.0% by mass, based on the total solid content of the composition.

(Surfactants)

The composition according to the present invention preferably further contains a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are particularly preferable.

Examples of the surfactant include Megapac F176 and Megafac R08 manufactured by Dainippon Ink and Chemicals, Inc., PF656 and PF6320 available from OMNOVA, Troyzol S-366 available from Toray Chemical Co., (Trade name: Florad FC430 manufactured by Shin-Etsu Chemical Co., Ltd.) and polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Surfactants other than the fluorine-based and / or silicon-based surfactants may also be used. More specifically, examples thereof include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

Other known surfactants can be suitably used. Examples of the surfactant that can be used include surfactants described later in the specification of US Patent 2008/0248425 A1.

The surfactant may be used singly or in combination of two or more kinds.

The amount of the surfactant to be used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total solid content of the composition.

(solvent)

The solvent that can be used in preparing the composition is not particularly limited as long as it dissolves the respective components, and examples thereof include alkylene glycol monoalkyl ether carboxylates (such as propylene glycol monomethyl ether acetate), alkylene glycol monoalkyl (Such as propylene glycol monomethyl ether and the like), lactic acid alkyl ester (ethyl lactate and lactate methyl), cyclic lactone (? -Butyrolactone and the like, preferably having 4 to 10 carbon atoms), chain or cyclic ketone (Preferably carbon atoms of 4 to 10), alkylene carbonates (such as ethylene carbonate and propylene carbonate), carboxylic acid alkyl (preferably acetic acid alkyl such as butyl acetate) and alkoxyacetate Ethyl ethoxypropionate) and the like. Examples of other solvents that can be used include solvents described later in US2008 / 0248425A1 specification.

Of these solvents, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers and ethyl lactate are particularly preferred.

These solvents may be used alone or in combination of two or more kinds. When two or more of them are used in combination, it is preferable to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10 and more preferably from 20/80 to 60/40.

As the solvent having a hydroxyl group, alkylene glycol monoalkyl ether or lactic acid alkyl ester is preferable, and as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether carboxylate is preferable.

The amount of the solvent to be used is not particularly limited, but the total solids concentration of the composition is preferably 0.5 to 30% by weight, more preferably 1.0 to 10% by weight. Particularly, when electron beam or EUV lithography is performed using the composition of the present invention, the amount is preferably 2.0 to 6.0% by mass, and more preferably 2.0 to 4.5% by mass.

(A dissolution inhibiting compound having a molecular weight of 3,000 or less which is decomposed by the action of an acid to increase its solubility in an alkali developing solution)

As a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as &quot; dissolution inhibiting compound &quot;) which is decomposed by the action of an acid to increase its solubility in an alkali developer, Proceeding of SPIE 2724, 355 (1996), and the like. The alicyclic or aliphatic compound is preferably an alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group. Examples of the acid-decomposable group include the same ones as described above for the acid-decomposable unit.

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

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

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

(Other additives)

The composition according to the present invention may contain a compound (for example, an alicyclic or aliphatic compound having a phenol compound or a carboxyl group having a molecular weight of 1000 or less) promoting dissolution of the dye, a plasticizer, a photosensitizer, a light absorber and a developer Can be further contained. Compounds having a proton acceptor functional group described in JP-A-2006-208781 and JP-A-2007-286574 can also be preferably used.

&Lt; Pattern formation method >

The composition according to the invention is typically used as follows. That is, the composition according to the present invention is typically applied on a support such as a substrate to form a film. The thickness of this film is preferably 0.02 to 0.1 mu m. As a method of coating on a substrate, spin coating is preferable, and the number of revolutions is preferably 1000 to 3000 rpm.

For example, the composition is applied onto a substrate (e.g., a silicon / silicon dioxide coating, a silicon nitride and a chromium-deposited quartz substrate, etc.) used for the production of precision integrated circuit devices and the like by a suitable application method such as a spinner and a coater . Thereafter, this is dried to obtain an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as a photosensitive film). In addition, a known antireflection film may be applied in advance.

Subsequently, the photosensitive film is irradiated with an actinic ray or radiation, preferably baked (heated), and then developed. By baking, the generation of sulfonic acid from the above-described acid-proliferating agent or acid-proliferating unit can be promoted. Therefore, it becomes possible to obtain a better pattern. From the viewpoints of sensitivity and stability, the baking temperature is preferably 80 to 150 캜, and more preferably 90 to 130 캜.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, extraneous light, X-rays and electron beams. It is more preferable that these actinic rays or radiation have a wavelength of, for example, 250 nm or less, particularly 220 nm or less. Examples of such active light or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray and electron beam. As the particularly preferable active ray or radiation, ArF excimer laser, F ₂ excimer laser, EUV (13 nm) and electron beam can be exemplified.

Further, at the time of irradiation of actinic rays or radiation, exposure (liquid immersion exposure) in which a liquid (pure water or the like) having a refractive index higher than that of air is filled between the photosensitive film and the lens may be performed. Thus, the resolution can be increased. In this case, between the film and the immersion liquid, an immersion liquid resistant film (also referred to as &quot; top coat &quot;) may be formed on the film in order to avoid contact between the film and the immersion liquid. As another means for avoiding contact between the membrane and the immersion liquid, a hydrophobic resin (HR) may be previously added to the composition. Specific examples of the hydrophobic resin (HR) include resins described in paragraphs 0172 to 0253 of US2008 / 0305432A1.

In the development step, an alkali developing solution is usually used.

Examples of the alkali developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia water, primary amines such as ethylamine and n-propylamine, Tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tertiary amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and tertiary amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. And an alkaline aqueous solution containing a cyclic amine such as pyrrole and piperidine.

To the alkali developing solution, an appropriate amount of an alcohol and / or a surfactant may be added.

The concentration of the alkali developing solution is usually 0.1 to 20% by mass. The pH of the alkali developing solution is usually 10.0 to 15.0.

The details of the process for producing the imprint mold using the composition according to the present invention are described in, for example, Japanese Patent No. 4109085, Japanese Patent Application Laid-Open No. 2008-162101, and " · Application development - Please refer to the board technology of nanoimprint and the latest technology development - edited by Yoshihiko Hirai (Frontier Publishing).

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[First Embodiment]

<Sulfonic Acid Generating Compound>

[synthesis]

As the sulfonic acid generating compound, the compounds 1 to 13 shown in the following Table 1 were synthesized as follows. For the purpose of comparison, Comparative Compounds 1 to 5 were synthesized as follows.

[Table 1-1]

[Table 1-2]

[Table 1-3]

&Lt; Synthesis of Compound (1)

Alcohol (3.9 g, 20.1 mmol) represented by the following formula was mixed with 30 ml of methylene chloride and 7.8 g (77.5 mmol) of triethylamine.

Then, troisopropylbenzenesulfonyl chloride (6.1 g, 20.2 mmol) and dimethylaminopyridine (98.1 mg, 0.8 mmol) were added to the resulting mixed solution, and the mixture was stirred at room temperature for 2 hours. Subsequently, 50 ml of water was added, and the organic layer was extracted with 100 ml of ethyl acetate. The organic layer was further washed three times with 50 ml of water. The organic layer was further washed with 50 ml of a saturated aqueous sodium hydrogencarbonate solution and 50 ml of an aqueous saturated sodium chloride solution, dried over magnesium sulfate, and then distilled off under reduced pressure. The obtained crystals were recrystallized with isopropyl alcohol to obtain 3.0 g of Compound 1. [

^{1 H-NMR (400MHz, CDCl} 3): δ1.22-1.26 (m, 18H), 2.32 (t, 2H, J = 8.0Hz), 2.90 (m, 1H), 3.73 (t, 2H, J = 6.8 2H), 7.16 (s, 2H), 7.30-7.40 (m, 5H), 4.18 (t, 2H, J =

<Synthesis of Compounds 2 to 16>

Compounds 2 to 16 were synthesized in the same manner as described for compound 1 above. That is, these compounds were synthesized by reacting corresponding alcohols and sulfonic acid halides under basic conditions.

[Calculation of the volume of the acid]

The volumes of the sulfonic acids that the compounds 1 to 16 and the comparative compounds 1 to 5 can generate were calculated as follows. That is, it was obtained as follows using &quot; WinMOPAC &quot; manufactured by Fujitsu Kabushiki Kaisha. First, we have entered the chemical structure of the acid that each compound can generate. Then, using this structure as an initial structure, the most stable steric body of each acid was determined by calculating the molecular force field using the MM3 method. Thereafter, the "accessible volume" of each acid was calculated by performing molecular orbital calculation using the PM3 method for these most stable three-dimensional fundus.

The results are shown in Table 1 above. As can be seen from these results, the volume of the sulfonic acid that the compounds 1 to 13 can generate was 240 Å ³ or more. On the other hand, the volume of the sulfonic acid which the comparative compounds 1 to 5 can generate was less than 240 Å ³ .

&Lt;

As the photoacid generator, the following compounds A to G were used.

Compound B was synthesized as follows.

<Synthesis of tricyclohexylbenzene>

Benzene 20.0 g was added 6.83 g of aluminum chloride, the mixture was cooled and stirred at 3 캜, and 40.4 g of cyclohexyl chloride was slowly added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 5 hours, and then transferred to ice water. The organic layer was extracted with ethyl acetate, and the obtained organic layer was distilled off under reduced pressure at 40 占 폚. After further distillation under reduced pressure at 170 deg. C, the mixture was cooled to room temperature, and 50 ml of acetone was added thereto, followed by recrystallization. The precipitated crystals were collected by filtration to obtain 14 g of tricyclohexylbenzene.

<Synthesis of sodium tricyclohexylbenzenesulfonate>

30 g of tricyclohexylbenzene was dissolved in 50 ml of methylene chloride, followed by cooling and stirring at 3 캜, and 15.2 g of chlorosulfonic acid was slowly added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 5 hours, 10 g of ice was added, and 40 g of a 50% sodium hydroxide aqueous solution was added. Further, 20 g of ethanol was added, and after stirring at 50 DEG C for 1 hour, the insoluble matter was removed by filtration, and the residue was distilled off under reduced pressure at 40 deg. The precipitated crystals were collected by filtration and washed with hexane to obtain 30 g of sodium 1,3,5-tricyclohexylbenzenesulfonate.

&Lt; Synthesis of compound B >

4.0 g of triphenylsulfonium bromide was dissolved in 20 ml of methanol, and 5.0 g of sodium 1,3,5-tricyclohexylbenzenesulfonate dissolved in 20 ml of methanol was added. After stirring at room temperature for 2 hours, 50 ml of ion-exchanged water was added, and the mixture was extracted with chloroform. The obtained organic layer was washed with water, and then distilled off under reduced pressure at 40 占 폚. The resulting crystals were recrystallized from a methanol / ethyl acetate solvent. Thus, 5.0 g of Compound B was obtained.

^{1 H-NMR (400MHz, CDCl} 3) δ = 7.85 (d, 6H), 7.68 (t, 3H), 7.59 (t, 6H), 6.97 (s, 2H), 4.36-4.27 (m, 2H), 2.48 -2.38 (m, 1 H), 1.97-1.16 (m, 30H).

&Lt; Basic compound >

As the basic compound, the following compounds C-1 to C-3 were used.

C-1: 2,4,5-triphenylimidazole

C-2: Tetrabutylammonium hydroxide

C-3: 1,5-Diazabicyclo [4.3.0] non-5-ene

<Surfactant>

As the surfactant, the following W-1 to W-4 were used.

W-1: Megapack F176 (manufactured by Dainippon Ink and Chemicals, Incorporated; Fluorine system}

W-2: Megapack R08 (manufactured by Dainippon Ink and Chemicals, Incorporated; Fluorine and silicon systems}

W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; Silicon system}

W-4: Toroizol S-366 (manufactured by Toray Chemical Co., Ltd.; Fluorine system}

<Solvent>

As the solvent, the following A1 to A4 and B1 and B2 were used. In addition, these solvents were mixed as appropriate.

A1: Propylene glycol monomethyl ether acetate

A2: 2-heptanone

A3: Cyclohexanone

A4:? -Butyrolactone

B1: Propylene glycol monomethyl ether

B2: Ethyl acetate

<Example A>

(Examples 1A to 11A and Comparative Examples 1A to 6A)

(Resist preparation)

The components shown in Table 2 below were dissolved in a solvent to prepare a solution having a solid content concentration of 4.0% by mass. This solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 mu m to obtain a positive type resist solution.

(Resist evaluation)

First, 60 nm of the antireflection film DUV-42 made by SEIENCE CO., LTD. Was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, dried on a hot plate at 100 DEG C for 90 seconds, Lt; 0 &gt; C for 240 seconds. Thereafter, each positive resist solution was applied using a spin coater and dried at 120 캜 for 90 seconds to form a resist film having a film thickness of 0.12 탆.

The resist film was exposed to light by an ArF excimer laser stepper (manufactured by ISI, NA = 0.6) through a mask, and immediately after exposure, heated on a hot plate at 120 캜 for 90 seconds. Further, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 캜 for 60 seconds, rinsed with pure water for 30 seconds, and dried to obtain a line pattern.

[Sensitivity, resolution (γ)]

The surface was exposed while changing the exposure dose by 0.5 mJ in the range of 10 to 40 mJ / cm 2, and further baked at 110 캜 for 90 seconds. Thereafter, the dissolution rate at each exposure dose was measured using an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution to obtain a dissolution rate curve.

In this dissolution rate curve, the resolution (gamma value) was calculated from the gradient of the linear portion of the dissolution rate curve with the exposure amount as sensitivity when the dissolution rate of the resist saturates. The larger the? value, the better the dissolution contrast.

[Pattern shape, line edge roughness (LER)]

An exposure amount for reproducing a mask pattern of a line-and-space (L / S = 1/1) having a line width of 150 nm was defined as an optimum exposure amount, and a profile at an optimum exposure amount was observed by a scanning type microscope (SEM). Further, in this pattern, the distance from the reference line on which an edge was present was measured by using a scanning electron microscope (S-9220, manufactured by Hitachi Seisakusho Co., Ltd.) for arbitrary 30 points included in the longitudinal direction of 50 m . Then, the standard deviation of this distance was calculated to calculate 3σ.

[Stability over time]

Each composition was stored at room temperature for one month. Then, the degree of fluctuation of the sensitivity before and after the storage (by the measurement of the sensitivity by the surface exposure) was evaluated. This evaluation was made on the basis of the following criteria.

(Criteria)

Good (Good): When the sensitivity variation was less than 1 mJ / cm 2

? (Fair): when the variation in sensitivity was 1 mJ / cm2 or more and 3 mJ / cm2 or less

Insufficient: The sensitivity variation was greater than 3mJ / cm2.

The results of these measurements are shown in Table 2 below.

[Table 2-1]

[Table 2-2]

The photoacid generator, sulfonic acid generating compound, basic compound, surfactant and solvent were appropriately selected from those shown above.

As the resin, any one of the following (RA-1), (RA-20), (RA-23) and (RA-25) was used. In the following formula, the number on the right side of the repeating unit indicates a molar ratio. Mw represents the weight average molecular weight, and Mw / Mn represents the degree of dispersion.

From the results shown in Table 2, it can be seen that the composition according to the first embodiment is excellent in sensitivity, resolution, roughness characteristics and aged stability in ArF exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition in ArF excimer laser exposure.

<Example B>

A resist solution was prepared and applied in the same manner as in Example A except that 0.06 g of the following polymer was added to the composition of Example 1A, to obtain a resist film. The obtained resist film was subjected to pattern exposure through an immersion liquid (pure water) using an ArF excimer laser immersion scanner (XT1250i; NA 0.85 by ASML) to form a pattern in the same manner as in Example A. It was confirmed that the same evaluation results were obtained with respect to the obtained patterns in terms of sensitivity, resolution (?), Roughness characteristics, pattern shape and aging stability.

&Lt; Example C >

(Examples 1C to 19C and Comparative Examples 1C to 6C)

(Resist preparation)

After dissolving the components shown in Table 3 below in a solvent, the solution was filtered with a polytetrafluoroethylene filter having a pore size of 0.1 占 퐉 to prepare a positive resist solution having a solid content concentration of 9.0% by mass.

(Resist evaluation)

The prepared positive resist solution was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 100 캜 for 90 seconds to form a resist film having a film thickness of 0.4 탆.

This resist film was subjected to pattern exposure using a KrF excimer laser stepper (NA = 0.63) using a line and space mask, and immediately after exposure, the resist film was heated on a hot plate at 110 캜 for 90 seconds. Thereafter, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 DEG C for 60 seconds, rinsed with pure water for 30 seconds, and dried to form a line pattern.

[Sensitivity, resolution (γ)]

Sensitivity and resolution (gamma value) were obtained in the same manner as described for Example A, except that the apparatus and process conditions were applied.

[Pattern shape, line edge roughness (LER)]

An exposure amount for reproducing a mask pattern of a line-and-space (L / S = 1/1) with a line width of 180 nm was taken as an optimum exposure amount, and a profile at an optimum exposure amount was observed by a scanning type microscope (SEM). Further, distances from baselines where edges had to exist were measured using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) relative to arbitrary 30 points included in the longitudinal direction of the formed pattern in a length of 50 mu m. Then, the standard deviation of this distance was calculated to calculate 3σ.

[Stability over time]

The stability with time was evaluated in the same manner as described for Example A.

The evaluation results are shown in Table 3 below.

[Table 3-1]

[Table 3-2]

[Table 3-3]

[Table 3-4]

The photoacid generator, sulfonic acid generating compound, basic compound, surfactant and solvent were appropriately selected from those shown above.

The resin was appropriately selected from (R-1) to (R-27) exemplified above. (R-2), (R-10), (R-14), (R-17), (R- The molar ratios and weight average molecular weights of the respective repeating units in (R-18 (L)), (R-22), (R-23) and (R-27) are shown in Table 4 below.

[Table 4]

From the results shown in Table 3, it can be seen that the composition according to the first embodiment is excellent in sensitivity, resolution, roughness characteristics and aged stability in KrF exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition in KrF excimer laser exposure.

<Example D>

(Examples 1D to 25D and Comparative Examples 1D to 6D)

(Resist preparation)

The components shown in the following Table 5 were dissolved in a solvent and then filtered with a polytetrafluoroethylene filter having a pore size of 0.1 탆 to prepare a positive type resist solution having a solid content concentration of 4.0% by mass.

(Resist evaluation)

The prepared positive resist solution was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 100 캜 for 60 seconds to form a resist film having a film thickness of 0.12 탆 .

The resist film was irradiated with an electron beam projection lithography apparatus (accelerating voltage: 100 keV) manufactured by Nikon Corporation, and immediately after irradiated, it was heated on a hot plate at 110 캜 for 90 seconds. Thereafter, the resist film was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 DEG C for 60 seconds, rinsed with pure water for 30 seconds, and dried to form a line and space pattern.

〔Sensitivity〕

The amount of electron beam irradiation at the time of resolving a line-and-space (L / S = 1/1) having a line width of 0.10 mu m was taken as sensitivity.

[Pattern shape, line edge roughness (LER)]

An exposure amount for reproducing a pattern of a line-and-space (L / S = 1/1) having a line width of 50 nm was defined as an optimum exposure amount. The profile at this optimum exposure amount was observed by a scanning type microscope (SEM). Further, the LER was obtained in the same manner as described for Example A.

[Out gas performance: Film thickness variation rate by exposure]

After irradiating with an electron beam at an irradiation dose of 2.0 times the irradiation amount giving the sensitivity (sensitivity determined in the plane exposure), the film thickness before and after the post-heating was measured, and from the film thickness at the time of non- .

Film thickness variation rate (%) = [(film thickness at unexposed light - film thickness after exposure) / film thickness at unexposed state] × 100

[Stability over time]

After each composition was stored at room temperature for one month, the degree of fluctuation of the sensitivity before and after storage (the sensitivity measured in the above-mentioned surface exposure) was evaluated. This evaluation was made on the basis of the following criteria.

(Criteria)

Good (Good): When the variation in sensitivity was less than 1 占 폚 / ㎠

(Fair): When the fluctuation of the sensitivity was 1 占 폚 / cm2 or more and 3 占 폚 / cm2 or less

× (Insufficient): When the sensitivity variation is larger than 3 μC / cm 2.

The evaluation results are shown in Table 5 below.

[Table 5-1]

[Table 5-2]

[Table 5-3]

[Table 5-4]

[Table 5-5]

From the results shown in Table 5, it can be seen that the composition according to the first embodiment is excellent in sensitivity, roughness characteristics, outgas performance, and aged stability in electron beam exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition by electron beam irradiation.

<Example E>

(Examples 1E to 14E and Comparative Examples 1E to 6E)

(Resist preparation)

After dissolving the components shown in Table 6 below in a solvent, the solution was filtered with a polytetrafluoroethylene filter having a pore size of 0.1 占 퐉 to prepare a negative type resist solution having a solid content concentration of 4.0% by mass.

(Resist evaluation)

The prepared negative resist solution was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 120 캜 for 60 seconds to form a resist film having a film thickness of 0.12 탆 .

The resist film was irradiated with an electron beam projection lithography apparatus (accelerating voltage: 100 keV) manufactured by Nikon Corporation, and immediately after irradiated, it was heated on a hot plate at 110 캜 for 90 seconds. Thereafter, the resist film was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 DEG C for 60 seconds, rinsed with pure water for 30 seconds, and dried to form a line and space pattern.

Evaluation was carried out in the same manner as described for Example D. The results are shown in Table 6.

[Table 6-1]

[Table 6-2]

[Table 6-3]

The structure, molecular weight and molecular weight distribution of the alkali-soluble resin and the structure of the acid crosslinking agent are shown below.

From the results shown in Table 6, it can be seen that the composition according to the first embodiment is excellent in sensitivity, roughness characteristics, outgas performance and aged stability in electron beam exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a negative resist composition by electron beam irradiation.

&Lt; Example F >

(Examples 1F to 25F and Comparative Examples 1F to 6F)

(Resist preparation)

The components shown in Table 7 below were dissolved in a solvent, and the resulting solution was filtered with a polytetrafluoroethylene filter having a pore size of 0.1 탆 to prepare a positive resist solution having a solid content concentration of 4.0% by mass.

(Resist evaluation)

The prepared positive resist solution was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 100 캜 for 60 seconds to form a resist film having a film thickness of 0.12 탆 .

〔Sensitivity〕

The resist film thus obtained was exposed to EUV light (wavelength 13 nm) while changing the exposure dose in the range of 0 to 35.0 mJ / cm 2 by 0.5 mJ / cm 2, and then baked at 110 ° C for 90 seconds. Thereafter, the dissolution rate at each exposure dose was measured using an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution to obtain a dissolution rate curve. The amount of exposure when the dissolution rate of the resist was saturated in the dissolution rate curve was taken as sensitivity.

[Pattern shape, line edge roughness (LER)]

An exposure amount for reproducing a mask pattern of a line-and-space (L / S = 1/1) having a line width of 50 nm was taken as an optimum exposure amount, and a profile at an optimum exposure amount was observed by a scanning type microscope (SEM). Further, the distance from the reference line where an edge was present was measured by using a scanning electron microscope (Hitachi SEISAKUSHO S-9220) relative to arbitrary 30 points included in the 50 mu m length direction of this pattern. Then, the standard deviation of this distance was calculated to calculate 3σ.

[Out gas performance: Film thickness variation rate by exposure]

The film thickness variation ratio by EUV exposure was obtained in the same manner as described for Example D.

The stability with time was evaluated in the same manner as described for Example A.

The evaluation results are shown in Table 7 below.

[Table 7-1]

[Table 7-2]

[Table 7-3]

From the results shown in Table 7, it can be seen that the composition according to the first embodiment is excellent in sensitivity, roughness characteristics, outgas performance, and aged stability in EUV exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition by EUV irradiation.

<Example G>

(Examples 1G to 8G and Comparative Examples 1G to 6G)

(Resist preparation)

The components shown in Table 8 below were dissolved in a solvent, and the solution was filtered with a polytetrafluoroethylene filter having a pore size of 0.1 占 퐉 to prepare a negative resist solution having a solid content concentration of 4.0% by mass.

&Lt; Evaluation of resist &

The prepared negative resist solution was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 120 캜 for 60 seconds to form a resist film having a film thickness of 0.12 탆 .

This resist film was evaluated in the same manner as described for Example F. The results are shown in Table 8 below.

[Table 8-1]

[Table 8-2]

From the results shown in Table 8, it can be seen that the composition according to the first embodiment is excellent in sensitivity, roughness characteristics, outgas performance, and aged stability in EUV exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a negative resist composition by EUV irradiation.

[Second embodiment]

&Lt; acid-proliferating agent carrying resin >

[synthesis]

Resins P-1 to P-26 shown in Table 1 below were synthesized as follows as the acid-proliferating agent-carrying resin. In Table 9, the columns of "monomers (1)" to "(4)" show the structures of the monomers used as raw materials for the respective resins. In the column of the composition ratio, the molar ratio of each repeating unit corresponding to each monomer is described. In the column of &quot; Mw &quot;, the weight average molecular weight in terms of polystyrene measured by GPC (solvent: NMP) is described. The column of &quot; MWD &quot; shows the degree of dispersion (Mw / Mn).

[Table 9-1]

[Table 9-2]

[Table 9-3]

[Table 9-4]

[Table 9-5]

[Table 9-6]

[Table 9-7]

[Table 9-8]

[Table 9-9]

[Table 9-10]

&Lt; Synthesis of Compound (A-1) >

Compound (A-1) used as monomer (3) of Resin P-6 was synthesized as follows. That is, first, alcohol (3.9 g, 20.1 mmol) represented by the following formula was mixed with 30 ml of methylene chloride and triethylamine (7.8 g, 77.5 mmol).

Then, 4-vinylbenzenesulfonyl chloride (4.1 g, 20.1 mmol) and dimethylaminopyridine (98.1 mg, 0.8 mmol) were added to the resulting mixed solution, and the mixture was stirred at room temperature for 2 hours. Subsequently, 50 ml of water was added, and the organic layer was extracted with 100 ml of ethyl acetate. The organic layer was further washed three times with 50 ml of water. The organic layer was further washed with 50 ml of a saturated aqueous sodium hydrogencarbonate solution and 50 ml of an aqueous saturated sodium chloride solution, dried over magnesium sulfate, and then distilled off under reduced pressure. The obtained crystals were recrystallized with isopropyl alcohol to obtain 3.2 g of the compound (A-1).

^{1 H-NMR (400MHz, CDCl} 3): δ2.28 (t, 2H, J = 7.2Hz), 3.75-3.68 (m, 2H), 4.80-4.90 (m, 2H), 4.18 (t, 2H, J = 7.2 Hz), 5.47 (d, IH, J = 11.2 Hz), 5.91 (d, IH, J = 17.6 Hz), 6.76 (dd, 1H, J = 17.6,11.2 Hz), 7.25-7.40 ), 7.54 (d, 2H, J = 8.0 Hz), 7.82 (d, 2H, J = 9.2 Hz)

&Lt; Synthesis of other monomers >

This compound was synthesized in the same manner as described for Compound (A-1). That is, it was synthesized by reacting the corresponding alcohol and sulfonic acid halide under basic conditions.

[Synthesis Example 1: Synthesis of Resin (P-6)]

4.02 parts by mass of monomer (M-4), 1.01 parts by mass of monomer (A-1), 9.29 parts by mass of 1-methoxy-2-propanol and 1.02 parts by mass of 2, 2'-azobis (2,4-dimethylvaleronitrile) [V-65; Manufactured by Wako Pure Chemical Industries, Ltd.) was prepared.

9.29 parts by mass of 1-methoxy-2-propanol was heated to 65 占 폚 under a nitrogen stream. Thereafter, the mixed solution was added dropwise over 2 hours while stirring the solution. After completion of the dropwise addition, the mixture was further stirred at 65 DEG C for 2 hours. Subsequently, 1.02 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was further added, and the mixture was further stirred at 65 ° C for 2 hours .

The reaction solution was allowed to cool, and reprecipitated using a large amount of hexane / ethyl acetate. This was then subjected to vacuum drying to obtain 7.0 parts by mass of a resin (P-6).

Synthesis Example 2: Synthesis of Resins (P-1) to (P-5) and (P-7) to (P-26)

Resins (P-1) to (P-5) and (P-7) to (P-26) were synthesized in the same manner as Resin (P-6) except that the monomers to be used were changed.

[Comparative compound]

Comparative compounds 1 to 4 shown in Table 1 were prepared. In addition, the following compound X was prepared.

&Lt;

As the photoacid generator, at least one of (z1) to (z102) listed above was used.

&Lt; Basic compound >

As the basic compound, any one of the following compounds C-1 to C-5 was used.

C-1: 2,4,5-triphenylimidazole

C-2: Tetrabutylammonium hydroxide

C-3: 1,5-Diazabicyclo [4.3.0] non-5-ene

C-4:

<Surfactant>

As the surfactant, any one of the following W-1 to W-4 was used.

W-1: Megapack F176 (manufactured by Dainippon Ink and Chemicals, Incorporated; Fluorine system}

W-2: Megapack R08 (manufactured by Dainippon Ink and Chemicals, Incorporated; Fluorine and silicon systems}

W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; Silicon system}

W-4: Toroizol S-366 (manufactured by Toray Chemical Co., Ltd.; Fluorine system}

<Solvent>

As the solvent, the following A1 to A4 and B1 and B2 were used. In addition, these solvents were mixed as appropriate.

A1: Propylene glycol monomethyl ether acetate

A2: 2-heptanone

A3: Cyclohexanone

A4:? -Butyrolactone

B1: Propylene glycol monomethyl ether

B2: Ethyl acetate

<Example A>

(Examples 1A to 12A and Comparative Examples 1A to 3A)

(Resist preparation)

The components shown in Table 10 below were dissolved in a solvent to prepare a solution having a solid content concentration of 4.0% by mass. This solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 mu m to obtain a positive resist solution.

(Resist evaluation)

First, on a silicon substrate subjected to hexamethyldisilazane treatment, a bracket and an antireflection film DUV-42 made by Siren Co., Ltd. were uniformly coated with a thickness of 60 nm using a spin coater. Subsequently, it was dried on a hot plate at 100 DEG C for 90 seconds, and then heated and dried at 190 DEG C for 240 seconds. Thereafter, each positive resist solution was applied using a spin coater and dried at 120 캜 for 90 seconds to form a resist film having a film thickness of 0.12 탆.

The resist film was exposed to light by an ArF excimer laser stepper (manufactured by ISI, NA = 0.6) through a mask, and immediately after exposure, heated on a hot plate at 120 캜 for 90 seconds. Further, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 캜 for 60 seconds, rinsed with pure water for 30 seconds, and dried to obtain a line pattern.

[Sensitivity, resolution (γ)]

The surface was exposed while changing the exposure dose by 0.5 mJ in the range of 10 to 45 mJ / cm 2, and further baked at 110 캜 for 90 seconds. Thereafter, the dissolution rate at each exposure dose was measured using an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution to obtain a dissolution rate curve.

In this dissolution rate curve, the resolution (gamma value) was calculated from the gradient of the linear portion of the dissolution rate curve with the exposure amount as sensitivity when the dissolution rate of the resist saturates. The larger the? value, the better the dissolution contrast.

[Pattern shape, line edge roughness (LER)]

An exposure amount for reproducing a mask pattern of a line-and-space (L / S = 1/1) having a line width of 150 nm was defined as an optimum exposure amount, and a profile at an optimum exposure amount was observed by a scanning type microscope (SEM). Further, in this pattern, distances from baselines where edges had to exist were measured by using a scanning electron microscope (Hitachi SEISAKUSHO S-9220) relative to arbitrary 30 points included in the longitudinal direction of 50 mu m . Then, the standard deviation of this distance was calculated to calculate 3σ.

[Stability over time]

Each composition was stored at room temperature for one month. Then, the degree of fluctuation of the sensitivity before and after storage was evaluated. This evaluation was made on the basis of the following criteria.

(Criteria)

Good (Good): When the sensitivity variation was less than 1 mJ / cm 2

? (Fair): when the variation in sensitivity was 1 mJ / cm2 or more and 3 mJ / cm2 or less

Insufficient: The sensitivity variation was greater than 3mJ / cm2.

The measurement results are shown in Table 10 below.

[Table 10-1]

[Table 10-2]

From the results shown in Table 10, it can be seen that the composition according to the second embodiment is excellent in sensitivity, resolution, LER, pattern shape and aged stability in ArF exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition in ArF excimer laser exposure.

<Example B>

A resist solution was prepared and applied in the same manner as in Example A except that 0.06 g of the following polymer was added to the composition of Example 1A, to obtain a resist film. The obtained resist film was subjected to pattern exposure through an immersion liquid (pure water) using an ArF excimer laser immersion scanner (XT1250i; NA 0.85 by ASML) to form a pattern in the same manner as in Example A. It was confirmed that evaluation results identical to each other in sensitivity, resolution (?), LER, pattern shape, and aging stability were obtained with respect to the obtained patterns.

&Lt; Example C >

(Examples 1C to 24C and Comparative Examples 1C to 3C)

(Resist preparation)

The components shown in the following Table 11 were dissolved in a solvent and then filtered with a polytetrafluoroethylene filter having a pore size of 0.1 탆 to prepare a positive resist solution having a solid concentration of 9.0%.

(Resist evaluation)

The prepared positive resist solution was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 120 캜 for 90 seconds to form a resist film having a film thickness of 0.4 탆.

The resist film was subjected to pattern exposure through a mask for line and space using a KrF excimer laser stepper (NA = 0.63), and immediately after exposure, the resist film was heated on a hot plate at 110 DEG C for 90 seconds. Thereafter, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 DEG C for 60 seconds, rinsed with pure water for 30 seconds, and dried to form a line pattern.

[Sensitivity, resolution (γ)]

Sensitivity and resolution (gamma value) were obtained in the same manner as described for Example A, except that the apparatus and process conditions were applied.

[Pattern shape, line edge roughness (LER)]

An exposure amount for reproducing a mask pattern of a line-and-space (L / S = 1/1) with a line width of 180 nm was taken as an optimum exposure amount, and a profile at an optimum exposure amount was observed by a scanning type microscope (SEM). In addition, the distance from the reference line where an edge was present was measured by using a scanning electron microscope (Hitachi SEISAKUSHO S-9220) relative to arbitrary 30 points included in the length direction 50 mu m of the formed pattern. Then, the standard deviation of this distance was calculated to calculate 3σ.

[Stability over time]

The stability with time was evaluated in the same manner as described for Example A.

The evaluation results are shown in Table 11 below.

[Table 11-1]

[Table 11-2]

[Table 11-3]

From the results shown in Table 11, it can be seen that the composition according to the second embodiment is excellent in sensitivity, resolution, LER, pattern shape and aged stability in KrF exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition in KrF excimer laser exposure.

<Example D>

(Examples 1D to 28D and Comparative Examples 1D to 3D)

(Resist preparation)

The components shown in Table 12 below were dissolved in a solvent and then filtered with a polytetrafluoroethylene filter having a pore size of 0.1 탆 to prepare a positive resist solution having a solid content concentration of 4.0% by mass.

(Resist evaluation)

The positive resist solution thus prepared was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 120 캜 for 60 seconds to form a resist film having a film thickness of 0.12 탆 .

The resist film was irradiated with an electron beam projection lithography apparatus (accelerating voltage: 100 keV) manufactured by Nikon Corporation, and immediately after irradiated, it was heated on a hot plate at 110 캜 for 90 seconds. Thereafter, the resist film was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 DEG C for 60 seconds, rinsed with pure water for 30 seconds, and dried to form a line and space pattern.

〔Sensitivity〕

The obtained pattern was observed using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.). The amount of electron beam irradiation at the time of resolving a line-and-space (L / S = 1/1) having a line width of 0.10 m was defined as sensitivity (E ₀ ).

〔definition〕

The resolution (the minimum line width at which lines and spaces are separated and resolved) of the 1: 1 line space in the exposure amount representing the sensitivity (E ₀ ) is defined as resolution (dense).

[Line edge roughness (LER)]

LER was obtained in the same manner as described for Example A.

[Out gas performance: Film thickness variation rate by exposure]

The film thickness before the post-exposure was measured after irradiating with the electron beam at an irradiation amount 2.0 times the irradiation amount giving the sensitivity (the sensitivity determined in the surface exposure), and the film thickness was measured from the film thickness at the time of unexposed The variation rate was obtained.

Film thickness variation rate (%) = [(film thickness at unexposed light - film thickness after exposure) / film thickness at unexposed state] × 100

[Stability over time]

After each composition was stored at room temperature for 1 month, the degree of fluctuation of the sensitivity before and after storage was evaluated by visual inspection. This evaluation was made on the basis of the following criteria.

(Criteria)

Good (Good): When the variation in sensitivity was less than 1 占 폚 / ㎠

(Fair): When the fluctuation of the sensitivity was 1 占 폚 / cm2 or more and 3 占 폚 / cm2 or less

× (Insufficient): When the sensitivity variation is larger than 3 μC / cm 2.

The evaluation results are shown in Table 12 below.

[Table 12-1]

[Table 12-2]

[Table 12-3]

From the results shown in Table 12, it can be seen that the composition according to the second embodiment is excellent in sensitivity, resolution, LER, outgas performance, and long-term stability in electron beam exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition by electron beam irradiation.

<Example E>

(Examples 1E to 24E and Comparative Examples 1E to 3E)

(Resist preparation)

The components shown in Table 13 below were dissolved in a solvent, which was then filtered through a polytetrafluoroethylene filter having a pore size of 0.1 탆 to prepare a positive resist solution having a solid content concentration of 4.0% by mass.

(Resist evaluation)

The positive resist solution thus prepared was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 120 캜 for 60 seconds to form a resist film having a film thickness of 0.12 탆 .

〔Sensitivity〕

The resist film thus obtained was subjected to surface exposure while changing the exposure dose in the range of 0 to 15.0 mJ / cm 2 by 0.5 mJ / cm 2 using EUV light (wavelength 13 nm), and baked at 110 ° C for 90 seconds. Thereafter, the dissolution rate at each exposure dose was measured using an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution to obtain a dissolution rate curve.

[Line edge roughness (LER)]

An exposure amount for reproducing a mask pattern of a line-and-space (L / S = 1/1) having a line width of 50 nm was taken as an optimum exposure amount, and a profile at an optimum exposure amount was observed by a scanning type microscope (SEM). Further, a distance from a reference line where an edge was present was measured by using a scanning electron microscope (Hitachi Seisakusho S-9220) for arbitrary 30 points included in the longitudinal direction of this pattern. Then, the standard deviation of this distance was calculated to calculate 3σ.

[Out gas performance: Film thickness variation rate by exposure]

The film thickness variation ratio by EUV exposure was obtained in the same manner as described for Example D.

[Stability over time]

The stability with time was evaluated in the same manner as described for Example A.

The evaluation results are shown in Table 13 below.

[Table 13-1]

[Table 13-2]

[Table 13-3]

From the results shown in Table 13, it can be seen that the composition according to the second embodiment is excellent in sensitivity, LER, outgas performance, and long-term stability in EUV exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition by EUV irradiation.

[Third embodiment]

&Lt; acid-proliferating agent carrying resin >

[synthesis]

Resins P-1 to P-26 shown in Table 14 below were synthesized as follows as the acid-proliferating agent-carrying resin. In Table 14, the columns of "monomers (1)" to "(4)" show the structures of the monomers used as raw materials for the respective resins. In the column of the composition ratio, the molar ratio of each repeating unit corresponding to each monomer is described. In the column of &quot; Mw &quot;, the weight average molecular weight in terms of polystyrene measured by GPC (solvent: NMP) is described. The column of &quot; MWD &quot; shows the degree of dispersion (Mw / Mn).

[Table 14-1]

[Table 14-2]

[Table 14-3]

[Table 14-4]

[Table 14-5]

[Table 14-6]

[Table 14-7]

[Table 14-8]

[Table 14-9]

<Synthesis of Monomer>

The compound (A-1) used as the monomer (3) of Resin P-6 was synthesized by referring to the description of Non-Patent Documents 2 and 3. Other monomers were synthesized in the same manner as the compound (A-1).

[Synthesis Example 1: Synthesis of Resin (P-6)]

4.00 parts by mass of 4-hydroxystyrene, 3.50 parts by mass of monomer (M-4), 1.88 parts by mass of monomer (A-1), 9.29 parts by mass of 1-methoxy- 2'-azobis (2,4-dimethylvaleronitrile) [V-65; Manufactured by Wako Pure Chemical Industries, Ltd.) was prepared.

9.29 parts by mass of 1-methoxy-2-propanol was heated to 65 占 폚 under a nitrogen stream. Thereafter, the mixed solution was added dropwise over 2 hours while stirring the solution. After completion of the dropwise addition, the mixture was further stirred at 65 DEG C for 2 hours. Subsequently, 0.99 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was further added, and the mixture was further stirred at 65 ° C for 2 hours .

The reaction solution was allowed to cool, and reprecipitated using a large amount of hexane / ethyl acetate. This was then subjected to vacuum drying to obtain 7.0 parts by mass of a resin (P-6).

Synthesis Example 2: Synthesis of Resins (P-1) to (P-5) and (P-7) to (P-26)

Resins (P-1) to (P-5) and (P-7) to (P-26) were synthesized in the same manner as Resin (P-6) except that the monomers to be used were changed.

[Comparative compound]

Comparative compounds 1 to 4 shown in Table 14 were prepared. In addition, the following compound X was prepared.

&Lt;

As the photoacid generator, at least one of (z1) to (z102) listed above was used.

&Lt; Basic compound >

As the basic compound, any one of the following compounds C-1 to C-5 was used.

C-1: 2,4,5-triphenylimidazole

C-2: Tetrabutylammonium hydroxide

C-3: 1,5-Diazabicyclo [4.3.0] non-5-ene

C-4:

<Surfactant>

As the surfactant, any one of the following W-1 to W-4 was used.

W-1: Megapack F176 (manufactured by Dainippon Ink and Chemicals, Incorporated; Fluorine system}

W-2: Megapack R08 (manufactured by Dainippon Ink and Chemicals, Incorporated; Fluorine and silicon systems}

W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; Silicon system}

W-4: Toroizol S-366 (manufactured by Toray Chemical Co.,

<Solvent>

As the solvent, the following A1 to A4 and B1 and B2 were used. In addition, these solvents were mixed in an appropriate amount.

A1: Propylene glycol monomethyl ether acetate

A2: 2-heptanone

A3: Cyclohexanone

A4:? -Butyrolactone

B1: Propylene glycol monomethyl ether

B2: Ethyl acetate

<Example A>

(Examples 1A to 12A and Comparative Examples 1A to 3A)

(Resist preparation)

The components shown in Table 15 below were dissolved in a solvent to prepare a solution having a solid content concentration of 4.0% by mass. This solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 mu m to obtain a positive resist solution.

(Resist evaluation)

First, on a silicon substrate subjected to hexamethyldisilazane treatment, a bracket and an antireflection film DUV-42 made by Siren Co., Ltd. were uniformly coated with a thickness of 60 nm using a spin coater. Subsequently, it was dried on a hot plate at 100 DEG C for 90 seconds, and then heated and dried at 190 DEG C for 240 seconds. Thereafter, each positive resist solution was applied using a spin coater and dried at 120 캜 for 90 seconds to form a resist film having a film thickness of 0.12 탆.

The resist film was exposed to light by an ArF excimer laser stepper (manufactured by ISI; NA = 0.6) through a mask, and immediately after exposure, the resist film was heated on a hot plate at 120 캜 for 90 seconds. Further, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 캜 for 60 seconds, rinsed with pure water for 30 seconds, and dried to obtain a line pattern.

[Sensitivity, resolution (γ)]

The surface was exposed while changing the exposure dose by 0.5 mJ in the range of 10 to 45 mJ / cm 2, and further baked at 110 캜 for 90 seconds. Thereafter, the dissolution rate at each exposure dose was measured using an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution to obtain a dissolution rate curve.

In this dissolution rate curve, the resolution (gamma value) was calculated from the gradient of the linear portion of the dissolution rate curve with the exposure amount as sensitivity when the dissolution rate of the resist saturates. The larger the? value, the better the dissolution contrast.

[Pattern shape, line edge roughness (LER)]

An exposure amount for reproducing a mask pattern of a line-and-space (L / S = 1/1) having a line width of 150 nm was defined as an optimum exposure amount, and a profile at an optimum exposure amount was observed by a scanning type microscope (SEM). Further, in this pattern, distances from baselines where edges had to exist were measured by using a scanning electron microscope (Hitachi SEISAKUSHO S-9220) relative to arbitrary 30 points included in the longitudinal direction of 50 mu m . Then, the standard deviation of this distance was calculated to calculate 3σ.

[Stability over time]

Each composition was stored at room temperature for one month. Then, the degree of fluctuation of the sensitivity before and after storage was evaluated. This evaluation was made on the basis of the following criteria.

(Criteria)

Good (Good): When the sensitivity variation was less than 1 mJ / cm 2

? (Fair): when the variation in sensitivity was 1 mJ / cm2 or more and 3 mJ / cm2 or less

Insufficient: The sensitivity variation was greater than 3mJ / cm2.

The measurement results are shown in Table 15 below.

[Table 15-1]

[Table 15-2]

From the results shown in Table 15, it can be seen that the composition according to the third embodiment is excellent in sensitivity, resolution, LER, pattern shape and aged stability in ArF exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition for ArF excimer laser exposure.

<Example B>

A resist solution was prepared and applied in the same manner as in Example A except that 0.06 g of the following polymer was added to the composition of Example 1A to obtain a resist film. The obtained resist film was subjected to pattern exposure through an immersion liquid (pure water) using an ArF excimer laser immersion scanner (XT1700i; NA1.2 manufactured by ASML) to form a pattern in the same manner as in Example A. It was confirmed that the same evaluation results were obtained with respect to the obtained patterns in terms of sensitivity, resolution (?), LER, pattern shape and aging stability.

&Lt; Example C >

(Examples 1C to 24C and Comparative Examples 1C to 3C)

(Resist preparation)

The components shown in Table 16 below were dissolved in a solvent and then filtered with a polytetrafluoroethylene filter having a pore size of 0.1 탆 to prepare a positive type resist solution having a solid content concentration of 4.5%.

(Resist evaluation)

The prepared positive resist solution was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 120 캜 for 90 seconds to form a resist film having a film thickness of 0.4 탆.

The resist film was subjected to pattern exposure through a mask for line and space using a KrF excimer laser stepper (NA = 0.63), and immediately after exposure, the resist film was heated on a hot plate at 110 DEG C for 90 seconds. Thereafter, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 DEG C for 60 seconds, rinsed with pure water for 30 seconds, and dried to form a line pattern.

[Sensitivity, resolution (γ)]

Sensitivity and resolution (gamma value) were obtained in the same manner as described for Example A, except that the apparatus and process conditions were applied.

[Pattern shape, line edge roughness (LER)]

An exposure amount for reproducing a mask pattern of a line-and-space (L / S = 1/1) with a line width of 180 nm was taken as an optimum exposure amount, and a profile at an optimum exposure amount was observed by a scanning type microscope (SEM). In addition, the distance from the reference line where an edge was present was measured by using a scanning electron microscope (Hitachi SEISAKUSHO S-9220) relative to arbitrary 30 points included in the length direction 50 mu m of the formed pattern. Then, the standard deviation of this distance was calculated to calculate 3σ.

〔flaw〕

Using the mask pattern having a mask size of 180 nm and a pitch of 360 nm, the pattern was exposed at 78 positions within the wafer plane at an exposure amount at which a resist pattern with a line width of 180 nm was obtained. The wafer on which the obtained pattern was formed was measured for the number of development defects by using KLA-2360 manufactured by KL Tencor Co., At this time, the inspection area was 205 cm 2 in total, the pixel size was 0.25 μm, and the threshold was 30. Visible light was used as inspection light. The value obtained by dividing the obtained numerical value by the inspection area was evaluated as the number of defects (pieces / cm 2).

[Stability over time]

The stability with time was evaluated in the same manner as described for Example A.

The evaluation results are shown in Table 16 below.

[Table 16-1]

[Table 16-2]

[Table 16-3]

[Table 16-4]

[Table 16-5]

From the results shown in Table 16, it can be seen that the composition according to the third embodiment is excellent in sensitivity, resolution, LER, pattern shape, defect characteristics and aged stability in KrF exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition for KrF excimer laser exposure.

<Example D>

(Examples 1D to 30D and Comparative Examples 1D to 4D)

(Resist preparation)

The components shown in the following Table 17 were dissolved in a solvent and then filtered with a polytetrafluoroethylene filter having a pore size of 0.1 탆 to prepare a positive type resist solution having a solid content concentration of 4.0% by mass.

(Resist evaluation)

The positive resist solution thus prepared was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 120 캜 for 60 seconds to form a resist film having a film thickness of 0.12 탆 .

The resist film was irradiated with an electron beam projection lithography apparatus (accelerating voltage: 100 keV) manufactured by Nikon Corporation, and immediately after irradiated, it was heated on a hot plate at 110 캜 for 90 seconds. Thereafter, the resist film was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 DEG C for 60 seconds, rinsed with pure water for 30 seconds, and dried to form a line and space pattern.

〔Sensitivity〕

The obtained pattern was observed using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.). The amount of electron beam irradiation at the time of resolving a line-and-space (L / S = 1/1) having a line width of 0.10 m was defined as sensitivity (E ₀ ).

〔definition〕

The resolution (the minimum line width at which lines and spaces are separated and resolved) of the 1: 1 line space in the exposure amount representing the sensitivity (E ₀ ) is defined as resolution (dense).

[Line edge roughness (LER)]

LER was obtained in the same manner as described for Example A.

[Out gas performance: Film thickness variation rate by exposure]

The film thickness before the post-exposure was measured after irradiating with the electron beam at an irradiation amount 2.0 times the irradiation amount giving the sensitivity (the sensitivity determined in the surface exposure), and the film thickness was measured from the film thickness at the time of unexposed The variation rate was obtained.

Film thickness variation rate (%) = [(film thickness at unexposed light - film thickness after exposure) / film thickness at unexposed state] × 100

[Stability over time]

After each composition was stored at room temperature for 1 month, the degree of fluctuation of the sensitivity before and after storage was evaluated by visual confirmation. This evaluation was made on the basis of the following criteria.

(Criteria)

Good (Good): When the variation in sensitivity was less than 1 占 폚 / ㎠

(Fair): When the fluctuation of the sensitivity was 1 占 폚 / cm2 or more and 3 占 폚 / cm2 or less

× (Insufficient): When the sensitivity variation is larger than 3 μC / cm 2.

The evaluation results are shown in Table 17 below.

[Table 17-1]

[Table 17-2]

[Table 17-3]

From the results shown in Table 17, it can be seen that the composition according to the third embodiment is excellent in sensitivity, resolution, LER, outgas performance, and aged stability in electron beam exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition for electron beam irradiation.

<Example E>

(Examples 1E to 25E and Comparative Examples 1E to 4E)

(Resist preparation)

The components shown in Table 18 below were dissolved in a solvent, and this was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 탆 to prepare a positive resist solution having a solid content concentration of 4.0% by mass.

(Resist evaluation)

The positive resist solution thus prepared was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater and heated and dried on a hot plate at 120 캜 for 60 seconds to form a resist film having a film thickness of 0.12 탆 .

〔Sensitivity〕

The resist film thus obtained was subjected to surface exposure while changing the exposure dose in the range of 0 to 15.0 mJ / cm 2 by 0.5 mJ / cm 2 using EUV light (wavelength 13 nm), and baked at 110 ° C for 90 seconds. Thereafter, the dissolution rate at each exposure dose was measured using an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution to obtain a dissolution rate curve.

[Line edge roughness (LER)]

An exposure amount for reproducing a mask pattern of a line-and-space (L / S = 1/1) having a line width of 50 nm was taken as an optimum exposure amount, and a profile at an optimum exposure amount was observed by a scanning type microscope (SEM). Further, the distance from the reference line where an edge was present was measured by using a scanning electron microscope (Hitachi SEISAKUSHO S-9220) relative to arbitrary 30 points included in the 50 mu m length direction of this pattern. Then, the standard deviation of this distance was calculated to calculate 3σ.

[Out gas performance: Film thickness variation rate by exposure]

The film thickness variation ratio by EUV exposure was obtained in the same manner as described for Example D.

[Stability over time]

The stability with time was evaluated in the same manner as described for Example A.

The evaluation results are shown in Table 18 below.

[Table 18-1]

[Table 18-2]

[Table 18-3]

From the results shown in Table 18, it can be seen that the composition according to the third embodiment is excellent in sensitivity, LER, outgas performance, and long-term stability in EUV exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition for EUV irradiation.

Claims (17)

A sulfonic acid generating compound which decomposes by the action of an acid to generate a sulfonic acid having a volume of 240 Å ³ or more; And
An active radiation or radiation-sensitive resin composition containing a compound capable of generating an acid upon irradiation with an actinic ray or radiation,
The acid generating compound is represented by the following general formula (1) to (5) of and the compound represented by any one of the sulfonic acid is a sense of an actinic ray or last radiation-sensitive resin, characterized in that expressed with the formula A-SO ₃ H Composition.

[Wherein,
Each of R ₁ to R ₄ , R ₇ to R ₁₃ and R ₁₅ to R ₁₉ represents a hydrogen atom or a monovalent substituent.
Each of R ₅ , R ₆ and R ₁₄ represents a monovalent substituent. R ₅ and R ₆ may be bonded to each other to form a cyclic acetal structure.
A represents a substituted or unsubstituted alkyl, cycloalkyl or aromatic group, and the substituent is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acyl group, an alkylsulfanyl group, an arylsulfanyl group, , An aryl group, a hydroxy group, a carboxy group, a formyl group, a cyano group, an alkylaminocarbonyl group, an arylaminocarbonyl group, a sulfonamido group, a silyl group, an amino group, a thioxy group or a combination thereof. delete The method according to claim 1,
Wherein the sulfonic acid-generating compound is a compound represented by the general formula (1). The method according to claim 1,
Wherein the resin further contains a resin which is decomposed by the action of an acid to increase its solubility in an alkali developing solution. The method according to claim 1,
A resin soluble in an alkali developing solution; And
Wherein the resin further contains an acid crosslinking agent that crosslinks with the resin by the action of an acid. The method according to claim 1,
Wherein the composition is exposed to electron beams, X-rays or EUV light. A resin containing a repeating unit decomposing by the action of an acid to generate a sulfonic acid and a repeating unit represented by the following formula (VI), wherein the repeating unit generating the sulfonic acid is a resin having an acetal structure; And
And a compound which generates an acid upon irradiation with an actinic ray or radiation.

[Wherein,
R ₀₁ , R ₀₂ and R ₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₀₃ represents an alkylene group and may be bonded to Lp or Ar ₁ to form a ring.
Ar ₁ represents aromatic ring.
n represents an integer of 1 or more.
Lp represents a single bond or a divalent linking group.] 8. The method of claim 7,
Wherein at least a part of the repeating unit for generating the sulfonic acid has a structure represented by the following general formula (I).

[Wherein,
Each of R ₁ to R ₄ represents a hydrogen atom or a substituent. Two or more of R ₁ to R ₄ may be bonded to each other to form a ring structure.
Each of R ₅ and R ₆ represents a substituent. R ₅ and R ₆ may be bonded to each other to form a cyclic acetal structure.] 9. The method of claim 8,
Wherein at least a part of the repeating unit for generating the sulfonic acid is represented by the following general formula (II).

[Wherein,
Ra and Rb each independently represent a hydrogen atom, an alkyl group or a cyano group.
Rc represents a hydrogen atom or a substituent.
L represents a single bond or a linking group. When Rc is the above substituent and L is the above linking group, Rc and L may be bonded to each other to form a ring structure.
Each of R ₁ to R ₄ represents a hydrogen atom or a substituent. Two or more of R ₁ to R ₄ may be bonded to each other to form a ring structure.
Each of R ₅ and R ₆ represents a substituent. R ₅ and R ₆ may be bonded to each other to form a cyclic acetal structure.] delete 8. The method of claim 7,
Wherein the composition is exposed to electron beams, X-rays or EUV light. A resin containing a repeating unit represented by the following general formula (II); And
And a compound which generates an acid upon irradiation with an actinic ray or radiation.

[Wherein,
Each of R ₁ to R ₅ represents a hydrogen atom or a substituent. Two or more of R ₁ to R ₅ may be bonded to each other to form a ring.
In the above general formula (II), the following partial structures including Ra, Rb, Rc and L

Has a structure represented by the following general formula (III-1), (III-2), or (III-3).

Wherein,
Ar _1a represents an arylene group.
R ₀₁ represents a hydrogen atom, an alkyl group or a cyano group.
R ₀₂ represents a single bond or a divalent linking group.
R ₀₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. delete 13. The method of claim 12,
Wherein the resin further contains a repeating unit represented by the following general formula (VI).

[Wherein,
R ₀₁ , R ₀₂ and R ₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₀₃ represents an alkylene group and may be bonded to Lp or Ar ₁ to form a ring.
Ar ₁ represents aromatic ring.
n represents an integer of 1 or more.
Lp represents a single bond or a divalent linking group.] 13. The method of claim 12,
Wherein the composition is exposed to electron beams, X-rays or EUV light. Characterized in that it is formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1, 3 to 9, 11, 12, 14 and 15 . Forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1, 3 to 9, 11, 12, 14 and 15 ;
Exposing the film; And
And developing the exposed film.