JP2016212241A - Resist composition, sulfonic acid derivative, production method of the sulfonic acid derivative, and method for manufacturing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition comprising a photoacid generator including a sulfonic acid derivative, and a compound that reacts by an acid, which has excellent resolution in lithography and can reduce line width roughness (LWR) in a fine pattern.SOLUTION: The resist composition comprises: a photoacid generator including a sulfonic acid derivative represented by general formula (1) below; and a compound that reacts by an acid. In formula (1), Rrepresents a monovalent organic group having 1 to 30 carbon atoms; Rrepresents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms; X represents a direct bond or a divalent connecting group; and Mrepresents a counter cation.SELECTED DRAWING: None

Description

Some embodiments of the present invention relate to sulfonic acid derivatives useful as photoacid generators for chemically amplified photoresist compositions. In addition, some aspects of the present invention can be easily performed by irradiation with active energy rays such as deep UV, KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, electron beam, X-ray or EUV (extreme ultraviolet). The present invention relates to a resist composition containing a photoacid generator that decomposes into an acid to generate an acid.

  In a highly integrated circuit element typified by a semiconductor device such as a DRAM, there is a high demand for higher density, higher integration, or higher speed. Accordingly, in various electronic device manufacturing fields, there is an increasing demand for the establishment of microfabrication technology on the order of half a micron, for example, the development of photolithography technology for forming fine patterns. In order to form a fine pattern in the photolithography technique, it is necessary to improve the resolution. Here, the resolution (R) of the reduction projection exposure apparatus is expressed by the Rayleigh equation R = k · λ / NA (where λ is the wavelength of exposure light, NA is the numerical aperture of the lens, and k is a process factor). Therefore, the resolution can be improved by shortening the wavelength λ of the active energy ray (exposure light) used in forming the resist pattern.

  As a photoresist suitable for a short wavelength, a chemically amplified type has been proposed. A characteristic of chemically amplified photoresists is that proton acid is generated from the photoacid generator that is a component when exposed to exposure light, and this proton acid undergoes an acid-catalyzed reaction with the resist compound and the like by heat treatment after exposure. is there. Most of the photoresists currently being developed are chemically amplified.

  As the acid generated from the photoacid generator upon exposure, alkanesulfonic acid, partially or completely fluorinated alkanesulfonic acid, and the like are used.

  Photoacid generators that generate alkanesulfonic acid generally have a weak acid strength. Therefore, for example, a compound used for a positive chemically amplified resist in the case of using an alkaline developer as a developer has been studied for miniaturization by introducing a protective group that is easily deprotected. In order to use a protective group that is easy to deprotect, a sulfonic acid having a large molecule such as camphorsulfonic acid and a small acid diffusion length has been used as an effective sulfonic acid. However, the use of a sulfonic acid having a small acid diffusion length requires a large amount of generated acid, resulting in a problem that the exposure amount increases and the productivity decreases.

  Photoacid generators that generate fully fluorinated alkanesulfonic acids have sufficient acid strength for deprotection reactions of protecting groups that are difficult to deprotect, and many of them have been put to practical use. However, when the acid strength is too strong, an unexpected reaction occurs in the elimination reaction of the protecting group that converts the dissolution contrast of the compound, and there is a problem that foreign matter is generated after development or at the time of peeling of the resist. In addition, there are problems such as bioconcentration derived from hydrophobicity and lipophilicity.

  In order to solve the above-mentioned problems, a patent has been solved that uses a known sulfonic acid having a medium acid strength in which the alkyl group of the alkanesulfonic acid is partially replaced by a fluorine atom, a nitro group or the like as an electron-withdrawing group It is reported in Document 1 and Patent Document 2. Patent Document 3 reports a compound that generates a sulfonic acid in which an alkyl group and a perfluoroalkyl group are introduced into the α carbon atom of methanesulfonic acid.

Japanese Patent Laid-Open No. 10-7650 JP 2008-7410 A JP 2003-327572 A

  The photoacid generator preferably has a high acid strength to some extent, but on the other hand, it is preferable that the acid diffusion length is small for fine patterning. In general, when the acid strength is high, the acid diffusion length tends to be large and the two are in a trade-off relationship, but it is required to satisfy both the strong acid strength and the moderately small acid diffusion length. The photoacid generators described in Patent Documents 1 to 3 have a problem in terms of an appropriate acid diffusion length.

  In view of such circumstances, some aspects of the present invention provide a fine resolution in lithography when the acid generated has sufficient acid strength and the acid diffusion length is moderately small and is used as a photoacid generator. A resist composition containing a photoacid generator containing a sulfonic acid derivative capable of reducing LWR (Line width roughness) in a fine pattern and an acid and a compound that reacts with an acid, the sulfonic acid derivative, and a method for producing the same The issue is to provide. It is another object of the present invention to provide a device manufacturing method using the resist composition.

  Prior to the present invention, the inventors of the present invention have no acid and the acid generated has sufficient acid strength, and is a sulfonic acid suitable as a photoacid generator and a photogenerated acid used in a resist composition material. A derivative has been proposed (International Publication WO2011 / 093139). The present invention is an improvement of the invention described in International Publication No. WO2011 / 093139, and is a sulfonic acid derivative that has excellent resolution in lithography and can further reduce LWR (Line width roughness) in a fine pattern. It is an object of the present invention to provide a resist composition containing a photoacid generator containing a compound that reacts with an acid.

  One embodiment of the present invention that solves the above problems is a resist composition containing a photoacid generator containing a sulfonic acid derivative represented by the following general formula (1) and a compound that reacts with an acid.

(In the above formula (1), R ¹ represents a monovalent organic group having 1 to 30 carbon atoms, R ² represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X represents a direct bond or (Denotes a divalent linking group, and M ⁺ represents a counter cation.)

  Another embodiment of the present invention is the above sulfonic acid derivative.

  In another embodiment of the present invention, a hydroxy group-containing sulfonic acid compound represented by the following general formula (2) is reacted with chlorosulfonyl isocyanate to produce N-chloro represented by the following general formula (3). Obtaining a sulfonylcarbamoyl group-containing sulfonic acid compound derivative;

(In the above formula (2), ^{M +} is the same counter cation and ^{M +} in the formula (1).)

(In the above formula (3), ^{R 2} is a monovalent organic group hydrogen atom or a C1-30, ^{M +} is the same counter cation and ^{M +} in the formula (1).)

An N-chlorosulfonylcarbamoyl group-containing sulfonic acid compound derivative represented by the general formula (3), and R ¹ Z (wherein, in the formula, when X in the formula (1) is a direct bond, R ¹ represents the formula ( 1) a carbanion having the same R ¹ and R ¹ represented by and Z is a metal cation; when X in the above formula (1) is a divalent linking group, R ¹ is the formula ( 1) and the same as R ¹ represented by 1) and Z is XH.) By reacting with a compound represented by formula (1) to obtain a sulfonic acid derivative represented by the above general formula (1); It is a manufacturing method of the said sulfonic acid derivative which has this.

  Another embodiment of the present invention includes a resist film forming step of forming a resist film on a substrate using the resist composition, and a photolithography step of exposing the resist film in a pattern using active energy rays. And a pattern forming step of developing the exposed resist film to obtain a photoresist pattern.

  A resist composition containing a photoacid generator containing a sulfonic acid derivative according to one embodiment of the present invention and a compound that reacts with an acid generates an acid having sufficient acid strength upon irradiation with active energy rays, and The acid diffusion length has an appropriately small effect. In addition, the resist composition according to one aspect of the present invention is excellent in resolution in lithography, and has an effect of reducing LWR (Line width roughness) in a fine pattern.

Hereinafter, the present invention will be described in detail.
<1> Sulfonic acid derivative The sulfonic acid derivative of one embodiment of the present invention is represented by the general formula (1). In addition, a sulfonic acid derivative means a sulfonic acid and its salt. The sulfonic acid derivative represented by the general formula (1) of the present invention may be optically active or inactive.

The sulfonic acid derivative of one embodiment of the present invention has a specific structure in which all of the α-position and the β-position are partially fluorine-substituted, as shown by the general formula (1), and a sulfonyl group ( A compound having —SO ₂ —) and a carbamate group (—N (R ² ) —COO—). With the above configuration, when used as a photoacid generator of a resist composition, it generates an acid having sufficient acid strength upon irradiation with active energy rays, has an appropriate acid diffusion length, and has high resolution in lithography. It is excellent and LWR (Line width roughness) in a fine pattern can be reduced. In particular, by having a sulfonyl group (—SO ₂ —) and a carbamate group (—N (R ² ) —COO—), the sulfonic acid derivative has a photoacid generator, for example, an acrylate structure or a hydroxyl group. When used together with the base polymer, the acid diffusion length is reduced by an interaction such as hydrogen bonding between the base polymer and the sulfonic acid derivative.

R ^{1 in the} general formula (1) represents a monovalent organic group having 1 to 30 carbon atoms. The organic group for R ¹ may have a substituent.
R ¹ represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms; an aromatic hydrocarbon group having 1 to 30 carbon atoms; and —O—, —CO—, and —COO. -, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH-, -NH-, -S-, -SO- and A monovalent group selected from: an aliphatic heterocyclic group having 1 to 30 carbon atoms or an aromatic heterocyclic group containing at least one group selected from the group consisting of —SO ₂ — in its skeleton; Is preferred.

In the case where R ¹ has a substituent, including the number of carbon atoms of the substituent is preferably 1 to 30 carbon atoms, more preferably 6 to 30 carbon atoms, 10 carbon atoms More preferably, it is -28.

Examples of the substituent include a hydroxy group, a carboxy group, a carbonyl group, an alkoxy group (—OR ³ ), an acyl group (—COR ³ ), an alkoxycarbonyl group (—COOR ³ ), an aryl group (—Ar ¹ ), and an aryloxy group. (—OAr ¹ ), amino group, alkylamino group (—NHR ³ ), dialkylamino group (—N (R ³ ) ₂ ), arylamino group (—NHAr ¹ ), diarylamino group (—N (Ar ¹ )) ₂ ), N-alkyl-N-arylamino group (—NR ³ Ar ¹ ) phosphino group, silyl group, halogen atom, trialkylsilyl group (—Si— (R ³ ) ₃ ), alkyl of the trialkylsilyl group at least one silyl group substituted with Ar ¹ group, an alkylthio group ^(-SR 3), an arylthio group (-SAr ¹⁾ and thienyl While such may be mentioned, without being restricted thereto.

R ³ is preferably an alkyl group having 1 or more carbon atoms. Specific examples of the alkyl group having 1 or more carbon atoms include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group and n-decyl group. Linear alkyl groups such as isopropyl groups, isobutyl groups, tert-butyl groups, isopentyl groups, tert-pentyl groups, 2-ethylexyl groups, etc .; one of these hydrogens is a trimethylsilyl group, triethylsilyl group And a silyl group-substituted alkyl group substituted with a trialkylsilyl group such as a dimethylethylsilyl group; an alkyl group in which at least one of these hydrogen atoms is substituted with a cyano group or a halogen group;

Ar ¹ in the above substituent is preferably an aryl group. Specific examples of the aryl group of Ar ¹ include a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a naphthyl group, an anthryl group, a phenanthrenyl group, a pentarenyl group, an indenyl group, an indacenyl group, an acenaphthyl group, and a fluorenyl group , Heptalenyl group, naphthacenyl group, pyrenyl group, chrysenyl group, tetracenyl group, furanyl group, thienyl group, pyranyl group, thiopyranyl group, pyrrolyl group, imidazolyl group, oxazolyl group, thiazolyl group, pyrazoyl group, pyridyl group, pyridyl group, isobenzofuran Nyl group, benzofuranyl group, isochromenyl group, chromenyl group, indolyl group, isoindolyl group, benzoimidazolyl group, xanthenyl group, aquadinyl group, carbazoyl group and the like are preferable.

Specific examples of the unsubstituted linear or branched monovalent aliphatic hydrocarbon group represented by R ^{1 in} the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group, n-octyl group, i-octyl group, 2-ethylhexyl group, n-dodecyl group, etc. An alkyl group of
An alkenyl group or an alkynyl group in which at least one of the carbon-carbon single bonds of the alkyl group is substituted with a carbon-carbon double bond or a carbon-carbon triple bond;

Examples of the unsubstituted cyclic monovalent aliphatic hydrocarbon group represented by R ^{1 in} the general formula (1) include a monocyclic aliphatic hydrocarbon group, a spirocyclic aliphatic hydrocarbon group, and a bridged cyclic aliphatic hydrocarbon group. , Condensed polycyclic aliphatic hydrocarbon groups, and linked polycyclic aliphatic hydrocarbon groups in which at least two of these groups are directly bonded by a single bond or a linking group containing a double bond, and the like It is done.
Examples of the monocyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the spirocycloaliphatic hydrocarbon group include spiro [3,4] octane and spirobicyclopentane.
Examples of the bridged cycloaliphatic hydrocarbon group include those having a skeleton in which two or more monocyclic hydrocarbons such as norbornane, tricyclodecane, tetracyclododecane and adamantane are bridged.

  Examples of the condensed polycyclic aliphatic hydrocarbon group include decalin and groups having a steroid skeleton shown below.

  Examples of the linked polycyclic aliphatic hydrocarbon group include groups having a bicyclohexane skeleton.

  The monovalent cyclic aliphatic hydrocarbon group may be a group in which at least one carbon-carbon single bond is substituted with a carbon-carbon double bond or a carbon-carbon triple bond.

Examples of the linear, branched or cyclic monovalent aliphatic hydrocarbon group having the substituent of R ^{1 in} the general formula (1) include the above-described unsubstituted monovalent aliphatic hydrocarbon groups. Specifically, for example, benzyl group, methoxymethyl group, methylthiomethyl group, ethoxymethyl group, phenoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, acetylmethyl group, fluoromethyl Group, trifluoromethyl group, chloromethyl group, trichloromethyl group, 2-fluoropropyl group, trifluoroacetylmethyl group, trichloroacetylmethyl group, pentafluorobenzoylmethyl group, aminomethyl group, cyclohexylaminomethyl group, diphenylphosphino Methyl group, trimethylsilylmethyl group, 2-phenylethyl group, 3- Examples thereof include a phenylpropyl group and a 2-aminoethyl group.

Examples of the monovalent aromatic hydrocarbon group represented by R ^{1 in} the general formula (1) include a monocyclic aromatic hydrocarbon group, and a condensed polycyclic aromatic hydrocarbon group in which the monocyclic aromatic hydrocarbon is condensed with at least two rings. And a linked polycyclic aromatic hydrocarbon group in which at least two of the monocyclic aromatic hydrocarbons are directly bonded by a single bond or a linking group containing a double bond. These aromatic hydrocarbon groups may have the above substituents.
Examples of the monocyclic aromatic hydrocarbon group include groups having a skeleton such as cyclopentene and benzene.
Examples of the condensed polycyclic aromatic hydrocarbon group include groups having a skeleton such as indene, naphthalene, azulene, anthracene, phenanthrene, naphthacene, and fluorene.
Examples of the linked polycyclic aromatic hydrocarbon group include groups having a skeleton such as biphenyl, terphenyl and stilbene.

Examples of the monovalent aliphatic heterocyclic group represented by R ^{1 in} the general formula (1) include —O—, —CO—, —COO—, —OCO—, —O—CO—O—, —NHCO—, — CONH—, —NH—CO—O—, —O—CO—NH—, —NH—, —S—, —SO—, —SO ₂ — and the like as a skeleton Examples thereof include groups having a skeleton such as pyrrolidine, piperidine, piperazine, morpholine, and quinuclidine. In addition, other examples include those in which at least one of the carbon atoms in the cyclic aliphatic hydrocarbon group is substituted with a hetero atom. These aliphatic heterocyclic groups may have the above substituents.
In the monovalent aliphatic heterocyclic group, at least one of a carbon-carbon single bond or a single bond of carbon and an atom other than carbon (heteroatom) is substituted with a double bond or a triple bond. It may be a group.

The monovalent aromatic heterocyclic group represented by R ^{1 in} the general formula (1) includes a monocyclic aromatic heterocyclic group; at least one of the monocyclic aromatic heterocyclic rings is the above aromatic hydrocarbon group or aliphatic heterocyclic group. A condensed polycyclic aromatic heterocyclic group condensed with a ring group or the like; and at least one of the monocyclic aromatic heterocyclic ring and the aromatic hydrocarbon group or the aliphatic heterocyclic group or the like directly in a single bond or double Examples thereof include a linked polycyclic aromatic heterocyclic group bonded by a linking group containing a bond. These aromatic heterocyclic groups may have the above substituents.

Examples of the monocyclic aromatic heterocyclic group include groups having a skeleton such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, and pyrazine.
Examples of the condensed polycyclic aromatic heterocyclic group include groups having a skeleton such as indole, purine, quinoline, isoquinoline, chromene, thianthrene, dibenzothiophene, phenothiazine, phenoxazine, xanthene, acridine, phenazine and carbazole.
Examples of the linked polycyclic aromatic heterocyclic group include 4-phenylpyridine, 9-phenylacridine, butophenanthroline and the like.

X in the general formula (1) is a direct bond or a divalent linking group. Examples of the divalent linking group for X include —O—, —CO—, —COO—, —OCO—, —O—CO—O—, —NHCO—, —CONH—, and —NH—CO—O—. And any group selected from the group consisting of —O—CO—NH—, —NH—, —S—, —CO—O—CH ₂ —CO—O— and the like. X in the general formula (1) is preferably —O—, —NH—, —S— or the like.

R ¹ is preferably a monovalent cyclic aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a polycyclic group thereof from the viewpoint of reducing the acid diffusion length. More preferably, a spirocyclic aliphatic hydrocarbon group, a condensed polycyclic aliphatic hydrocarbon group, a linked polycyclic aliphatic hydrocarbon group, a condensed polycyclic aromatic hydrocarbon group, a linked polycyclic aromatic hydrocarbon group, and the like. .

Specific examples of R ^{1 in} the above formula (1) include the structures shown below. In the following structural formulas, "*" is _{^{"-SO 2 -N (R 2) -COO}} -CH 2 CH 2 CFHCF 2 SO 3 - M + " in the above formula (1) shows a. That is, the following structural formula shows the structure of R ¹ —X—.
In the following structure, the steric position is not limited to the following.

Among the specific examples of R ^{1 in} the above formula (1), those having an adamantane skeleton and those having the steroid skeleton are preferable from the viewpoint of reducing the acid diffusion length.

Examples of R ² in the above formula (1) include a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Examples of the monovalent organic group having 1 to 30 carbon atoms of R ² include a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms.
The aliphatic hydrocarbon group for R ² is —O—, —CO—, —COO—, —OCO—, —O—CO—O—, —NHCO—, —CONH—, —NH—CO—O—, The aliphatic hydrocarbon group has at least one group selected from the group consisting of —O—CO—NH—, —NH—, —S—, —CO—O—CH ₂ —CO—O— and the like. May be. Further, a part of hydrogen of the aliphatic hydrocarbon group for R ² may be substituted with halogen such as fluorine atom or chlorine atom. The aliphatic hydrocarbon group for R ² may have a substituent, and examples of the substituent include the same as the substituent for R ¹ described above.

Specific examples of R ^{2 in} the above formula (1) include the structures shown below. In the following formula, “**” is a site bonded to N of the carbamate group.

  Specific examples of the cation M + that forms a salt with sulfonic acid include a hydrogen ion, a metal ion, an onium ion, and the like.

  Specific examples of the metal ion of the cation M + include a monovalent cation by a first group element such as lithium ion, sodium ion, and potassium ion, and a second group element such as magnesium ion (II) and calcium ion (II). Transition metal ions such as divalent cations, iron ions (II), iron ions (III), copper ions (I), copper ions (II), nickel ions (II), nickel ions (III), lead ions ( II) and the like, and these metal ions may form a complex with the ligand.

Examples of the onium ion of the cation M ⁺ include an onium salt cation composed of a nitrogen atom, a sulfur atom, a halogen atom, a phosphorus atom, or the like. Specifically, for example, ammonium ion, methyl ammonium ion, dimethyl ammonium ion, trimethyl ammonium ion, tetramethyl ammonium ion, phenyl ammonium ion, diphenyl ammonium ion, triphenyl ammonium ion, dimethyl phenyl ammonium ion, trimethyl phenyl ammonium ion, Pyridinium ion, alkylpyridinium ion, fluoropyridinium ion, chloropyridinium ion, bromopyridinium ion, tetramethylammonium ion, imidazolium ion, onium salt cation composed of nitrogen atoms, trimethylsulfonium ion, Tributylsulfonium ion, dimethyl (2-oxocyclohexyl) Rufonium ion, bis (2-oxocyclohexyl) methylsulfonium ion, (10-campenoyl) methyl (2-oxocyclohexyl) sulfonium ion, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium ion, triphenylsulfonium ion, Diphenyltolylsulfonium ion, diphenylxylylsulfonium ion, mesityldiphenylsulfonium ion, (t-butylphenyl) diphenylsulfonium ion, (octylphenyl) diphenylsulfonium ion, (cyclohexylphenyl) diphenylsulfonium ion, biphenyldiphenylsulfonium ion, (hydroxyl Methylphenyl) diphenylsulfonium ion, (methoxymethylphenyl) diphenyl Rufonium ion, (acetylphenyl) diphenylsulfonium ion, (benzoylphenyl) diphenylsulfonium ion, (hydroxycarbonylphenyl) diphenylsulfonium ion, (methoxycarbonylphenyl) diphenylsulfonium ion, (trifluoromethylphenyl) diphenylsulfonium ion, (fluoro (Phenyl) diphenylsulfonium ion, (chlorophenyl) diphenylsulfonium ion, (bromophenyl) diphenylsulfonium ion, (iodophenyl) diphenylsulfonium ion, pentafluorophenyldiphenylsulfonium ion, (hydroxyphenyl) diphenylsulfonium ion, (methoxyphenyl) diphenylsulfonium ion Ion, (butoxypheny ) Diphenylsulfonium ion, (acetyloxyphenyl) diphenylsulfonium ion, (benzoyloxyphenyl) diphenylsulfonium ion, (dimethylcarbamoylphenyl) diphenylsulfonium ion, (acetylamidophenyl) diphenylsulfonium ion, phenylditolylsulfonium ion, phenyldioxy Silylsulfonium ion, dimesitylphenylsulfonium ion, bis (t-butylphenyl) phenylsulfonium ion, bis (octylphenyl) phenylsulfonium ion, bis (cyclohexylphenyl) phenylsulfonium ion, dibiphenylphenylsulfonium ion, bis (hydroxymethyl) Phenyl) phenylsulfonium ion, bis (methoxymethylphenol) L) phenylsulfonium ion, bis (acetylphenyl) phenylsulfonium ion, bis (benzoylphenyl) phenylsulfonium ion, bis (hydroxycarbonylphenyl) phenylsulfonium ion, bis (methoxycarbonylphenyl) phenylsulfonium ion, bis (trifluoromethylphenyl) ) Phenylsulfonium ion, bis (fluorophenyl) phenylsulfonium ion, bis (chlorophenyl) phenylsulfonium ion, bis (bromophenyl) phenylsulfonium ion, bis (iodophenyl) phenylsulfonium ion, dipentafluorophenylphenylsulfonium ion, bis ( Hydroxyphenyl) phenylsulfonium ion, bis (methoxyphenyl) pheny Sulfonium ion, bis (butoxyphenyl) phenylsulfonium ion, bis (acetyloxyphenyl) phenylsulfonium ion, bis (benzoyloxyphenyl) phenylsulfonium ion, bis (dimethylcarbamoylphenyl) phenylsulfonium ion, bis (acetylamidophenyl) phenylsulfonium Ion, tristolylsulfonium ion, trischisilylsulfonium ion, trismesitylphenylsulfonium ion, tris (t-butylphenyl) sulfonium ion, tris (octylphenyl) sulfonium ion, tris (cyclohexylphenyl) sulfonium ion, tribiphenylsulfonium ion , Tris (hydroxymethylphenyl) sulfonium ion, tris (meth) Xymethylphenyl) sulfonium ion, tris (acetylphenyl) sulfonium ion, tris (benzoylphenyl) sulfonium ion, tris (hydroxycarbonylphenyl) sulfonium ion, tris (methoxycarbonylphenyl) sulfonium ion, tris (trifluoromethylphenyl) sulfonium ion , Tris (fluorophenyl) sulfonium ion, tris (chlorophenyl) sulfonium ion, tris (bromophenyl) sulfonium ion, tris (iodophenyl) sulfonium ion, dipentafluorophenylsulfonium ion, tris (hydroxyphenyl) sulfonium ion, tris (methoxy) Phenyl) sulfonium ion, tris (butoxyphenyl) sulfonium ion, Lis (acetyloxyphenyl) sulfonium ion, tris (benzoyloxyphenyl) sulfonium ion, tris (dimethylcarbamoylphenyl) sulfonium ion, tris (acetylamidophenyl) sulfonium ion, methyldiphenylsulfonium ion, ethyldiphenylsulfonium ion, butyldiphenylsulfonium ion , Hexyldiphenylsulfonium ion, octyldiphenylsulfonium ion, cyclohexyldiphenylsulfonium ion, 2-oxocyclohexyldiphenylsulfonium ion, norbornyldiphenylsulfonium ion, campenoyldiphenylsulfonium ion, pinanoyldiphenylsulfonium ion, naphthyldiphenylsulfonium ion, anne Lanyldiphenylsulfonium ion, benzyldiphenylsulfonium ion, trifluoromethyldiphenylsulfonium ion, methoxycarbonylmethyldiphenylsulfonium ion, butoxycarbonylmethyldiphenylsulfonium ion, benzoylmethyldiphenylsulfonium ion, (methylthiophenyl) diphenylsulfonium ion, (phenylthiophenyl) ) Diphenylsulfonium ion, (acetylphenylthiophenyl) diphenylsulfonium ion, dimethylphenylsulfonium ion, diethylphenylsulfonium ion, dibutylphenylsulfonium ion, dihexylphenylsulfonium ion, dioctylphenylsulfonium ion, dicyclohexylphenylsulfonium ion ON, bis (2-oxocyclohexyl) phenylsulfonium ion, dinorbornylphenylsulfonium ion, dicamphenoylphenylsulfonium ion, dipinanoylphenylsulfonium ion, dinaphthylphenylsulfonium ion, dibenzylphenylsulfonium ion, trifluoromethyl Diphenylsulfonium ion, bis (methoxycarbonylmethyl) phenylsulfonium ion, bis (butoxycarbonylmethyl) phenylsulfonium ion, dibenzoylmethylphenylsulfonium ion, bis (methylthiophenyl) phenylsulfonium ion, bis (phenylthiophenyl) phenylsulfonium ion, Bis (acetylphenylthiophenyl) phenylsulfonium ion, dimethyl ( -Oxocyclohexyl) sulfonium ion, bis (2-oxocyclohexyl) methylsulfonium ion, (10-campenoyl) methyl (2-oxocyclohexyl) sulfonium ion, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium ion, trimethylsulfonium Ion, triethylsulfonium ion, tributylsulfonium ion, dihexylmethylsulfonium ion, trioctylsulfonium ion, dicyclohexylethylsulfonium ion, methyltetrahydrothiophenium ion, methyltetrahydrothiophenium ion, triphenyloxosulfonium ion, bis [4- (diphenylsulfone) Nio) phenyl] composed of sulfur atoms such as sulfide-bision Cation of the onium salts, there are cations, etc. constituted onium salt by phosphorus atoms, such as tetraphenylphosphonium ion. Examples of the halonium salt include diphenyliodonium ion, bis- (t-butylphenyl) iodonium cation, (methoxyphenyl) phenyliodonium ion, (butoxyphenyl) phenyliodonium ion, trifluoroethylphenyliodonium ion, pentafluorophenylphenyliodonium ion, and the like. Of these, sulfonium ions and iodonium ions are preferable.

Since the sulfonic acid derivative represented by the general formula (1) has a specific structure in which all of the α-position and the β-position are partially fluorine-substituted, KrF excimer laser light, ArF excimer laser light, F ₂ excimer It is useful as a photoacid generator that efficiently decomposes upon irradiation with active energy rays such as laser light, electron beams, X-rays and EUV to generate an acid having sufficient acid strength. The sulfonic acid derivative represented by the general formula (1) has an effect of reducing the acid diffusion length by having a sulfonyl group and a carbamate group in the anion portion. Therefore, when used as a photoacid generator of a resist composition, it has excellent resolution in lithography and an effect of reducing LWR (Line width roughness) in a fine pattern.

  In addition, when used as a photoacid generator for resist compositions, side reactions are unlikely to occur, and since the anion portion has a highly polar sulfonyl group and carbamate group, it has a high affinity for an alkaline developer, so after development or There is an effect that foreign matter is hardly generated when the resist is peeled off.

  Here, since the sulfonic acid derivative of Patent Document 2 is a compound having all four of the α-position and β-position substituted with fluorine and having four fluorines, the acid strength is too strong or the acid diffusion length tends to be large. . In Patent Document 3, there is no idea about the sulfonic acid derivative represented by the above general formula (1) of the present invention in which all of the α-position and the β-position are partially fluorine-substituted. Furthermore, based on the production method described in Patent Document 2, the sulfonic acid derivative of one embodiment of the present invention cannot be produced even if, for example, the raw material is changed. Further, a sulfonic acid derivative having two fluorine atoms at the α position or the like does not have sufficient acid strength.

Furthermore, in general, a sulfonic acid derivative having three fluorine atoms has a problem that the diffusion length is not appropriate, but the sulfonic acid derivative having a specific structure represented by the general formula (1) of the present invention By doing so, it has sufficient acid strength and can have an appropriate acid diffusion length.
In the present invention, the present invention is not limited to aqueous development using an alkali developer, but can also be applied to aqueous development using a neutral developer or organic solvent development using an organic solvent developer.

<2> Resist Composition One aspect of the present invention is a resist composition containing a photoacid generator containing the sulfonic acid derivative and a compound that reacts with an acid.
One embodiment of the photoacid generator in the present invention has a property of releasing an acid upon irradiation with the active energy ray, and can act on an acid-reactive organic substance to cause decomposition or polymerization. Therefore, the sulfonic acid derivative of one embodiment of the present invention can be preferably used as a photoacid generator for positive and negative resist compositions.

  Examples of the compound that reacts with an acid include a compound having a protecting group that is deprotected by an acid, a compound having a polymerizable group that is polymerized by an acid, and a crosslinking agent having a crosslinking action by an acid.

The compound having a protecting group that is deprotected by an acid is a compound whose solubility in a developer is changed by deprotecting the protecting group by an acid. For example, in the case of aqueous development using an alkaline developer or the like, it is insoluble in an alkaline developer, but the protective group is deprotected in the exposed area by an acid generated from the photoacid generator upon exposure, whereby an alkaline developer. It is a compound that becomes soluble in.
In the present invention, the developer is not limited to an alkaline developer, and may be a neutral developer or an organic solvent development. Therefore, when an organic solvent developer is used, the compound having a protecting group that is deprotected by an acid is deprotected in the exposed area by the acid generated from the photoacid generator upon exposure, and the organic solvent developer Is a compound whose solubility is reduced.

  Specific examples of the protecting group to be deprotected with an acid include an ester group, an acetal group, a tetrahydropyranyl group, a siloxy group, and a benzyloxy group. As the compound having the protecting group, a compound having a styrene skeleton, a methacrylate or an acrylate skeleton pendant with these protecting groups is preferably used.

The compound having a polymerizable group that is polymerized with an acid is a compound whose solubility in a developer is changed by polymerization of the polymerizable group with an acid. For example, in the case of aqueous development, it is soluble in an aqueous developer, but the polymerizable group is polymerized in the exposed area by the acid generated from the photoacid generator upon exposure, and is soluble in the aqueous developer. It is a compound that decreases. Also in this case, an organic solvent developer may be used instead of the aqueous developer.
Examples of the polymerizable group that is polymerized with an acid include an epoxy group, an acetal group, and an oxetanyl group. As the compound having a polymerizable group, a compound having a styrene skeleton, a methacrylate or an acrylate skeleton having these polymerizable groups is preferably used.

  A crosslinking agent having a crosslinking action with an acid is a compound that changes the solubility in a developer by crosslinking with an acid. For example, in the case of aqueous development, it acts on a compound that is soluble in an aqueous developer, and reduces the solubility of the compound in an aqueous developer after crosslinking. Specific examples include a crosslinking agent having an epoxy group, an acetal group, an oxetanyl group, and the like. At this time, examples of the cross-linking partner compound include compounds having a phenolic hydroxyl group.

Specific examples of the resist composition according to one embodiment of the present invention include the following.
A resist composition comprising a compound having a protecting group to be deprotected by the acid and the photoacid generator; a resist composition comprising a compound having a polymerizable group to be polymerized by the acid and the photoacid generator; And a resist composition comprising a crosslinking agent having a crosslinking action, a compound that reacts with the crosslinking agent to change the solubility in a developer, and a photoacid generator.

The content of the photoacid generator in the resist composition of one embodiment of the present invention is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resist composition component excluding the photoacid generator. More preferably, it is 30 mass parts, and it is still more preferable that it is 1-15 mass parts. By containing the photoacid generator in the resist composition within the above range, for example, even when used as a permanent film such as an insulating film such as a display body, the light transmittance can be increased.
In addition to the above-mentioned components, the resist composition according to one embodiment of the present invention includes, as necessary, optional components, organic solvents, quenchers, acidic compounds, dissolution inhibitors, stabilizers and dyes used in ordinary resist compositions, and May contain other photoacid generators in combination.
In the calculation of the content of the photoacid generator, the organic solvent is not included in 100 parts by mass of the resist composition component.

<3> Method for producing sulfonic acid derivative The sulfonic acid derivative represented by the above general formula (1) is a hydroxy group-containing sulfonic acid compound represented by the following general formula (2) (hereinafter referred to as “compound (2)”). And chlorosulfonyl isocyanate to react with each other to obtain an N-chlorosulfonylcarbamoyl group-containing sulfonic acid compound derivative (hereinafter also referred to as “compound (3)”) represented by the following general formula (3): ,

(In the above formula (2), ^{M +} is the same counter cation and ^{M +} in the formula (1).)

(In the above formula (3), ^{R 2} is a monovalent organic group hydrogen atom or a C1-30, ^{M +} is the same counter cation and ^{M +} in the formula (1).)
An N-chlorosulfonylcarbamoyl group-containing sulfonic acid compound derivative represented by the above general formula (3), and R ¹ Z (in the formula, when X in the above formula (1) is a direct bond, R ¹ represents the above formula (1) a carbanion having the same R ¹ and R ¹ represented by and Z is a metal cation; when X in the above formula (1) is a divalent linking group, R ¹ is the formula A compound represented by the same formula (1) as R ¹ and Z is XH) to obtain a sulfonic acid derivative represented by the above general formula (1); Can be manufactured by a manufacturing method including:
Hereinafter, the compound represented by R ¹ Z is also referred to as “compound (4)”.

Moreover, in the method for producing a sulfonic acid derivative according to one aspect of the present invention, the step of obtaining the sulfonic acid derivative represented by the general formula (1) is such that R ² in the general formula (3) is a hydrogen atom. After reacting the N-chlorosulfonylcarbamoyl group-containing sulfonic acid compound derivative and the compound (4) to obtain a sulfonic acid derivative in which R ² in the formula (1) is a hydrogen atom,
The formula sulfonic acid derivative and ^R in 2 Y (wherein ^{R 2} is a hydrogen atom in (1), ^{R 2} represents a monovalent organic group having 1 to 30 carbon atoms, Y represents a leaving group. ) And a sulfonic acid in which R ² in the general formula (1) is a monovalent organic group having 1 to 30 carbon atoms. This is a method for producing a sulfonic acid derivative, which is a step of obtaining a derivative.
Incidentally, ^{R 2} in the above ^{R 2} Y is a monovalent organic group having 1 to 30 carbon atoms, a monovalent organic group having 1 to 30 carbon atoms as ^{R 2} represented in the general formula (1) The same thing is mentioned.

  More specifically, the sulfonic acid derivative represented by the general formula (1) can be synthesized, for example, by the following reaction pathway. First, 4-bromo-1,1,2-trifluoro-1-butene is used as a starting material, acetylation with sodium acetate, subsequent hydrolysis with a base, etc., and further sulfonation with bisulfite, Obtained as the acid salt. And this salt is salt-exchanged based on M + mentioned above and a conventional method, The hydroxy group containing sulfonic acid compound represented by the said General formula (2) is obtained.

Thereafter, the hydroxy group-containing sulfonic acid compound (compound (2)) and chlorosulfonyl isocyanate are reacted in a solvent such as acetonitrile at 0 to 30 ° C. for about 15 minutes to 24 hours, and the following general formula (3a) The represented N-chlorosulfonylcarbamoyl group-containing sulfonic acid compound is obtained. The N-chlorosulfonylcarbamoyl group-containing sulfonic acid compound represented by the following general formula (3a) is an N-chlorosulfonylcarbamoyl group-containing sulfonic acid compound derivative represented by the general formula (3) in which R ² is hydrogen. It corresponds to. Next, the N-chlorosulfonylcarbamoyl group-containing sulfonic acid compound represented by the following general formula (3a) is reacted with the above compound (4) to obtain a sulfonic acid derivative represented by the following general formula (1a). obtain. The sulfonic acid derivative represented by the following general formula (1a) corresponds to the sulfonic acid derivative represented by the above general formula (1) in which R ² is hydrogen.
The hydroxy group-containing sulfonic acid compound is preferably reacted with about 1 to 2 equivalents of chlorosulfonyl isocyanate.

R ^{1 Z} as the compound (4), when X is a direct bond in the formula (1), an organic metal compound having the R ¹ identical R ¹ and represented by the above formula (1); the when X in formula (1) is a divalent linking group, an ^R 1 -XH having respectively ^{R 1} and X the same ^{R 1} and X represented by the above formula (1).
When the compound (4) is an organometallic compound, ^{R 1} in ^{R 1} Z is a monovalent carbanion ^{(R 1-),} as the ^{Z Li +, MgBr +, MgCl} +, CuLi +, ZnCl ^And monovalent metal cations (Z ⁺ ) such as ⁺ , ZnBr ⁺ , K ⁺ and Na ⁺ .
When the compound (4) is R ¹ -XH, R ¹ Z is a nucleophilic terminal-containing compound having “—XH” which is a nucleophilic terminal.

In order to obtain a sulfonic acid derivative represented by the following general formula (1b) in which R ^{2 of the} sulfonic acid derivative represented by the general formula (1) is a monovalent organic group having 1 to 30 carbon atoms, A sulfonic acid derivative represented by (1a) and R ² Y (wherein R ² is a monovalent organic group having 1 to 30 carbon atoms, and Y represents a leaving group). A reaction with the group-containing compound may be performed.

Y in R ² Y is a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; a trifluoromethanesulfonyloxy group (CF ₃ SO ₃ —), a methanesulfonyloxy group (CH ₃ SO ₃ —), p-toluene. And a leaving group such as a sulfonic acid ester group such as a sulfonyloxy group (p-CH ₃ C ₆ H ₄ SO ₃ —). The compound represented by the general formula (1a) is preferably reacted at 0 to 40 ° C. for 2 to 48 hours in a solvent such as THF using 1 to 2 equivalents of R ² Y.

As the compound (4) having the R ¹ group and the leaving group-containing compound having the R ² group and the Y leaving group, which are used as raw materials for the synthesis of the sulfonic acid derivative, those available are used, or A corresponding raw material may be prepared and appropriately synthesized by a normal method.

It is also within the scope of the present invention to partially improve the method for producing the sulfonic acid derivative represented by the general formula (1) to obtain the sulfonic acid derivative represented by the following general formula (5). In the following general formula (5), R ¹ , R ² and M ⁺ are the same as R ¹ , R ² and M ⁺ represented by the above formula (1), respectively.

  Specifically, it is as shown in the reaction formula below. That is, instead of the step of obtaining the compound (3) by reacting the compound (2) with chlorosulfonyl isocyanate, the compound (4) and chlorosulfonyl isocyanate are reacted to form the following general formula (6). After obtaining the compound represented, the compound represented by the following general formula (6) and the compound (2) are reacted to obtain a sulfonic acid derivative represented by the following general formula (5).

More details are as follows. 7.1 g of chlorosulfonyl isocyanate is dissolved in 22 g of tetrahydrofuran and cooled to 5 ° C. Next, 6.8 g of 2-adamantanol is added and stirred for 2 hours. Next, 84 g of acetonitrile solution of 28.2 g of triphenylsulfonium-1,1,2-trifluoro-4-hydroxybutanesulfonate was dropped over 15 minutes, and then 6.2 g of triethylamine was added and the temperature was raised to 40 ° C. for 2 hours. Stir. The reaction mixture is ice-cooled and 5% by mass aqueous potassium carbonate solution is added to stop the reaction. The aqueous layer is washed 5 times with 47 g of hexane and then neutralized with dilute aqueous hydrochloric acid. After adding 235 g of methylene chloride to the aqueous layer and stirring for 30 minutes, it is washed 5 times with 80 g of pure water. The obtained organic layer was concentrated under reduced pressure to obtain triphenylsulfonium 4- [N- (adamantyloxycarbonyl) aminosulfonyloxy) -1,1,2-trifluorobutanesulfonate (7.2 g, yield 30%). ) Can be obtained. The measurement result of 1H NMR of this substance is shown below.
¹ H-NMR (400 MHz, DMSO-D ₆ )) δ 12.05 (bs, 1H), 8.04-7.35 (m, 15H), 5.12-4.88 (m, 1H), 4 .73 (t, 1H), 3.96-3.51 (m, 2H), 2.44-2.27 (m, 1H), 2.12-1.44 (m, 15H)

<4> Device Manufacturing Method In one aspect of the present invention, the resist film is formed using a resist film forming step of forming the resist film by, for example, applying the resist composition on a substrate, and active energy rays. It is a device manufacturing method including a photolithography step of exposing in a pattern and a pattern forming step of developing the exposed resist film to obtain a photoresist pattern.

The active energy ray used for exposure in the photolithography process may be any light that can activate the sulfonic acid derivative of the present invention to generate an acid, such as KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, Meaning electron beam, UV, visible light, X-ray, electron beam, ion beam, i-ray, EUV and the like.
Except using the resist composition containing the said photo-acid generator, what is necessary is just to follow the manufacturing method of a normal device.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.

[Synthesis of sulfonic acid derivative 1]
(Example 1-1)
Synthesis of sodium 1,1,2-trifluoro-4-hydroxybutanesulfonate

<First step>
4-Bromo-1,1,2-trifluoro-1-butene (36.9 g) and sodium acetate (65.4 g) are dissolved in acetic acid (156.5 g), and the temperature is raised to 115 ° C. The mixture is stirred for 40 hours, the reaction solution is cooled to 90 ° C., and 626 g of distilled water is added. Then, it cools to room temperature and extracts twice using 128 g of t-butyl methyl ether. Next, the remaining acid is removed by washing with 165 g of an aqueous sodium carbonate solution. Thereafter, the solvent is distilled off with a rotary evaporator to obtain 4-acetoxy-1,1,2-trifluoro-1-butene. It is 25.6 g in the crude state. The 1H NMR measurement result of this substance is shown below.
1H NMR (400 MHz, CDCl ₃ ) δ 2.07 (s, 3H), 2.63 (d, t, d, d, 2H), 4.24 (t, 2H)

<Second step>
4-Acetoxy-1,1,2-trifluoro-1-butene (25.0 g) and potassium carbonate (40.3 g) are dissolved in methanol (49 g) and distilled water (49 g). And after stirring at room temperature for 15 hours and removing the solid content which precipitated by reaction by filtration, the target object is extracted with a dichloromethane. Thereafter, 13.8 g of 3,4,4-trifluoro-3-buten-1-ol is obtained by distillation purification. The 1H NMR measurement result of this substance is shown below.
1H NMR (400 MHz, CDCl ₃ ) δ2.2 (s, 1H), 2.55 (d, t, d, d, 2H), 3.83 (t, 2H)

<Third step>
11.9 g of 3,4,4-trifluoro-3-buten-1-ol, 29.5 g of sodium hydrogen sulfite and 14.3 g of sodium sulfite are dissolved in 214 g of distilled water, and then the temperature is raised to 90 ° C. And it stirs for 15 hours and cools a reaction liquid to 25 degrees C or less. Next, the aqueous layer is washed with 24 g of toluene. Then, the solvent is distilled off with a rotary evaporator to obtain 18.46 g of sodium 1,1,2-trifluoro-4-hydroxybutanesulfonate. From the measurement results by 1H NMR and ion chromatography, it is confirmed that this compound is the target product. 1H NMR measurement results are shown below.
1H NMR (400 MHz, CDCl ₃ ) δ1.9-2.4 (m, 2H), 3.5-3.7 (m, 2H), 4.9-5.2 (m, 1H)

(Example 1-2)
Synthesis of triphenylsulfonium 4- [N- (2-adamantyloxysulfonyl)] carbonyloxy-1,1,2-trifluorobutanesulfonate

<First step>
17.6 g of sodium 1,1,2-trifluoro-4-hydroxybutanesulfonate and 34.4 g of triphenylsulfonium methanesulfonate are added to 106 g of water and 360 g of dichloromethane, and the mixture is stirred for 3 hours. After liquid separation, the organic layer is distilled off with a rotary evaporator to obtain 32.4 g of triphenylsulfonium 1,1,2-trifluoro-4-hydroxybutanesulfonate. The 1H NMR measurement result of this substance is shown below.
_{1H NMR (400MHz, CDCl 3)} δ1.9-2.4 (m, 2H), 3.5-3.7 (m, 2H), 4.9-5.2 (m, 1H), 7.66 -7.80 (m, 15H)

<Second step>
4.0 g of chlorosulfonyl isocyanate is dissolved in 34.9 g of acetonitrile and cooled to 5 ° C. Next, 49.1 g of an acetonitrile solution containing 14.2 g of triphenylsulfonium 1,1,2-trifluoro-4-hydroxybutanesulfonate is added dropwise over 30 minutes and stirred at 5 ° C. After 1 hour of stirring, this solution is dropped into 11.7 g of an acetonitrile suspension containing 3.9 g of 2-adamantanol, and 3.5 g of triethylamine is added and stirred at 20 ° C. for 18 hours. After diluting the reaction mixture with 100 g of methylene chloride, the organic layer is separated and washed 5 times with 50 g of pure water. The obtained organic layer was concentrated under reduced pressure to obtain triphenylsulfonium 4- [N- (2-adamantyloxysulfonyl)] carbonyloxy-1,1,2-trifluorobutanesulfonate (sulfonic acid derivative 1) 12. 0 g is obtained (77% yield). The 1H NMR measurement result of this substance is shown below.
1H NMR (400 MHz, DMSO-D ₆ ) δ 12.13 (s, 1H), 8.04-7.40 (m, 15H), 5.16-4.82 (m, 1H), 4.73 (t , 1H), 4.41-4.06 (m, 2H), 2.45-2.29 (m, 1H), 2.14-1.27 (m, 15H)

(Example 1-3)
[Preparation and characterization of photoresist composition]

(A = 0.4, b = 0.4, c = 0.2, Mw = 9300)

  5 parts by mass of the sulfonic acid derivative 1 synthesized above and a polymer having a structural unit represented by the above formula (7) (wherein a = 0.4, b = 0.4, c = 0.2) 100 Part by mass and 0.2 part by mass of triethanolamine are dissolved in 1150 parts by mass of propylene glycol monomethyl ether acetate and filtered through a PTFE filter to prepare a photoresist composition solution. Next, after a photoresist composition solution is spin-coated on a silicon wafer, it is pre-baked on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 300 nm. This film is exposed by an ArF excimer laser stepper (wavelength 193 nm), and then post-baked at 110 ° C. for 90 seconds. Thereafter, development is carried out in an aqueous solution of 2.38% tetramethylammonium hydroxide for 60 seconds, followed by rinsing with pure water for 30 seconds.

  The resolution and LWR (Line width roughness) are evaluated as follows. Using the resist composition prepared in Comparative Example 3 below, resolution and LWR are measured. Each of these values is set to 1, and the resolution and LWR of the sulfonic acid derivative 1 are calculated as relative ratios. The results are shown in Table 1.

[Synthesis of sulfonic acid derivative 2]
6.1 g of the sulfonic acid derivative 1 obtained in Example 1 is dissolved in 30 g of dehydrated THF under a nitrogen stream and cooled to 0 ° C. A solution of LDA (lithium diisopropylamide) in THF (concentration: about 1.5 mol / L: 8 g) is added dropwise over 15 minutes and stirred at 0 ° C.
After 15 minutes, 8 g of a dehydrated THF solution containing 2.1 g of methyl iodide is added dropwise. The reaction solution is warmed to 22 ° C. and stirred at room temperature for 24 hours. The reaction mixture is diluted with 80 g of methylene chloride, and 50 g of 1% dilute hydrochloric acid aqueous solution is added and stirred. The organic layer is separated and washed once with 50 g of pure water, twice with 50 g of a 10% aqueous sodium carbonate solution and seven times with 50 g of pure water. 4. The organic layer is concentrated under reduced pressure to give triphenylsulfonium 4- [N- (2-adamantyloxysulfonyl) -N-methyl] carbonyloxy-1,1,2-trifluorobutanesulfonate represented by the following formula. 0 g (yield 79%) is obtained.

The 1H NMR measurement result of this substance is shown below.
1H NMR (400 MHz, DMSO-D ₆ ) δ 8.08-7.38 (m, 15H), 5.19-4.84 (m, 1H), 4.74 (t, 1H), 4.45-4 0.09 (m, 2H), 2.74 (s, 3H), 2.47-2.25 (m, 1H), 2.16-1.25 (m, 15H)

[Preparation and characterization of photoresist composition]
Instead of using 5 parts by mass of the sulfonic acid derivative 1, using 5.1 parts by mass of the sulfonic acid derivative 2 obtained above, a resist composition was prepared in the same manner as in Example 1 to obtain a resist film. Exposure, post-bake, and development. In the same manner as in Example 1, the resolution and LWR of the resist composition are evaluated. The results are shown in Table 1.

[Synthesis of sulfonic acid derivative 3]
4.8 g of chlorosulfonyl isocyanate is dissolved in 22 g of acetonitrile and cooled to 5 ° C. Next, 55 g of an acetonitrile solution containing 17.0 g of triphenylsulfonium 1,1,2-trifluoro-4-hydroxybutanesulfonate obtained in <First Step> of (Example 1-2) of Example 1 Is added dropwise over 30 minutes and stirred at 5 ° C. After 1 hour of stirring, this solution is dropped into 9 g of an acetonitrile solution containing 3.1 g of cyclohexanol, 4.2 g of triethylamine is added, and the mixture is stirred at 20 ° C. for 18 hours. After diluting the reaction mixture with 120 g of methylene chloride, the organic layer is separated and washed 5 times with 55 g of pure water. By concentrating the obtained organic layer under reduced pressure, triphenylsulfonium 4- [N- (cyclohexyloxysulfonyl)] carbonyloxy-1,1,2-trifluorobutanesulfonate represented by the following formula (sulfonic acid derivative 3) ) 12.6 g is obtained (55% yield). The 1H NMR measurement result of this substance is shown below.
1H NMR (400 MHz, DMSO-D ₆ ) δ 12.11 (s, 1H), 8.04-7.42 (m, 15H), 5.14-4.82 (m, 1H), 4.72 (t , 1H), 4.29-4.06 (m, 2H), 2.45-2.29 (m, 1H), 1.08-1.85 (m, 11H)

[Preparation and characterization of photoresist composition]
Instead of using 5 parts by mass of the sulfonic acid derivative 1, using 4.6 parts by mass of the sulfonic acid derivative 3 obtained above, a resist composition was prepared in the same manner as in Example 1 to obtain a resist film. Exposure, post-bake, and development. In the same manner as in Example 1, the resolution and LWR of the resist composition are evaluated. The results are shown in Table 1.

Comparative Example 1

  Instead of using 5 parts by mass of the sulfonic acid derivative 1, a resist composition was prepared in the same manner as in Example 1 by using 4.6 parts by mass of the sulfonic acid derivative represented by the following general formula (8). A film is obtained and exposed, post-baked and developed. In the same manner as in Example 1, the resolution and LWR of the resist composition are evaluated. The results are shown in Table 1.

The sulfonic acid derivative represented by the general formula (8) is synthesized as follows.
<First step>
56.6 g of 1-bromo-3,4,4-trifluoro-3-butene and 63.0 g of sodium sulfite are dissolved in 360 g of pure water, and then heated to 90 ° C. and stirred for 18 hours. Next, 55.5 g of sodium bisulfite is added and stirred for 21 hours, and then the reaction solution is cooled to 25 ° C. or lower. Next, the aqueous layer is washed with 45 g of toluene. Thereafter, the solvent is distilled off by a rotary evaporator to obtain 175 g of a crude 1,1,2-trifluorobutane-1,4-disulfonic acid sodium salt. This compound is used in the next step without further purification.

<Second step>
Under a nitrogen stream, 172 g of crude 1,1,2-trifluorobutane-1,4-disulfonate is added to 345 g of thionyl chloride. After 30 minutes, 8 g of N, N-dimethylformamide is slowly added dropwise and stirred at room temperature for 6 hours. Next, after the solvent is distilled off from the reaction mixture with a rotary evaporator, 345 g of tetrahydrofuran is added, and then cooled to 10 ° C. or lower. After adding 35.5 g of 2-adamantanol and 26.1 g of triethylamine, the mixture is warmed to room temperature and stirred for 24 hours. After adding 305 g of pure water to the reaction mixture, washing is performed using 100 g of toluene. Thereafter, the solvent is distilled off by a rotary evaporator to obtain 147 g of a crude product of sodium 4- (adamantyloxysulfonyl) -1,1,2-trifluorobutanesulfonate. This compound is used in the next step without further purification.

<Third step>
A crude product 136 g of sodium 4- (adamantyloxy) sulfonyl-1,1,2-trifluorobutanesulfonate is suspended in 136 g of pure water. Next, 80.5 g of triphenylsulfonium chloride and 272 g of methylene chloride are added and stirred for 1 hour. After separating the organic layer, it is washed 5 times with 135 g of pure water. Thereafter, 19.6 g of triphenylsulfonium 4- (adamantyloxysulfonyl) -1,1,2-trifluorobutanesulfonate (total yield from the first step to the third step) was obtained by distilling off the solvent using a rotary evaporator. 9.7%). The 1H NMR measurement result of this substance is shown below.
1H NMR (400 MHz, DMSO-D ₆ ) δ 8.06-7.41 (m, 15H), 5.14-4.82 (m, 1H), 4.70 (t, 1H), 3.49-3 .27 (m, 2H), 2.47-2.28 (m, 1H), 2.14-1.27 (m, 15H)

Comparative Example 2

  A resist composition was prepared in the same manner as in Example 1 using 4.1 parts by mass of the sulfonic acid derivative represented by the following general formula (9) instead of using 5 parts by mass of the sulfonic acid derivative 1. A film is obtained and exposed, post-baked and developed. In the same manner as in Example 1, the resolution and LWR of the resist composition are evaluated. The results are shown in Table 1.

The sulfonic acid derivative represented by the general formula (9) is synthesized as follows.
3.2 g of cyclohexyl isocyanate is dissolved in 10 g of methylene chloride and cooled to 5 ° C. Next, 46 g of a methylene chloride solution containing 12.0 g of triphenylsulfonium-1,1,2-trifluoro-4-hydroxybutanesulfonate is dropped over 20 minutes and stirred at 5 ° C. for 1 hour. After adding 18 g of pure water to the reaction mixture and stirring, the organic layer is separated. The obtained organic layer is washed 5 times with 18 g of pure water. Then, 12.0 g of 4- (N-cyclohexylcarbonyloxy) -1,1,2-trifluorobutanesulfonate is obtained with a yield of 79% by distilling off the solvent with a rotary evaporator. The 1H NMR measurement result of this substance is shown below.
1H NMR (400 MHz, DMSO-D ₆ ) δ 5.07 (bs, 1H), 8.02-7.41 (m, 15H), 5.14-4.82 (m, 1H), 4.12-4 .03 (m, 2H), 3.56 (m, 1H), 2.45-2.29 (m, 1H), 1.08-1.85 (m, 11H)

Comparative Example 3

  A resist composition was prepared in the same manner as in Example 1 using 4.3 parts by mass of the sulfonic acid derivative represented by the following general formula (10) instead of using 5 parts by mass of the sulfonic acid derivative 1. A film is obtained and exposed, post-baked and developed. In the same manner as in Example 1, the resolution and LWR of the resist composition are evaluated. The results are shown in Table 1. Further, the resolution and LWR of the resist composition are set to 1 because the comparative example 3 is used as a reference.

The sulfonic acid derivative represented by the general formula (10) is synthesized as follows.
5.0 g of adamantane carboxylic acid chloride is dissolved in 20 g of methylene chloride and cooled to 10 ° C. 36 g of acetonitrile solution containing 10.7 g of triphenylsulfonium-1,1,2-trifluoro-4-hydroxybutanesulfonate and 3.1 g of triethylamine is added dropwise over 15 minutes. The reaction mixture is warmed to 23 ° C. and stirred for 6 hours. The reaction is stopped by adding 30 g of pure water, and diluted with 45 g of methylene chloride. After separating the organic layer, it is washed 5 times with 30 g of pure water. The obtained organic layer is concentrated under reduced pressure to obtain 10.6 g of triphenylsulfonium 4-adamantanecarbonyloxy) -1,1,2-trifluorobutanesulfonate, yield 74%). The 1H NMR measurement result of this substance is shown below.
1H NMR (400 MHz, DMSO-D ₆ ) δ 8.13-7.54 (m, 15H), 5.16-4.85 (m, 1H), 4.43-4.02 (m, 2H), 2 .45-2.29 (m, 1H), 2.14-1.57 (m, 15H)

The resolution and LWR in Table 1 indicate that the smaller the value, the better the effect.
From the above results, it can be seen that the sulfonic acid derivative according to the present invention is excellent in resolution in lithography and has an effect of reducing LWR in a fine pattern. From this, it is estimated that the sulfonic acid derivative in the present invention has a small acid diffusion length. This effect, -OSO ₂ to spacer groups anion -, - NH- and -CO ₂ - believed to be due to having a high polar linking group having a. In addition, the sulfonic acid derivative in which R ² in Formula (1) is hydrogen has protons with an appropriate acidity, and thus is considered to have high resolution and LWR reduction effect.

  Since the sulfonic acid derivative which is one embodiment of the present invention generates an acid having sufficient acid strength upon irradiation with active energy rays, it is useful as a photoacid generator for a resist composition. In addition, when the photoacid generator is used in a resist composition, it has excellent resolution in lithography and has an effect of reducing LWR (Line width roughness) in a fine pattern.

Claims (9)

The resist composition containing the photo-acid generator containing the sulfonic acid derivative represented by following General formula (1), and the compound which reacts with an acid.

(In the formula (1), R ¹ represents a monovalent organic group having 1 to 30 carbon atoms, R ² represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X represents a direct bond or (Denotes a divalent linking group, and M ⁺ represents a counter cation.) The organic group represented by R ¹ is a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms; an aromatic hydrocarbon group having 1 to 30 carbon atoms; and —O— and —CO—. , —COO—, —OCO—, —O—CO—O—, —NHCO—, —CONH—, —NH—CO—O—, —O—CO—NH—, —NH—, —S—, — At least one group of the aliphatic heterocyclic group or an aromatic heterocyclic group having 1 to 30 carbon atoms containing a skeleton selected from the group consisting of - SO- and -SO _2; any monovalent group selected from The resist composition according to claim 1.   The resist composition according to claim 1, wherein M + is a hydrogen ion, a metal ion, or an onium ion. A sulfonic acid derivative represented by the following general formula (1).

(In the formula (1), R ¹ represents a monovalent organic group having 1 to 30 carbon atoms, R ² represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X represents a direct bond or (Denotes a divalent linking group, and M ⁺ represents a counter cation.) The organic group represented by R ¹ is a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms; an aromatic hydrocarbon group having 1 to 30 carbon atoms; and —O— and —CO—. , —COO—, —OCO—, —O—CO—O—, —NHCO—, —CONH—, —NH—CO—O—, —O—CO—NH—, —NH—, —S—, — At least one group of the aliphatic heterocyclic group or an aromatic heterocyclic group having 1 to 30 carbon atoms containing a skeleton selected from the group consisting of - SO- and -SO _2; any monovalent group selected from The sulfonic acid derivative according to claim 4, wherein   The sulfonic acid derivative according to claim 4 or 5, wherein the M + is a hydrogen ion, a metal ion, or an onium ion. A hydroxy group-containing sulfonic acid compound represented by the following general formula (2) is reacted with a chlorosulfonyl isocyanate to obtain an N-chlorosulfonylcarbamoyl group-containing sulfonic acid compound derivative represented by the following general formula (3). Process,

(In the formula (2), M ⁺ is the same counter cation as M ⁺ in the formula (1).)

(In the formula (3), R ² is a hydrogen atom, and M ⁺ is the same counter cation as M ⁺ in the formula (1).)
An N-chlorosulfonylcarbamoyl group-containing sulfonic acid compound derivative represented by the general formula (3), and R ¹ Z (in the formula, when X in the formula (1) is a direct bond, R ¹ represents the formula (1) a carbanion having the same R ¹ and R ¹ represented by and Z is a metal cation; when X is a divalent linking group in the formula (1), R ¹ is the formula A compound represented by (1) and R ¹ represented by the same formula (1) and Z is XH) to obtain a sulfonic acid derivative represented by the general formula (1); The manufacturing method of the sulfonic acid derivative as described in any one of Claims 4-6 containing these. The step of obtaining the sulfonic acid derivative represented by the general formula (1) includes a chlorosulfonylcarbamoyl group-containing sulfonic acid compound derivative in which R ² in the general formula (3) is a hydrogen atom, and the R ¹ Z To obtain a sulfonic acid derivative in which R ² in the formula (1) is a hydrogen atom,
Formula ^{R 2} is a sulfonic acid derivative and ^R 2 Y (wherein a hydrogen atom in (1), ^{R 2} represents a monovalent organic group having 1 to 30 carbon atoms, Y represents a leaving group. The compound represented by formula (1) is a step of obtaining a sulfonic acid derivative in which R ² in the general formula (1) is a monovalent organic group having 1 to 30 carbon atoms. A method for producing an acid derivative. A resist film forming step of forming a resist film on the substrate using the resist composition according to claim 1;
A photolithographic step of exposing the resist film in a pattern using an active energy ray;
A pattern forming step of developing the exposed resist film to obtain a photoresist pattern.