JP4320579B2 - Acid generator, sulfonic acid, sulfonic acid derivative, halogen-containing bicyclooctane compound and radiation-sensitive resin composition - Google Patents

Description

The present invention relates to an acid generator, a sulfonic acid and its derivative, a halogen-containing norbornane-based compound, and a radiation-sensitive resin composition, and more particularly, particularly a KrF excimer laser, ArF excimer laser, F ₂ excimer laser, or EUV ( Positive type radiation sensitive resin used as a chemically amplified resist useful for fine processing using various kinds of radiation such as deep ultraviolet rays (such as extreme ultraviolet rays), X-rays such as synchrotron radiation, and charged particle beams such as electron beams Acid generator suitable as a radiation-sensitive acid generator for the composition, sulfonic acid generated from the acid generator, sulfonic acid derivatives useful as raw materials or intermediates for synthesizing the compounds forming the acid generator, and precursors thereof And a radiation-sensitive resin composition containing the acid generator.

In the field of microfabrication represented by the manufacture of integrated circuit elements, a lithography process capable of microfabrication at a level of 0.20 μm or less is recently required to obtain a higher degree of integration.
However, in the conventional lithography process, near ultraviolet rays such as i rays are generally used as radiation, and it is said that fine processing at the subquarter micron level is extremely difficult with this near ultraviolet rays.
Therefore, in order to enable microfabrication at a level of 0.20 μm or less, use of radiation having a shorter wavelength is being studied. Examples of such short-wavelength radiation include an emission line spectrum of a mercury lamp, deep ultraviolet rays typified by an excimer laser, X-rays, and electron beams. Among these, a KrF excimer laser (wavelength 248 nm) is particularly preferable. ), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), EUV (wavelength 13 nm, etc.), electron beam, and the like are attracting attention.

As a radiation-sensitive resin composition suitable for short-wave radiation, a component having an acid-dissociable functional group and a radiation-sensitive acid generator that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”) Many compositions utilizing the chemical amplification effect between them (hereinafter referred to as “chemically amplified radiation-sensitive composition”) have been proposed.
As a chemically amplified radiation sensitive composition, for example, Patent Document 1 contains a polymer having a t-butyl ester group of carboxylic acid or a t-butyl carbonate group of phenol and a radiation-sensitive acid generator. Compositions have been proposed. In this composition, the t-butyl ester group or t-butyl carbonate group present in the polymer is dissociated by the action of an acid generated by exposure, and the polymer is an acidic compound comprising a carboxyl group or a phenolic hydroxyl group. A group is formed, and as a result, a phenomenon that the exposed region of the resist film becomes readily soluble in an alkali developer is utilized.
By the way, properties required for a radiation-sensitive acid generator in a chemically amplified radiation-sensitive composition are excellent in transparency to radiation, have a high quantum yield in acid generation, and have a sufficiently strong acid to be generated. For example, the boiling point of the acid is sufficiently high, and the diffusion distance of the generated acid in the resist film (hereinafter referred to as “diffusion length”) is appropriate.

Among these, regarding the strength, boiling point, and diffusion length of the acid, the structure of the anion moiety is important in the ionic radiation-sensitive acid generator, and the nonionic property having a normal sulfonyl structure or sulfonate structure is used. In the radiation-sensitive acid generator, the structure of the sulfonyl moiety is important. For example, in the case of a radiation sensitive acid generator having a trifluoromethanesulfonyl structure, the acid generated is sufficiently strong and the resolution performance as a photoresist is sufficiently high, but the acid boiling point is low, and the acid diffusion length is also low. However, there is a drawback that the mask dependency as a photoresist is increased. Further, in the case of a radiation sensitive acid generator having a sulfonyl structure bonded to a large organic group such as 10-camphorsulfonyl structure, the boiling point of the generated acid is sufficiently high and the diffusion length of the acid is sufficiently short. Although the dependence becomes small, the strength of acid is not sufficient, so that the resolution performance as a photoresist is not sufficient.
On the other hand, a radiation-sensitive acid generator having a perfluoroalkylsulfonyl structure such as perfluoro-n-octanesulfonic acid (PFOS) has sufficient acidity, and the boiling point and diffusion length of the acid are generally appropriate. In recent years, it has attracted particular attention.

However, radiation sensitive acid generators having a perfluoroalkylsulfonyl structure, such as PFOS, are generally low in flammability and suspected to accumulate in the human body when considering environmental problems. The US Environmental Protection Agency (ENVIRONMENTAL In a report by PROTECTION AGENCY (see Non-Patent Document 1), a proposal for restricting use has been made.
In addition, when the device design dimension is sub-half micron or smaller and the line width control needs to be performed more precisely, using a chemically amplified resist with inferior film surface smoothness results in etching or other treatment on the substrate. When the resist pattern is transferred, an uneven shape (hereinafter referred to as “nano edge roughness”) on the film surface is transferred to the substrate. As a result, the dimensional accuracy of the pattern is lowered, and there is a possibility that the electrical characteristics of the device are eventually impaired (see, for example, Non-Patent Document 2, Non-Patent Document 3, Non-Patent Document 4, and Non-Patent Document 5). Therefore, when the design dimension is sub-half micron or less, it is important that the chemically amplified resist has not only excellent resolution performance but also excellent film surface smoothness after resist pattern formation. It has become.

Therefore, in the field of microfabrication, there is no drawback as in the case of the perfluoroalkylsulfonyl structure, and it is possible to realize a better chemically amplified resist with excellent resolution performance and small nanoedge roughness. There is an urgent need to develop an alternative component that is also excellent in function as a radiation-sensitive acid generator.
JP-B-2-27660 Perfluorooctyl Sulfonates; Proposed Significant New Use Rule J. Photopolym. Sci. Tech., P.571 (1998) Proc.SPIE, Vol.3333, p.313 Proc.SPIE, Vol.3333, p.634 J. Vac. Sci. Technol. B16 (1), p.69 (1998)

The subject of the present invention is excellent in transparency to actinic radiation, particularly KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV, and the like, and sensitive radiation sensitive to these actinic radiations. As an acidic acid generator or as a thermal acid generator, it exhibits good flammability, has no problem with human accumulation, has a sufficiently high acidity and boiling point, and is diffused in the resist film. A novel acid generator capable of obtaining a resist pattern having a moderately short length, small dependence on the sparse density of the mask pattern, and excellent surface and side wall smoothness, and sulfone generated from the acid generator Acids, sulfonic acid derivatives useful as raw materials or intermediates for synthesizing the acid generator and precursors thereof, and the acid generator And to provide a radiation-sensitive resin composition.

The present invention, first,
An acid generator (hereinafter referred to as an acid generator (I)) composed of a compound having a structure represented by the following general formula (I) (hereinafter referred to as “structure (I)”) The radiation-sensitive resin composition The radiation-sensitive acid generator used as an essential component is referred to as an acid generator (A)).

[In General Formula (I), R ¹ represents —OH, —CH ₃ , —OCH ₃ , —OCOCH ₃ , —COOCH ₃ , —SCH ₃ , —SOCH ₃ , —SO ₂ CH ₃ , or —SO ₂ (OCH ₃ ), and a plurality of R ¹ may be the same or different from each other , m is an integer of 0 to 2 , and n is an integer of 1 to 5, preferably 1 or 2. ]

Secondly, the present invention provides a halogen-containing bicyclooctene compound represented by the following general formula (3) and a halogen-containing bicyclooctane compound represented by the general formula (4) (hereinafter referred to as “halogen-containing bicyclooctane compound”). It is called "kind").

In [Formula (3) and (4), R ^1, m and n are each in the general formula (I) have the same meanings as R ^1, m and n, X represents a chlorine atom, a bromine atom or an iodine atom. Moreover, in General formula (3), a double bond can exist in arbitrary positions in a bicyclooctane structure. ]

Thirdly, the present invention comprises a sulfonic acid represented by the following general formula (IA) (hereinafter referred to as “sulfonic acid (IA)”).

[In general formula (IA), R < ¹ >, m, and n are synonymous with R < ¹ >, m, and n in general formula (I), respectively. ]

Fourthly, the present invention comprises a sulfonate represented by the following general formula (1C) (hereinafter referred to as “sulfonate (1C)”).

In [Formula (1C), R ^1, m and n have the same meanings as R ^1, m and n, respectively, in formula (I), M represents a Na, K or Li. ]

Fifthly, the present invention comprises a sulfonyl halide compound represented by the following general formula (IB) (hereinafter referred to as “sulfonyl halide compound (IB)”).

[In general formula (IB), R < ¹ >, m, and n are synonymous with R < ¹ >, m, and n in general formula (I), respectively, and Hal shows a halogen atom. ]

Sixthly, the present invention relates to (A) a radiation-sensitive acid generator having an acid generator as an essential component and (B) an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group, It consists of a positive radiation sensitive resin composition characterized by containing a resin that becomes readily soluble in alkali when the functional group is dissociated.

Seventhly, the present invention provides (A) a radiation-sensitive acid generator containing an acid generator as an essential component, (C) an alkali-soluble resin, and (D) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid. It consists of a negative radiation sensitive resin composition characterized by containing.

The acid generator (I) of the present invention exhibits good flammability and has no problem with human accumulation, and far ultraviolet rays such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser or EUV. Positive radiation sensitivity that is excellent in transparency to electron beams, etc., is a component that generates the sulfonic acid (IA) of the present invention in response to these radiations or by heating, and is particularly useful as a chemically amplified resist. It can be used very suitably as a radiation sensitive acid generator in resin compositions and negative radiation sensitive resin compositions.

Hereinafter, embodiments of the present invention will be described in detail.
Acid generator (I)
The acid generator (I) is a component that generates sulfonic acid (IA) by exposure or heating.
Since the acid generator (I) has a strong fluorine-containing electron withdrawing group at the α-position of the sulfonyl group in the structure (I), the generated sulfonic acid (IA) has high acidity and has a sufficient boiling point. Since it is high, it is difficult to volatilize during the photolithography process, and the acid diffusion length in the resist film is also reasonably short. Furthermore, since the fluorine content in the generated sulfonic acid (IA) is less than that of higher perfluoroalkanesulfonic acid, it exhibits good combustibility and low human accumulation.

In the general formula (I), examples of the monovalent or divalent substituent of R ¹ include an oxo group (═O), a hydroxyl group, a carboxyl group, a formyl group, a halogen atom, and a linear chain having 1 to 10 carbon atoms. Or branched alkyl group, linear or branched vinylidene group having 1 to 10 carbon atoms, monovalent cyclic organic group having 1 to 12 carbon atoms, aryl group having 6 to 20 carbon atoms, 1 to carbon atoms 10 linear or branched alkoxyl groups, aryloxy groups having 6 to 20 carbon atoms, linear or branched alkylcarbonyl groups having 2 to 10 carbon atoms, arylcarbonyl groups having 7 to 20 carbon atoms, carbon numbers A linear or branched alkylcarbonyloxy group having 2 to 10 carbon atoms, an arylcarbonyloxy group having 7 to 20 carbon atoms, a linear or branched alkoxycarbonyl group having 1 to 10 carbon atoms, a carbon number 20 aryloxycarbonyl group, and the like (S based functional group).

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, and n-pentyl. Group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
Examples of the linear or branched vinylidene group having 1 to 10 carbon atoms include carbenyl group, 1,1-ethylidenyl group, propylidenyl group, 1-methylpropylidenyl group, 1-ethylpropylidene group. A denyl group etc. can be mentioned.
Examples of the monovalent cyclic organic group having 1 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a camphoroyl group.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, p-hydroxyphenyl group, 1-naphthyl group, 1-anthracenyl group, A benzyl group etc. can be mentioned.
Examples of the linear or branched alkoxyl group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, and t-butoxy group. Can be mentioned.
Moreover, as said C6-C20 aryloxy group, a phenoxy group, p-hydroxyphenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group etc. can be mentioned, for example.

Examples of the linear or branched alkylcarbonyl group having 2 to 10 carbon atoms include a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an i-propylcarbonyl group, an n-butylcarbonyl group, Examples thereof include a t-butylcarbonyl group.
Examples of the arylcarbonyl group having 7 to 20 carbon atoms include a phenylcarbonyl group and a benzylcarbonyl group.
Examples of the linear or branched alkoxycarbonyl group having 2 to 10 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, Examples thereof include a t-butoxycarbonyl group.
Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include a phenoxycarbonyl group and a benzyloxycarbonyl group. In addition, these substituents can also have arbitrary substituents, for example, 1 or more types of the above-mentioned substituents.

In the general formula (I), R ¹ can be bonded to any carbon atom constituting the bicyclooctane ring in the formula, and a plurality of R ¹ may be the same or different from each other.
In the general formula (I), as R ¹ , for example, —R ⁷ , —COOR ⁸ , —SR ⁸ , —SOR ⁸ , —SO ₂ R ⁸ , —SO ₂ (OR ⁸ ) and the like are preferable. ₃ , —COOCH ₃ , —SCH ₃ , —SOCH ₃ , —SO ₂ CH ₃ , —SO ₂ (OCH ₃ ) and the like are preferable, and m is preferably 0 to 4, and more preferably 0 to 2. Here, R ⁷ and R ⁸ are synonymous with R ⁷ and R ⁸ in the general formula (2) described later.

Specific examples of preferred structure (I) include structures represented by the following formulas (I-1) to (I-12).

Of these structures, formula (1-1), formula (1-9) and the like are preferable.

In the general formula (1), examples of the monovalent onium cation of M ⁺ include onium cations such as O, S, Se, N, P, As, Sb, Cl, Br, and I.
Of these onium cations, the onium cation of S and the onium cation of I are preferred.

In the general formula (1), among the monovalent onium cations of M ⁺ , examples of the onium cation of S include those represented by the following general formula (5). For example, what is represented by following General formula (6) can be mentioned.

[In the general formula (5), R ² , R ³ and R ⁴ are each independently a linear or branched group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, which may have a substituent. Alkyl group, optionally having 3 to 30 carbon atoms which may have a substituent, preferably 6 to 18 monovalent hydrocarbon group, optionally having 6 to 30 carbon atoms, preferably 6 Or an aryl group of ˜18 or an unsubstituted monovalent heterocyclic organic group of 4 to 30 atoms, or any two or more of R ² , R ³ and R ⁴ are bonded via a sulfur atom bonded to each other may be Tei. ]

[In General formula (6), R < ⁵ > and R < ⁶ > are the C1-C30 which may have a substituent mutually independently, Preferably, a 1-10 linear or branched alkyl group, C3-C30 which may have a substituent, Preferably, it is a C6-C18 monovalent hydrocarbon group and C6-C30 which may have a substituent, Preferably it is 6-18. An aryl group or an unsubstituted monovalent heterocyclic organic group having 4 to 30 atoms may be shown, or R ⁵ and R ⁶ may be bonded to each other through an iodine atom to form a ring. ]

In general formula (5) or general formula (6), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each an unsubstituted straight-chain, branched monovalent hydrocarbon group having 1 to 30 carbon atoms. Alternatively, examples of the cyclic monovalent hydrocarbon group having 3 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 1-methylpropyl group, 2- Methylpropyl group, t-butyl group, n-pentyl group, i-pentyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, n-hexyl group, n-heptyl group, i-hexyl group, n-octyl group, i-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 4-t-butylcyclohex An alkyl group such as a syl group, a cyclohexenyl group, a group having a norbornene skeleton, a group having a norbornane skeleton, a group having an isobornyl skeleton, a group having a tricyclodecane skeleton, a group having a tetracyclododecane skeleton, or an adamantane skeleton Groups and the like.

Examples of the substituent for the hydrocarbon group include an aryl group having 6 to 30 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms, a halogen atom, an oxygen atom, a nitrogen atom, and sulfur. Examples thereof include groups having 1 to 30 atoms including heteroatoms such as atoms, phosphorus atoms, and silicon atoms. In addition, these substituents can also have arbitrary substituents, for example, 1 or more types of the above-mentioned substituents.
Examples of the linear, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms substituted with the substituent include benzyl, methoxymethyl, methylthiomethyl, ethoxymethyl, and ethylthio. Methyl group, phenoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, acetylmethyl group, fluoromethyl group, trifluoromethyl group, chloromethyl group, trichloromethyl group, 2-fluoropropyl group, (trifluoroacetyl) methyl Group, (trichloroacetyl) methyl group, (pentafluorobenzoyl) methyl group, aminomethyl group, (cyclohexylamino) methyl group, (diphenylphosphino) methyl group, (trimethylsilyl) methyl group, 2-phenylethyl group, 3- Phenylpropyl group, 2-aminoethyl group, etc. It can be mentioned.

Examples of the unsubstituted aryl group having 6 to 30 carbon atoms of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 1-anthryl group. , 1-phenanthryl group and the like.
Examples of the unsubstituted monovalent heterocyclic organic group having 4 to 30 atoms of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a furyl group, a thienyl group, a pyranyl group, a pyrrolyl group, Thianthrenyl group, pyrazolyl group, isothiazolyl group, isoxazolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 3-tetrahydrothiophene-1,1 -A dioxide group etc. can be mentioned.

Examples of the substituent for the aryl group and the monovalent heterocyclic organic group include a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. And a group having 1 to 30 atoms containing a hetero atom such as a silicon atom. In addition, these substituents can also have arbitrary substituents, for example, 1 or more types of the above-mentioned substituents.
Examples of the aryl group having 6 to 30 carbon atoms substituted by the substituent include, for example, o-tolyl group, m-tolyl group, p-tolyl group, p-hydroxyphenyl group, p-methoxyphenyl group, mesityl group, o-cumenyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, p-fluoro Examples thereof include a phenyl group, a p-trifluoromethylphenyl group, a p-chlorophenyl group, a p-bromophenyl group, and a p-iodophenyl group.

Examples of the monovalent heterocyclic organic group having 4 to 30 atoms substituted with the substituent include, for example, 2-bromofuryl group, 3-methoxythienyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl. Group, 4-methoxytetrahydrothiopyranyl group and the like.

The monovalent onium cation moiety of M ⁺ can be produced according to a general method described in, for example, Advances in Polymer Science, Vol. 62, p. 1-48 (1984).

Preferred monovalent onium cations include, for example, sulfonium cations represented by the following formulas (5-1) to (5-64) and iodonium cations represented by the following formulas (6-1) to (6-39). Etc.

Among these monovalent onium cations, the formula (5-1), formula (5-2), formula (5-6), formula (5-8), formula (5-13), formula (5- 19), a sulfonium cation represented by formula (5-25), formula (5-27), formula (5-29), formula (5-51) or formula (5-54); ) Or an iodonium cation represented by the formula (6-11) is preferable.

Moreover, as a preferable nonionic compound among the compounds which make an acid generator (1), the N-sulfonyloxyimide compound represented by following General formula (2) can be mentioned, for example.

[In the general formula (2), R ^1, m and n have the same meanings as R ^1, m and n, respectively, in the general formula (I), R ⁷ and R ⁸ are hydrogen atoms or each independently a substituted or unsubstituted Or R ⁷ and R ⁸ are bonded to each other to form a ring with the carbon atom to which they are bonded, and Y ¹ is a single bond, a double bond or 2 A valent organic group. ]
Hereinafter, the N-sulfonyloxyimide compound represented by the general formula (2) is referred to as “N-sulfonyloxyimide compound (2)”.

In the general formula (2), examples of the preferable imide group bonded to the sulfonyloxy group (SO ₂ —O—) in each formula include groups represented by the following formulas (7-1) to (7-9). be able to.

Of these imide groups, groups represented by formula (7-1), formula (7-4), formula (7-8) or formula (7-9) are preferred.

The acid generator (I) of the present invention has an action of generating sulfonic acid (IA) by exposure or heating, and is extremely useful as a radiation sensitive acid generator (A) in a radiation sensitive resin composition described later. It can be preferably used.

-Synthesis of sulfonic acid onium salt compound (1)-
The sulfonic acid onium salt compound (1) is described in, for example, Advances in Polymer Science, Vol. 62, p. 1-48 (1984) and Inorganic Chemistry, Vol. 32, p. 5007-5011 (1993). It can be synthesized according to a general method.

That is, as shown in the following reaction formula [1], the corresponding precursor compound (1a) is converted to a sulfinate (1b) by reacting with sodium dithionite in the presence of an inorganic base, This is oxidized to an sulfonate (1c) by oxidizing with an oxidizing agent such as hydrogen peroxide, and then subjected to an ion exchange reaction with a counter ion exchange precursor M ⁺ D ⁻ to obtain an onium sulfonate compound ( 1) can be obtained.

[In Scheme ^[1], R 1, m and n have the same meanings as R ^1, m and n, respectively, in the general formula (I), M ⁺ represents a monovalent onium cation, G is a leaving Represents a monovalent group, and D ⁻ represents a monovalent anion. ]

Examples of the detachable monovalent group of B in the precursor compound (1a) include halogen atoms such as chlorine atom, bromine atom and iodine atom, methanesulfonate group, p-toluenesulfonate group and the like. Preferably, they are a bromine atom and an iodine atom.

In the reaction of the precursor compound (1a) with sodium dithionite, the molar ratio of sodium dithionite to the precursor compound (1a) is usually 0.01 to 100, preferably 1.0 to 10.

Examples of the inorganic base include lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like, preferably sodium hydrogen carbonate, potassium hydrogen carbonate and the like.
The molar ratio of the inorganic base to sodium dithionite is usually 1.0 to 10.0, preferably 2.0 to 4.0.

This reaction is preferably performed in a mixed solvent of an organic solvent and water.
As the organic solvent, for example, a solvent having good compatibility with water, such as lower alcohols, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethylsulfoxide, and the like are preferable, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide and the like are preferable, and acetonitrile is particularly preferable.

The use ratio of the organic solvent is usually 5 parts by weight or more, preferably 10 parts by weight or more, and more preferably 20 to 90 parts by weight with respect to a total of 100 parts by weight of the organic solvent and water.
The reaction temperature is usually 40 to 200 ° C., preferably 60 to 120 ° C., and the reaction time is usually 0.5 to 72 hours, preferably 2 to 24 hours. When the reaction temperature is higher than the boiling point of the organic solvent or water, a pressure vessel such as an autoclave is used.

In the oxidation reaction of sulfinate (1b), as an oxidizing agent, in addition to hydrogen peroxide, metachloroperbenzoic acid, t-butyl hydroperoxide, potassium peroxysulfate, potassium permanganate, sodium perborate, sodium metaiodic acid Sodium, chromic acid, sodium dichromate, halogen, iodobenzene dichloride, iodobenzene diacetate, osmium oxide (VIII), ruthenium oxide (VIII), sodium hypochlorite, sodium chlorite, oxygen gas, ozone gas, etc. Preferred are hydrogen peroxide, metachloroperbenzoic acid, t-butyl hydroperoxide, and the like.
The molar ratio of the oxidizing agent to the sulfinate (1b) is usually 1.0 to 10.0, preferably 1.5 to 4.0.

In addition, a transition metal catalyst can be used in combination with the oxidizing agent.
Examples of the transition metal catalyst include disodium tungstate, iron (III) chloride, ruthenium (III) chloride, selenium oxide (IV), and the like, preferably disodium tungstate.
The molar ratio of the transition metal catalyst to the sulfinate (1b) is usually 0.001 to 2.0, preferably 0.01 to 1.0, and more preferably 0.03 to 0.5.

Furthermore, in addition to the oxidizing agent and the transition metal catalyst, a buffer may be used for the purpose of adjusting the pH of the reaction solution.
Examples of the buffer include disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate. The molar ratio of the buffer to the sulfinate (1b) is usually 0.01 to 2.0, preferably 0.03 to 1.0, and more preferably 0.05 to 0.5.

This reaction is usually performed in a reaction solvent.
The reaction solvent is preferably water or an organic solvent such as lower alcohols, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, acetic acid, trifluoroacetic acid, and more preferably. Is water, methanol, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide or the like, and particularly preferably water or methanol.
Further, if necessary, an organic solvent and water can be used in combination, and the use ratio of the organic solvent in that case is usually 5 parts by weight or more, preferably 100 parts by weight in total of the organic solvent and water. Is 10 parts by weight or more, more preferably 20 to 90 parts by weight. The usage-amount with respect to 100 weight part of sulfinates (1b) of a reaction solvent is 5-100 weight part normally, Preferably it is 10-100 weight part, More preferably, it is 20-50 weight part.

The reaction temperature is usually 0 to 100 ° C., preferably 5 to 60 ° C., more preferably 5 to 40 ° C., and the reaction time is usually 0.5 to 72 hours, preferably 2 to 24 hours.
Further, in the process of converting the precursor compound (1a) to the sulfinate (1b), potassium dithionite or lithium dithionite can be used instead of sodium dithionite. In these cases, Produces a sulfonate salt in which sodium is replaced with potassium or lithium in the sulfonate salt (1c).

The ion exchange reaction of the sulfonate (1c) is carried out according to a general method described in, for example, Advances in Polymer Science, Vol. 62, p. 1-48 (1984). It can be carried out according to the method or the method described in the synthesis examples described later.
Examples of the monovalent anion of D ⁻ in the counter ion exchange precursor include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ and PF _6. ^-, SbF ₆ ^-, an aliphatic sulfonate anion, aromatic sulfonate anion, trifluoromethanesulfonic acid anion, can be cited fluorosulfonic acid anion, ^{preferably, Cl -, Br -, HSO} 4 -, BF 4 ^- an aliphatic sulfonate ion and the like, more ^preferably, Cl ^-, Br -, HSO ₄ ^- is.
The molar ratio of the counter ion exchange precursor to the sulfonate (1c) is usually 0.1 to 10.0, preferably 0.3 to 4.0, and more preferably 0.7 to 2.0. is there.

This reaction is usually performed in a reaction solvent.
The reaction solvent is preferably water or an organic solvent such as lower alcohols, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, more preferably water, methanol, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide and the like, particularly preferably water.
Further, if necessary, water and an organic solvent can be used in combination. The use ratio of the organic solvent in this case is usually 5 parts by weight or more, preferably 100 parts by weight of water and the organic solvent in total. Is 10 parts by weight or more, more preferably 20 to 90 parts by weight. The use amount of the reaction solvent is usually 5 to 100, preferably 10 to 100 parts by weight, and more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the counter ion exchange precursor.
The reaction temperature is usually 0 to 80 ° C., preferably 5 to 30 ° C., and the reaction time is usually 10 minutes to 6 hours, preferably 30 minutes to 2 hours.

The sulfonic acid onium salt compound (1) thus obtained can be purified by extraction with an organic solvent, if necessary.
The organic solvent is preferably an organic solvent that does not mix with water, such as esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether; alkyl halides such as methylene chloride and chloroform.

Synthesis Method of N-Sulfonyloxyimide Compound (2) The N-sulfonyloxyimide compound (2) can be synthesized using the sulfinate (1b) shown in the above reaction formula [1].
That is, as shown in the following reaction formula [2], the sulfinate (1b) is converted into a sulfonyl halide compound such as a sulfonyl chloride compound (2a) using a halogenating agent such as chlorine gas, and this is dealt with. The N-sulfonyloxyimide compound (2) can be obtained by reacting with the N-hydroxyimide compound to be reacted in the presence of a base catalyst.

In [reaction formula [2], R ^1, m and n have the same meanings as R ^1, m and n, respectively, in the general formula ^{(I), R R 7,} R 8 and Y ¹ in the general formula (2) ⁷ , R ⁸ and Y ¹ . ]

The reaction of the sulfinate (1b) with the halogenating agent is described in, for example, the general method described in Advances in Polymer Science, Vol. 62, p. 1-48 (1984) or the synthesis example described later. It can implement according to the method which carried out.
As a method for adding the halogenating agent, for example, in the case of a gaseous halogenating agent such as chlorine gas, a method of blowing into the reaction solution can be adopted, and a liquid or solid halogenating agent such as bromine or iodine can be employed. In this case, it is possible to employ a method in which the reaction solution is added as it is or dissolved in a reaction solvent described later and dropped.
The amount of the halogenating agent used relative to the sulfinate (1b) is usually a large excess.

This reaction is usually performed in a reaction solvent.
The reaction solvent is preferably, for example, water or an organic solvent such as tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethylsulfoxide, and more preferably water, methanol, N, Organic solvents such as N-dimethylacetamide, acetonitrile and dimethyl sulfoxide are preferred, and water is particularly preferred.
Further, if necessary, water and the organic solvent can be used in combination, and the use ratio of the organic solvent in that case is usually 5 parts by weight or more with respect to a total of 100 parts by weight of the water and the organic solvent. Preferably it is 10 weight part or more, More preferably, it is 20-90 weight part.
The usage-amount with respect to 100 weight part of sulfinates (1b) of a reaction solvent is 5-100 weight part normally, Preferably it is 10-100 weight part, More preferably, it is 20-50 weight part.
The reaction temperature is usually 0 to 100 ° C., preferably 5 to 60 ° C., more preferably 5 to 40 ° C., and the reaction time is usually 5 minutes to 12 hours, preferably 10 minutes to 5 hours.

In the reaction of the sulfonyl chloride compound (2a) with the N-hydroxyimide compound, the molar ratio of the N-hydroxyimide compound to the sulfonyl chloride compound (2a) is usually 0.1 to 10.0, preferably 0.00. It is 3-5.0, More preferably, it is 0.5-2.0.

This reaction is usually performed in a reaction solvent.
The reaction solvent is preferably an organic solvent such as acetonitrile, dimethylformamide, pyridine, tetrahydrofuran, dioxane, dimethyl sulfoxide, methylene chloride, methylene bromide, chloroform, and more preferably acetonitrile, tetrahydrofuran, methylene chloride, or the like. .
The usage-amount with respect to 100 weight part of sulfonyl chloride compounds (2a) of a reaction solvent is 5-100 weight part normally, Preferably it is 10-100 weight part, More preferably, it is 20-50 weight part.

Examples of the base catalyst include triethylamine, pyridine, N, N-di-i-propylethylamine, 2,6-lutidine, N, N-diethylaniline, 4-dimethylaminopyridine, diazabicycloundecene. Etc. are preferred, and triethylamine, 4-dimethylaminopyridine and the like are more preferred. The molar ratio of the base catalyst to the sulfonyl chloride compound (2a) is usually 1.0 to 10.0, preferably 1.5 to 5.0, and more preferably 1.5 to 3.0.
The reaction temperature is usually 0 to 80 ° C., preferably 5 to 30 ° C., and the reaction time is usually 5 minutes to 6 hours, preferably 10 minutes to 2 hours.

Halogen-containing compound (1f)
The halogen-containing compound (1f) is extremely useful as a raw material for synthesizing the acid generator (I), and is also useful as a raw material for synthesizing various related derivatives and reaction intermediates.

Next, a method for synthesizing the halogen-containing compound (1f) will be described.
The halogen-containing compound (1f) can be synthesized according to a general method described in, for example, J. Org. Chem., Vol. 50, p.3269-3274 (1985).
That is, as shown in the following reaction formula [3], for example, the corresponding difluoromethylene derivative (1d) is added to the cyclooctadiene compound (1e) in the presence of a radical initiator to form a halogen-containing compound (1f). Can be synthesized. As described later, the halogen-containing bicyclooctene compound (3) is obtained by treating this compound with a base such as DBU to release HX.

In [reaction formula [3], R ^1, m and n have the same meanings as R ^1, m and n, respectively, in formula (I), X ¹ and X ² X ¹ in the general formula (1d) and X ² It is synonymous with. ]

In the difluoromethylene derivative (1d), examples of X ¹ and X ² include halogen atoms such as a chlorine atom, a bromine atom, and an iodine atom, preferably a bromine atom or an iodine atom. X ¹ and X ² may be the same or different from each other.

In the addition reaction, the molar ratio of the difluoromethylene derivative (1d) to the cyclooctadiene compound (1e) is usually 0.01 to 100, preferably 0.1 to 10, respectively.

Examples of the radical initiator include 2,2′-azobisisobutyronitrile (AIBN), dimethylazobisbutyrate, benzoyl peroxide, lauryl peroxide, sodium persulfate, potassium persulfate, and ammonium persulfate. And redox initiators in combination with reducing agents.
Further, in place of the radical initiator, metal compounds such as copper chloride (I), sodium hydrosulfite, potassium hydrosulfite, organic sulfinate, bis (triphenylphosphine) dichloropalladium, tetrakis (triphenylphosphine) palladium Can also be used.
Of these, AIBN, dimethylazobisbutyrate, benzoyl peroxide, redox initiators in combination with reducing agents, sodium hydrosulfite, organic sulfinates, bis (triphenylphosphine) dichloropalladium, etc. are preferred, Preferred are AIBN, dimethylazobisbutyrate, benzoyl peroxide, a redox initiator in combination with a reducing agent, and particularly preferred are AIBN, dimethylazobisbutyrate and the like.

The molar ratio of the radical initiator or the metal compound to the difluoromethylene derivative (1d) is usually 0.001 to 10, preferably 0.01 to 5.0, more preferably 0.01 to 1.0, particularly preferably. 0.03 to 0.2.
This reaction is carried out in the absence of a solvent or hydrocarbons such as heptane, cyclohexane, toluene and xylene; acetates such as ethyl acetate; alcohols such as methanol and ethanol; halogenation such as dichloromethane and 1,2-dichloroethane. Hydrocarbons: The reaction is carried out in a reaction solvent such as tetrahydrofuran, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide or the like. These reaction solvents can be appropriately selected according to the reaction raw material to be used and the radical initiator or metal compound.
Further, if necessary, an organic solvent and water can be used in combination, and the use ratio of the organic solvent in that case is usually 5 parts by weight or more, preferably 100 parts by weight in total of the organic solvent and water. Is 10 parts by weight or more, more preferably 20 to 90 parts by weight. The usage-amount with respect to 100 weight part of difluoromethylene derivatives (1d) of a reaction solvent is 5-100 weight part normally, Preferably it is 10-100 weight part, More preferably, it is 20-50 weight part.
The reaction temperature depends on the radical initiator or metal compound used, but is usually 20 to 150 ° C., preferably 20 to 100 ° C., and the reaction time is usually 0.5 to 24 hours, preferably 2 to 2 ° C. 10 hours. When the reaction temperature is higher than the boiling point of the reaction raw material or reaction solvent, a pressure vessel such as an autoclave is used.

Examples of the base used in the de-HX reaction of the halogen-containing compound (1f) include triethylamine, pyridine, N, N-di-i-propyl / ethylamine, 2,6-lutidine, N, N-diethylaniline, 4-dimethylaminopyridine, diazabicycloundecene and the like are preferable, and triethylamine, 4-dimethylaminopyridine, diazabicycloundecene and the like are more preferable. Further, the molar ratio of the base to the halogen-containing bicyclooctane compound (1f) is usually 1.0 to 10.0, preferably 1.5 to 5.0, and more preferably 1.5 to 3.0.

This reaction is usually performed in a reaction solvent.
As the reaction solvent, for example, organic solvents such as acetonitrile, dimethylformamide, pyridine, tetrahydrofuran, dioxane, dimethyl sulfoxide, methylene chloride, methylene bromide, chloroform and the like are preferable. The base can also be used as a solvent.
The usage-amount with respect to 100 weight part of halogen-containing bicyclooctane compounds (1f) of a reaction solvent is 5-100 weight part normally, Preferably it is 10-100 weight part, More preferably, it is 20-50 weight part.

The reaction temperature is usually 0 to 80 ° C., preferably 5 to 60 ° C., and the reaction time is usually 5 minutes to 6 hours, preferably 10 minutes to 3 hours.
When synthesizing the acid generator (I) or the like using the halogen-containing bicyclooctene compound (3) thus obtained as a starting material, it can be optionally selected during the entire synthesis step, for example, according to the method described later. In this stage, other substituents can be introduced into the double bond in the general formula (3). Furthermore, X ² in the intermediate (1f) can be converted into another substituent for use.

Halogen-containing bicyclooctane compound (4)
The halogen-containing bicyclooctane compound (4) is also extremely useful as a raw material for synthesizing the acid generator (I), and is also useful as a raw material for synthesizing various related derivatives and reaction intermediates.
The halogen-containing bicyclooctane compound (4) can be synthesized by bringing the halogen-containing compound (1f) or the halogen-containing bicyclooctene compound (3) into contact with hydrogen gas in a reaction solvent in the presence of a hydrogenation catalyst. it can.

Examples of the hydrogenation catalyst include transition metal catalysts such as Raney nickel, palladium-carbon, platinum (IV) oxide, rhodium-carbon, rhodium-alumina, ruthenium-carbon, and tris (triphenylphosphine) chlororhodium (I). Can be mentioned.
The weight ratio of the transition metal catalyst to the bicyclooctene compound (3) is usually 0.001-1, preferably 0.01-0.2.
Moreover, the pressure of the hydrogen gas during the hydrogenation reaction is usually 1 to 120 atmospheres, preferably 1 to 100 atmospheres, and more preferably 1 to 50 atmospheres.
This reaction is usually performed in a reaction solvent. As the reaction solvent, for example, organic solvents such as methanol, ethanol, ethyl acetate, toluene, xylene, tetrahydrofuran, and 1,2-dichloroethane are preferable.
The weight ratio of the reaction solvent to the bicyclooctene compound (3) is usually 1 to 100, preferably 5 to 100, more preferably 10 to 80.
The reaction temperature is usually 20 to 200 ° C., preferably 20 to 150 ° C., more preferably 20 to 100 ° C., and the reaction time is usually 0.5 to 24 hours, preferably 4 to 12 hours. When the reaction temperature is higher than the boiling point of the reaction raw material or reaction solvent, or when the pressure of the hydrogen gas used exceeds 1 atm, a pressure vessel such as an autoclave is used.

Sulfonate (1C)
The sulfonate (1C) is extremely useful as a reaction intermediate for synthesizing the sulfonic acid onium salt compound (1), and is also useful as a raw material and a reaction intermediate for synthesizing related derivatives.

Sulfonic acid (IA)
The sulfonic acid (IA) is an acid generated when the acid generator (I) is exposed to light, and a resist pattern is formed using a positive radiation sensitive resin composition and a negative radiation sensitive resin composition described later. In the process, it is a component that acts as an acid catalyst. Further, it is useful as a raw material and a reaction intermediate for synthesizing various related sulfonic acid derivatives, in addition to the constituent components of the antireflection film for lower layer or upper layer provided when forming a resist pattern.

Sulfonyl halide compounds (IB)
The sulfonyl halide compound (IB) is extremely useful as a reaction intermediate when synthesizing the N-sulfonyloxyimide compound (2), and also useful as a raw material and a reaction intermediate for synthesizing related derivatives.

Positive-type radiation-sensitive resin composition and negative-type radiation-sensitive resin composition- component (A)-
The component (A) in the positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention comprises a radiation-sensitive acid generator containing the acid generator (I) as an essential component.
In the positive radiation sensitive resin composition and the negative radiation sensitive resin composition of the present invention, the acid generator (I) can be used alone or in admixture of two or more.
In the positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention, the amount of the acid generator (I) used is the acid generator (I) or the following other acid generators used depending on circumstances. Although it varies depending on the type of the agent, it is usually 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.1 to 0.1 parts by weight with respect to 100 parts by weight of the acid-dissociable group-containing resin or alkali-soluble resin. 2 to 12 parts by weight. In this case, if the amount of the acid generator (I) used is less than 0.1 parts by weight, the desired effect of the present invention may not be sufficiently exhibited, whereas if it exceeds 20 parts by weight, the transparency to radiation is likely to be present. In addition, the pattern shape, heat resistance and the like may be reduced.

In the positive radiation sensitive resin composition and the negative radiation sensitive resin composition of the present invention, a radiation sensitive acid generator other than the acid generator (I) (hereinafter referred to as "other acid generator"). Can be used in combination of one or more.
Examples of other acid generators include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, diazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, and the like.

Examples of the onium salt compounds include iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like.
Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof.
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.

Of these other acid generators, one or more of the group of onium salt compounds, sulfonimide compounds and diazomethane compounds are preferred.

Other particularly preferred acid generators include, for example, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium 2-trifluoromethylbenzene. Sulfonate, diphenyliodonium 4-trifluoromethylbenzenesulfonate, diphenyliodonium 2,4-difluorobenzenesulfonate, diphenyliodonium 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, diphenyliodonium 2 -(5-t-butoxycarbonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1, , 2-tetrafluoroethanesulfonate, diphenyliodonium 2- (6-tert-butoxycarbonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, diphenyl Iodonium 1,1-difluoro-2- (bicyclo [2.2.1] heptan-2-yl) ethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) Iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium 2 -Trifluoromethylbenzene Zensulfonate, bis (4-tert-butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium 2,4-difluorobenzenesulfonate, bis (4-tert-butylphenyl) iodonium 1 , 1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, bis (4-tert-butylphenyl) iodonium 1,1-difluoro-2- (bicyclo [2.2.1] heptane -2-yl) ethanesulfonate,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4- Trifluoromethylbenzenesulfonate, triphenylsulfonium 2,4-difluorobenzenesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, triphenylsulfonium 2- (5 -T-butoxycarbonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroe Sulfonate, triphenylsulfonium 2- (5-t-butoxycarbonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (5-Pivaloyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (6-pivaloyloxy-bicyclo [2.2.1] ] Hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (5-hydroxy-bicyclo [2.2.1] hept-2-yl) -1,1, 2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (6-hydroxy-bicyclo [2.2.1 Hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (5-methanesulfonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1 , 2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (6-methanesulfonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, Triphenylsulfonium 2- (5-i-propanesulfonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (6- i-propanesulfonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroeta Sulfonate, triphenylsulfonium 2- (5-n-hexanesulfonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (6-n-hexanesulfonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (5-oxo-bicyclo [2 2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (6-oxo-bicyclo [2.2.1] hept-2-yl)- 1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 1,1-difluoro-2- (bicyclo [2.2.1 Heptan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nona Fluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (5-t-butoxycarbonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2- Tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Enium 2- (6-t-butoxycarbonyloxy-bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalene- 1-yl) tetrahydrothiophenium 1,1-difluoro-2- (bicyclo [2.2.1] heptan-2-yl) ethanesulfonate,

N- (trifluoromethanesulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) succinimide, N-[(5-methyl-5-carboxymethanebicyclo [2.2.1] heptan-2-yl) sulfonyloxy] Succinimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- [1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonyloxy] bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [ 2.1] hept-5-ene-2,3-dicarboximide, N- {2- (5-oxo-bicyclo [2.2.1] hept-2-yl) -1,1,2, 2-tetrafluoroethanesulfonyloxy} bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (6-oxo-bicyclo [2.2.1] hept- 2-yl) -1,1,2,2-tetrafluoroethanesulfonyloxy} bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [1,1-difluoro- 2- (bicyclo [2.2.1] heptan-2-yl) ethanesulfonyloxy] bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, bis (cyclohexanesulfonyl) diazomethane, Bis (t-butylsulf ) Diazomethane, bis (1,4-dioxaspiro [4.5] - can be exemplified decane-7-sulfonyl) diazomethane and the like.

The use ratio of the other acid generator can be appropriately selected according to the type of the other acid generator, but for a total of 100 parts by weight of the acid generator (I) and the other acid generator, Usually, it is 95 parts by weight or less, preferably 90 parts by weight or less, and more preferably 80 parts by weight or less. In this case, if the use ratio of the other acid generator exceeds 95 parts by weight, the intended effect of the present invention may be impaired.

-(B) component-
The component (B) in the positive-type radiation-sensitive resin composition of the present invention is an alkali-insoluble or hardly alkali-soluble resin having an acid-dissociable group, which is easily soluble in alkali when the acid-dissociable group is dissociated. (Hereinafter referred to as “acid-dissociable group-containing resin (B)”).
The term “alkali-insoluble or alkali-insoluble” as used herein is employed when a resist pattern is formed from a resist film formed using a radiation-sensitive resin composition containing the acid-dissociable group-containing resin (B). When developing a film using only the acid-dissociable group-containing resin (B) instead of the resist film under alkaline development conditions, 50% or more of the initial film thickness of the film remains after development. means.

The acid dissociable group in the acid dissociable group-containing resin (B) is, for example, a group in which a hydrogen atom in an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group is substituted, and in the presence of an acid. It means a group that dissociates.
Examples of such acid dissociable groups include substituted methyl groups, 1-substituted ethyl groups, 1-substituted n-propyl groups, 1-branched alkyl groups, alkoxycarbonyl groups, acyl groups, and cyclic acid dissociable groups. Etc.

Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, (2-methoxyethoxy) methyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, 4- Bromophenacyl group, 4-methoxyphenacyl group, 4-methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, 4-bromobenzyl group, 4-nitro Benzyl group, 4-methoxybenzyl group, 4-methylthiobenzyl group, 4-ethoxybenzyl group, 4-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i- Propoxycarbonylmethyl group, - it can be exemplified butoxycarbonyl methyl group, a t- butoxycarbonyl methyl group.

Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1- Diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropyloxyethyl group, 1 -Cyclohexyloxyethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethyl Groups, 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, etc. Can.

Examples of the 1-substituted-n-propyl group include 1-methoxy-n-propyl group and 1-ethoxy-n-propyl group.
Examples of the 1-branched alkyl group include i-propyl group, 1-methylpropyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, and the like. Can be mentioned.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, and a t-butoxycarbonyl group.

Examples of the acyl group include acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl Group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canphoroyl group Benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group Isonicotinoyl group, p- toluenesulfonyl group, and mesyl group.

Examples of the cyclic acid dissociable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, and a tetrahydro group. A thiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene-1,1-dioxide group and the like can be mentioned.

Among these acid dissociable groups, benzyl group, t-butoxycarbonylmethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 1-ethoxy-n-propyl group, t-butyl Group, 1,1-dimethylpropyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group and the like are preferable.
In the acid-dissociable group-containing resin (B), one or more acid-dissociable groups can be present.

Introduction rate of acid dissociable groups in the acid dissociable group-containing resin (B) (the number of acid dissociable groups relative to the total number of acidic functional groups and acid dissociable groups in the acid dissociable group-containing resin (B)) The ratio) can be appropriately selected depending on the acid-dissociable group and the type of resin into which the group is introduced, but is preferably 5 to 100%, and more preferably 10 to 100%.
In addition, the structure of the acid-dissociable group-containing resin (B) is not particularly limited as long as it has the above-described properties, and various structures can be used. In particular, the phenolic hydroxyl group in poly (4-hydroxystyrene) Of a phenolic hydroxyl group in a copolymer of 4-hydroxystyrene and / or 4-hydroxy-α-methylstyrene and (meth) acrylic acid, a resin in which part or all of the hydrogen atoms are substituted with an acid-dissociable group A resin in which part or all of the hydrogen atoms and / or carboxyl group hydrogen atoms are substituted with an acid dissociable group can be preferably used.

Moreover, the structure of acid dissociable group containing resin (B) can be variously selected according to the kind of radiation to be used.
For example, as an acid dissociable group-containing resin (B) particularly suitable for a positive radiation-sensitive resin composition using a KrF excimer laser, for example, a repeating unit represented by the following general formula (8) (hereinafter referred to as “repeating” Unit (8) ”) and a repeating unit in which the phenolic hydroxyl group in the repeating unit (8) is protected with an acid-dissociable group, is an alkali-insoluble or hardly alkali-soluble resin (hereinafter referred to as“ resin (B1) ”). .) Is preferred. The resin (B1) can also be suitably used for a positive-type radiation-sensitive resin composition that uses other radiation such as ArF excimer laser, F ₂ excimer laser, and electron beam.

[In General Formula (8), R ¹¹ represents a hydrogen atom or a monovalent organic group, a plurality of R ¹¹ may be the same as or different from each other, and e and f are each an integer of 1 to 3. ]

As the repeating unit (8), a unit in which a non-aromatic double bond of 4-hydroxystyrene is cleaved is particularly preferable.
Further, the resin (B1) may further contain other repeating units.
Examples of the other repeating unit include vinyl aromatic compounds such as styrene; (meth) acrylic acid such as t-butyl (meth) acrylate, adamantyl (meth) acrylate, and 2-methyladamantyl (meth) acrylate. Examples include units in which a polymerizable unsaturated bond of esters is cleaved.

Moreover, as an acid dissociable group-containing resin (B) particularly suitable for a positive radiation sensitive resin composition using an ArF excimer laser, for example, a repeating unit represented by the following general formula (9) (hereinafter referred to as “repeating”). Unit (9) ") and / or a repeating unit represented by the following general formula (10) (hereinafter referred to as" repeating unit (10) ") and a repeating unit represented by the following general formula (11). (Hereinafter, referred to as “repeating unit (11)”) is preferably an alkali-insoluble or hardly alkali-soluble resin (hereinafter referred to as “resin (B2)”). The resin (B2) can also be suitably used for a positive-type radiation-sensitive resin composition that uses other radiation such as KrF excimer laser, F ₂ excimer laser, and electron beam.

[In General Formula (9), General Formula (10), and General Formula (11), R ²⁴ , R ^26, and R ²⁷ each independently represent a hydrogen atom or a methyl group, and in General Formula (9), each R ²⁵ is independently of each other a hydrogen atom, a hydroxyl group, a cyano group, or —COOR ²⁹ (where R ²⁹ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. In general formula (11), each R ²⁸ independently of each other is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a straight chain having 1 to 4 carbon atoms. Alternatively, it represents a branched alkyl group, and at least one of R ²⁸ is the alicyclic hydrocarbon group or a derivative thereof, or any two R ²⁸ are bonded to each other, and each is bonded Divalent fat having 4 to 20 carbon atoms together with carbon atoms Forming an expression hydrocarbon group or a derivative thereof, the remainder of R ²⁸ is a monovalent alicyclic hydrocarbon group or a derivative thereof linear or branched alkyl group or 4 to 20 carbon atoms having 1 to 4 carbon atoms Indicates. ]

Preferable repeating units (9) include, for example, (meth) acrylic acid 3-hydroxyadamantan-1-yl, (meth) acrylic acid 3, 5-dihydroxyadamantan-1-yl, (meth) acrylic acid 3-cyanoadamantane -1-yl, (meth) acrylic acid 3-carboxyadamantan-1-yl, (meth) acrylic acid 3,5-dicarboxyadamantan-1-yl, (meth) acrylic acid 3-carboxy-5-hydroxyadamantane- Examples thereof include 1-yl and (meth) acrylic acid 3-methoxycarbonyl-5-hydroxyadamantan-1-yl.

Moreover, as a preferable repeating unit (11), (meth) acrylic acid 1-methylcyclopentyl, (meth) acrylic acid 1-ethylcyclopentyl, (meth) acrylic acid 1-methylcyclohexyl, (meth) acrylic acid 1- Ethylcyclohexyl, 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl (meth) acrylate, 2-n-propyladamantan-2-yl (meth) acrylate, (meth) Examples include 2-i-propyladamantan-2-yl acrylate and 1- (adamantan-1-yl) -1-methylethyl (meth) acrylate.

The resin (B2) can further have other repeating units.
Examples of the monomer giving the other repeating unit include (meth) acrylic acid 7-oxo-6-oxabicyclo [3.2.1] octane-4-yl, (meth) acrylic acid 2-oxotetrahydro Pyran-4-yl, (meth) acrylic acid 4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid 5-oxotetrahydrofuran-3-yl, (meth) acrylic acid 2-oxotetrahydrofuran-3 -(Meth) acrylic acid esters such as (yl) (meth) acrylic acid (5-oxotetrahydrofuran-2-yl) methyl, (meth) acrylic acid (3,3-dimethyl-5-oxotetrahydrofuran-2-yl) methyl Class: (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, fumar Unsaturated amide compounds such as amide, mesaconamide, citraconic amide, itaconic amide; unsaturated polycarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; bicyclo [2.2.1] hept-2-ene or derivatives thereof; Tetracyclo [6.2.1 ^{3, 6} . [0 ^{2, 7} ] monofunctional monomers such as dodec-3-ene or derivatives thereof, methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2,5-dimethyl-2,5-hexane Diol di (meth) acrylate, 1,2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth) acrylate, tricyclodecane dimethylol di ( Mention may be made of polyfunctional monomers such as (meth) acrylates.

Furthermore, as the acid dissociable group-containing resin (B) particularly preferably used for a positive radiation sensitive resin composition using an F ₂ excimer laser, a structural unit represented by the following general formula (12) (hereinafter, “ (Hereinafter referred to as “structural unit (12)”) and / or an alkali-insoluble or hardly alkali-soluble polysiloxane (hereinafter referred to as “structural unit (13)”) represented by the following general formula (13). , "Resin (B3)"). The resin (B3) can also be suitably used for a positive radiation sensitive resin composition using a KrF excimer laser, an ArF excimer laser, an electron beam or the like.

[In General Formula (12) and General Formula (13), each E independently represents a monovalent organic group having an acid dissociable group, and R ³⁰ is a substituted or unsubstituted straight chain having 1 to 20 carbon atoms. A chain, branched or cyclic monovalent hydrocarbon group is shown. ]

E in general formula (12) and general formula (13) is an acid-dissociable group on an alicyclic hydrocarbon group such as a cycloalkyl group, norbornyl group, tricyclodecanyl group, tetracyclododecanyl group, adamantyl group, or the like. And a group having an acid-dissociable group in the halogenated aromatic hydrocarbon group are preferred.

Particularly preferred structural units (12) in the resin (B3) include structural units represented by the following formulas (12-1) to (12-4).

Resin (B3) can have 1 or more types of structural units other than the above (henceforth "another structural unit").
Preferred other structural units include, for example, structural units obtained by hydrolysis and condensation of alkylalkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; ) To (13-4) can be listed as structural units.

The resin (B3) is manufactured by (co) polycondensation of one or more silane compounds having an acid dissociable group or by introducing one or more acid dissociable groups into a pre-synthesized organic polysiloxane. Can do.
In the case of (co) polycondensation of a silane compound having an acid dissociable group, it is preferable to use an acidic catalyst as the catalyst. In particular, after the polycondensation of the silane compound in the presence of an acidic catalyst, the basic catalyst is used. In addition, it is preferable to further react.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, titanium tetrachloride, zinc chloride, and aluminum chloride; formic acid, acetic acid, n-propionic acid, butyric acid, valeric acid, and oxalic acid. Organic acids such as malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, acetic anhydride, maleic anhydride, citric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, etc. Can be mentioned.
Of these acidic catalysts, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, acetic anhydride, maleic anhydride and the like are preferable.

Examples of the basic catalyst include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, and potassium carbonate; Examples thereof include organic bases such as triethylamine, tri-n-propylamine, tri-n-butylamine, and pyridine.

When the acid-dissociable group-containing resin (B) is produced by polymerization of a polymerizable unsaturated monomer or through the polymerization, the resin is a polyfunctional monomer having two or more polymerizable unsaturated bonds. A branched structure can be introduced by a unit derived from the above and / or an acetal crosslinking group. By introducing such a branched structure, the heat resistance of the acid-dissociable group-containing resin (B) can be improved.
In this case, the introduction rate of the branched structure in the acid dissociable group-containing resin (B) can be appropriately selected depending on the branched structure and the type of resin into which the branched structure is introduced. % Or less is preferable.

The molecular weight of the acid-dissociable group-containing resin (B) is not particularly limited and may be appropriately selected. The polystyrene-reduced weight molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC). Is usually 1,000 to 500,000, preferably 2,000 to 400,000, and more preferably 3,000 to 300,000.
The Mw of the acid-dissociable group-containing resin (B) having no branched structure is preferably 1,000 to 150,000, more preferably 3,000 to 100,000, and the acid dissociable having a branched structure. The Mw of the functional group-containing resin (B) is preferably 5,000 to 500,000, more preferably 8,000 to 300,000. By using the acid dissociable group-containing resin (B) having Mw in such a range, the resulting resist has excellent developability.

Further, the ratio (Mw / Mn) between the Mw of the acid dissociable group-containing resin (B) and the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by GPC is not particularly limited and is appropriately selected. However, it is usually 1 to 10, preferably 1 to 8, and more preferably 1 to 5. By using the acid dissociable group-containing resin (B) having Mw / Mn in such a range, the obtained resist has excellent resolution.
In the positive radiation sensitive resin composition of the present invention, the acid dissociable group-containing resin (B) can be used alone or in admixture of two or more.

Although there is no limitation in particular about the manufacturing method of acid dissociable group containing resin (B), For example, the method of introduce | transducing one or more acid dissociable groups into the acidic functional group in the alkali-soluble resin manufactured previously; A method of polymerizing one or more polymerizable unsaturated monomers having a group, optionally together with one or more other polymerizable unsaturated monomers; one or more polycondensable properties having an acid-dissociable group The component can be produced by a method such as polycondensation, optionally with other polycondensable components.

Polymerization of the polymerizable unsaturated monomer and the polymerization of the polymerizable unsaturated monomer having an acid dissociable group at the time of producing the alkali-soluble resin are the polymerizable unsaturated monomer and reaction medium used. The polymerization initiator or polymerization catalyst such as radical polymerization initiator, anion polymerization catalyst, coordination anion polymerization catalyst, cation polymerization catalyst, etc. is appropriately selected according to the type of polymer, bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization. , Suspension polymerization, bulk-suspension polymerization and the like.
The polycondensation of the polycondensable component having an acid dissociable group can be preferably carried out in an aqueous medium or a mixed medium of water and a hydrophilic solvent in the presence of an acidic catalyst.

In the positive radiation sensitive resin composition of the present invention, the amount of the radiation sensitive acid generator used can be variously selected according to the desired characteristics of the resist, but the acid dissociable group-containing resin (B ) Preferably it is 0.001-70 weight part with respect to 100 weight part, More preferably, it is 0.01-50 weight part, Most preferably, it is 0.1-20 mass part. In this case, when the amount of the radiation-sensitive acid generator used is 0.001 part by weight or more, a decrease in sensitivity and resolution can be suppressed, and when it is 70 parts by weight or less, the resist coatability and pattern shape are reduced. Can be suppressed.

-(C) component-
Component (C) in the negative radiation-sensitive resin composition of the present invention is a functional group having an affinity with an alkali developer, for example, one oxygen-containing functional group such as a phenolic hydroxyl group, an alcoholic hydroxyl group, or a carboxyl group. It consists of an alkali-soluble resin soluble in an alkali developer.
Examples of such an alkali-soluble resin include a repeating unit represented by the following general formula (14) (hereinafter referred to as “repeating unit (14)”) and a repeating unit represented by the following general formula (15) ( Hereinafter, addition polymerization having at least one selected from the group of “repeating units (15)” and repeating units represented by the following general formula (16) (hereinafter referred to as “repeating units (16)”). Based resins and the like.

[In General Formula (14) and General Formula (15), R ³¹ and R ³³ each independently represent a hydrogen atom or a methyl group, and R ³² represents a hydroxyl group or a carboxyl group. ]

The alkali-soluble resin may be composed of only the repeating unit (14), the repeating unit (15), or the repeating unit (16). However, as long as the produced resin is soluble in an alkali developer, other repeating units may be used. One or more units may be further included.
As said other repeating unit, the unit similar to the other repeating unit in resin (B1) mentioned above etc. can be mentioned, for example.

The total content of the repeating unit (14), the repeating unit (15), and the repeating unit (16) in the alkali-soluble resin cannot be defined unconditionally depending on the types of other repeating units that are optionally contained. It is 100 mol%, More preferably, it is 20-100 mol%.
When the alkali-soluble resin has a repeating unit having a carbon-carbon unsaturated bond such as the repeating unit (14), it can also be used as a hydrogenated product. In this case, the hydrogenation rate is usually 70% or less, preferably 50% or less, and more preferably 40% or less, of the carbon-carbon unsaturated bonds contained in the corresponding repeating unit. In this case, if the hydrogenation rate exceeds 70%, the developability of the alkali-soluble resin with an alkali developer may be lowered.

As the alkali-soluble resin in the present invention, in particular, poly (4-hydroxystyrene), 4-hydroxystyrene / 4-hydroxy-α-methylstyrene copolymer, 4-hydroxystyrene / styrene copolymer and the like are the main components. Resin is preferred.
The Mw of the alkali-soluble resin varies depending on the desired properties of the negative radiation-sensitive resin composition, but is usually 1,000 to 150,000, preferably 3,000 to 100,000.
In the negative radiation sensitive resin composition of the present invention, the alkali-soluble resins can be used alone or in admixture of two or more.

-(D) component-
(D) component in the negative radiation sensitive resin composition of this invention consists of a compound (henceforth a "crosslinking agent") which can bridge | crosslink alkali-soluble resin in presence of an acid.
Examples of the crosslinking agent include compounds having at least one functional group having a crosslinking reactivity with an alkali-soluble resin (hereinafter referred to as “crosslinkable functional group”).

Examples of the crosslinkable functional group include glycidyl ether group, glycidyl ester group, glycidyl amino group, methoxymethyl group, ethoxymethyl group, benzyloxymethyl group, acetoxymethyl group, benzoyloxymethyl group, formyl group, acetyl group, Examples thereof include a vinyl group, an isopropenyl group, a (dimethylamino) methyl group, a (diethylamino) methyl group, a (dimethylolamino) methyl group, a (diethylolamino) methyl group, and a morpholinomethyl group.

Examples of the crosslinking agent include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resole resin epoxy compounds, poly (hydroxystyrene) epoxy compounds, and methylol group-containing melamine. Compound, methylol group-containing benzoguanamine compound, methylol group-containing urea compound, methylol group-containing phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group-containing phenol compound, carboxymethyl Group-containing melamine resin, carboxymethyl group-containing benzoguanamine resin, carboxymethyl group-containing urea resin, carboxymethyl group-containing Phenol resins, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, mention may be made of carboxymethyl group-containing phenol compounds and the like.

Among these crosslinking agents, methylol group-containing phenol compounds, methoxymethyl group-containing melamine compounds, methoxymethyl group-containing phenol compounds, methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds and acetoxymethyl group-containing phenol compounds are preferred. More preferred are methoxymethyl group-containing melamine compounds (for example, hexamethoxymethyl melamine), methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds, and the like. The methoxymethyl group-containing melamine compound is a trade name such as CYMEL300, 301, 303, 305 (manufactured by Mitsui Cyanamid Co., Ltd.), and the methoxymethyl group-containing glycoluril compound is CYMEL1174 (manufactured by Mitsui Cyanamid Co., Ltd.). ) And methoxymethyl group-containing urea compounds are commercially available under trade names such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).

Moreover, as the crosslinking agent, a resin imparted with a property as a crosslinking agent by substituting the hydrogen atom of the oxygen-containing functional group in the alkali-soluble resin with the crosslinking functional group can be suitably used. The introduction rate of the crosslinkable functional group in that case cannot be unconditionally defined by the type of the crosslinkable functional group or the alkali-soluble resin into which the group is introduced, but with respect to the total oxygen-containing functional group in the alkali-soluble resin, Usually, it is 5 to 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol%. In this case, if the introduction ratio of the crosslinkable functional group is less than 5 mol%, the remaining film ratio tends to decrease, the pattern meanders or swells easily, and if it exceeds 60 mol%, the exposed area is developed. Tend to decrease.

As the crosslinking agent in the present invention, a methoxymethyl group-containing compound, more specifically dimethoxymethylurea, tetramethoxymethylglycoluril and the like are particularly preferable.
In the negative radiation sensitive resin composition of the present invention, the crosslinking agents can be used alone or in admixture of two or more.

In the negative radiation-sensitive resin composition of the present invention, the amount of the radiation-sensitive acid generator used is preferably 0.01 to 70 parts by weight, more preferably 0.1 to 100 parts by weight of the alkali-soluble resin. -50 parts by weight, particularly preferably 0.5-20 parts by weight. In this case, if the amount of the radiation-sensitive acid generator used is less than 0.01 parts by weight, the sensitivity and resolution tend to decrease. On the other hand, if it exceeds 70 parts by weight, the resist coatability and pattern shape deteriorate. It tends to be easy to do.
The amount of the crosslinking agent used is preferably 5 to 95 parts by weight, more preferably 15 to 85 parts by weight, and particularly preferably 20 to 75 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. In this case, if the amount of the crosslinking agent used is less than 5 parts by weight, the remaining film ratio tends to decrease, the pattern meanders or swells easily. There is a tendency to decrease.

-Other additives-
The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention control the diffusion phenomenon in the resist film of the acid generated from the radiation-sensitive acid generator by exposure, and in the non-exposed area. It is preferable to add an acid diffusion controller having an action of suppressing undesirable chemical reactions. By blending such an acid diffusion controller, the storage stability of the radiation-sensitive resin composition can be improved, the resolution as a resist is further improved, and the holding time from exposure to development processing is also improved. Changes in the line width of the resist pattern due to fluctuations in (PED) can be suppressed, and as a result, a radiation-sensitive resin composition having extremely excellent process stability can be obtained.

As such an acid diffusion controller, a nitrogen-containing organic compound whose basicity is not changed by exposure or heat treatment in the resist pattern forming step is preferable.
Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (17) (hereinafter referred to as “nitrogen-containing compound (α)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (α)”). , “Nitrogen-containing compound (β)”), polyamino compounds and polymers having three or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound (γ)”), amide group-containing compounds, urea compounds, nitrogen-containing compounds. A heterocyclic compound etc. can be mentioned.

[In the general formula (17), each R ³⁵ independently represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and each of these groups may be substituted. ]

In the general formula (17), examples of the alkyl group which may be substituted for R ³⁵ include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n- An octyl group, n-ethylhexyl group, n-nonyl group, n-decyl group, etc. can be mentioned.

Examples of the aryl group which may be substituted for R ³⁵ include those having 6 to 12 carbon atoms, specifically, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2, Examples include 3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, cumenyl group, 1-naphthyl group, and the like. be able to.
Furthermore, examples of the aralkyl group which may be substituted for R ³⁵ include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, specifically, benzyl group, α-methylbenzyl group, phenethyl group, 1 -A naphthylmethyl group etc. can be mentioned.

Examples of the nitrogen-containing compound (α) include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; di-n-butylamine, di-n- Dialkylamines such as pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine; triethylamine, tri-n-propylamine, Trialkylamines such as tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine Aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methyl Ruanirin, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, aromatic amines such as 1-naphthylamine; ethanolamine, diethanolamine, can be exemplified alkanolamines such as triethanolamine and the like.

Examples of the nitrogen-containing compound (β) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxy Ethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4 '-Diaminodiphenylamine, 2,2'-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- ( 3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) pro Pan, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and the like. it can.
Examples of the nitrogen-containing compound (γ) include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.

Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Can be mentioned.
Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butyl. Examples include thiourea.

Examples of the nitrogen-containing heterocyclic compound include imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 4-phenylimidazole, 4-methyl-2- Imidazoles such as phenylimidazole and 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4 -In addition to pyridines such as phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, acridine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 1-piperidineethanol 2-piperidine ethanol, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, and 1,4-diazabicyclo [2.2.2] octane.

In addition, as the nitrogen-containing organic compound, a compound having an acid dissociable group can also be used. Examples of the nitrogen-containing organic compound having an acid dissociable group include N- (t-butoxycarbonyl) piperidine, N- (t-butoxycarbonyl) imidazole, N- (t-butoxycarbonyl) benzimidazole, N- ( t-butoxycarbonyl) -2-phenylbenzimidazole, N- (t-butoxycarbonyl) di-n-octylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- And (t-butoxycarbonyl) diphenylamine.

Of these nitrogen-containing organic compounds, nitrogen-containing compounds (α), nitrogen-containing compounds (β), nitrogen-containing heterocyclic compounds, nitrogen-containing organic compounds having an acid-dissociable group, and the like are preferable. The acid diffusion controller can be used alone or in admixture of two or more.

The compounding amount of the acid diffusion controller is preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass, with respect to 100 parts by mass of the acid dissociable group-containing resin (B) or alkali-soluble resin (C). Especially preferably, it is 0.005-5 mass parts. In this case, by setting the blending amount of the acid diffusion control agent to 0.001 part by mass or more, a decrease in pattern shape and dimensional fidelity due to process conditions can be suppressed, and by setting it to 15 parts by mass or less, as a resist Sensitivity and developability of the exposed area can be further improved.

The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention can be blended with a dissolution control agent having a property of increasing the solubility in an alkali developer by the action of an acid.
As such a dissolution control agent, for example, a compound having an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group, or a compound in which the hydrogen atom of the acidic functional group in the compound is substituted with an acid dissociable group Etc.
The dissolution control agent may be a low molecular compound or a high molecular compound, and examples of the polymer dissolution control agent in the negative radiation sensitive resin composition include an acid-dissociable group-containing resin (B in the positive radiation sensitive resin composition). ) Can be used.
The said dissolution control agent can be used individually or in mixture of 2 or more types. The blending amount of the dissolution control agent is usually 50 parts by weight or less, preferably 20 parts by weight or less with respect to 100 parts by weight of the total resin components in the radiation-sensitive resin composition.

The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention are blended with a surfactant exhibiting the action of improving the coating property, striation, developability, etc. of the radiation-sensitive resin composition. You can also
As such a surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but nonionic surfactants are preferred.
Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names “KP” (Shin-Etsu Chemical Co., Ltd.). ), "Polyflow" (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), "F Top" (manufactured by Gemco), "Megafuck" (manufactured by Dainippon Ink & Chemicals), "Florard" (manufactured by Sumitomo 3M), "Asahi Guard" and Each series such as “Surflon” (Asahi Glass) can be listed.
The surfactants can be used alone or in admixture of two or more. The compounding amount of the surfactant is usually 2 parts by weight or less, preferably 1.5 parts by weight or less as an active ingredient of the surfactant with respect to 100 parts by weight of the total resin components in the radiation-sensitive resin composition. is there.

The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention absorbs radiation energy and transmits the energy to the radiation-sensitive acid generator, thereby generating an amount of acid. A sensitizer capable of increasing the apparent sensitivity and improving the apparent sensitivity of the radiation-sensitive resin composition can be blended.
Examples of such sensitizers include acetophenones, benzophenones, naphthalene, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like.
These sensitizers can be used alone or in admixture of two or more. The blending amount of the sensitizer is usually 50 parts by weight or less, preferably 30 parts by weight or less, with respect to 100 parts by weight of the total resin components in the radiation-sensitive resin composition.

Furthermore, in the positive radiation sensitive resin composition and the negative radiation sensitive resin composition of the present invention, additives other than those described above, for example, dyes, are included as long as the effects of the present invention are not impaired. A pigment, an adhesion assistant, an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, etc., specifically, 4-hydroxy-4′-methylchalcone or the like can be blended.
In this case, by blending a dye or pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be mitigated, and the adhesion to the substrate can be improved by blending an adhesion assistant. be able to.

Preparation of composition solution The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention are usually prepared by dissolving each component in a solvent at the time of use, and then required. Accordingly, the composition solution is prepared by, for example, filtering through a filter having a pore size of about 0.2 μm.

Examples of the solvent include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, (halogenated) hydrocarbons, and the like. Specifically, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, (non) cyclic Ketones, acetate esters, hydroxyacetate esters, alkoxyacetate esters, acetoacetate esters, propionate esters, lactic acid esters, other substituted propionate esters, (substituted) Acid esters, pyruvate esters, N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, (halogenated) aliphatic hydrocarbons, (halogenated) aromatic hydrocarbons Etc.

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether. , Diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4 Heptanone, cyclohexanone, ethyl acetate, n-propyl acetate, n-butyl acetate, isopropenyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl acetoacetate, aceto Ethyl acetate, isopropenyl propionate, 3-methyl-3-methoxybutyl propionate, methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl butyrate, methyl 2-hydroxy-3-methylbutyrate, ethyl 2-hydroxy-2-methylpropionate, N, N -Dimethylform Bromide, N, N- dimethylacetamide, N- methylpyrrolidone, toluene, xylene and the like.

Among these solvents, propylene glycol monoalkyl ether acetates, 2-heptanone, lactic acid esters, 2-hydroxypropionic acid esters, 3-alkoxypropionic acid esters, etc. have good in-plane uniformity during coating. It preferred in that door ing.
The said solvent can be used individually or in mixture of 2 or more types.

If necessary, other solvents such as benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1- Use high-boiling solvents such as octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, etc. Can do.
These other solvents can be used alone or in admixture of two or more.
The proportion of other solvents used is usually 50% by weight or less, preferably 30% by weight or less, based on the total solvent.

The total amount of the solvent used is such that the total solid concentration of the composition solution is usually 5 to 50% by weight, preferably 10 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 10 to 30% by weight. In particular, the amount is 10 to 25% by weight. By setting the total solid content concentration of the solution within this range, it is preferable in that the in-film uniformity during coating is good.

Formation of resist pattern When forming a resist pattern from the positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention, the composition solution prepared as described above is used. The resist film is formed by coating on a substrate such as a silicon wafer or a wafer coated with aluminum by an appropriate coating means such as spin coating, cast coating or roll coating. Thereafter, a heat treatment (hereinafter referred to as “PB”) is performed in advance in some cases, and then the resist film is exposed through a predetermined mask pattern.
The radiation that can be used in the exposure includes the emission line spectrum of a mercury lamp (wavelength 254 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength), depending on the type of radiation-sensitive acid generator used. 193 nm), far ultraviolet rays such as F ₂ excimer laser (wavelength 157 nm), EUV (wavelength 13 nm, etc.), X-rays such as synchrotron radiation, charged particle beams such as electron beams, etc., preferably far ultraviolet rays And a charged particle beam, particularly preferably a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excimer laser (wavelength 157 nm) and an electron beam.
The exposure conditions such as the radiation dose are appropriately selected according to the composition of the positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition, the types of additives, and the like.
In forming a resist pattern, it is preferable to perform a heat treatment (hereinafter referred to as “PEB”) after exposure from the viewpoint of improving the apparent sensitivity of the resist.
The heating conditions for PEB vary depending on the composition of the radiation-sensitive resin composition, the type of additive, and the like, but are usually 30 to 200 ° C, preferably 50 to 150 ° C.

Thereafter, the exposed resist film is developed with an alkaline developer to form a predetermined positive or negative resist pattern.
Examples of the alkali developer include alkali metal hydroxides, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo [5.4. 0.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene and the like, an alkaline aqueous solution in which one or more alkaline compounds are dissolved is used. An aqueous solution of ammonium hydroxides.
The concentration of the alkaline aqueous solution is preferably 10% by weight or less, more preferably 1 to 10% by weight, and particularly preferably 2 to 5% by weight. In this case, by setting the concentration of the alkaline aqueous solution to 10% by weight or less, dissolution of the non-exposed portion in the developer can be suppressed.
Further, it is preferable to add an appropriate amount of a surfactant or the like to the developer composed of the alkaline aqueous solution, whereby the wettability of the developer with respect to the resist film can be enhanced.
In addition, after developing with the developing solution which consists of the said alkaline aqueous solution, generally it wash | cleans with water and dries.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Here,% and parts are based on weight unless otherwise specified.

Mass analysis of the following acid generators (Ii) to (I-iii) was performed under the following conditions.
Apparatus: JMS-AX505W type mass spectrometer emitter current manufactured by JEOL Ltd .: 5 mA (gas used: Xe)
Acceleration voltage: 3.0 kV
10N MULTI: 1.3
Ionization method: Fast atom bombardment method (FAB)
Detection ion: Anion (-)
Measurement mass range: 20-1500 m / z
Scan: 30 sec
Resolution: 1500
Matrix: 3-nitrobenzyl alcohol In addition, ¹ H-NMR analysis of acid generators (Ii) to (I-iii) uses “JNM-EX270” manufactured by JEOL Ltd. and uses CDCl ₃ as a measurement solvent. Carried out using.

[Synthesis of Acid Generator (I)]

Synthesis example 1
A raw material solution was prepared by dissolving 65 g of cyclooctadiene and 184 g of 1-bromo-2-iodo-1,1,2,2-tetrafluoroethane in 300 ml of heptane previously bubbled with nitrogen.
Separately, 6.9 g of dimethylazobisbutyrate and 10% by volume of the raw material solution were charged into a 2,000 ml three-necked flask that had been sufficiently purged with nitrogen. Thereafter, the contents were heated to 80 ° C. under a nitrogen stream while stirring, and the remainder of the raw material solution was dropped over 2 hours using a dropping funnel. After completion of dropping, the mixture was further stirred at the same temperature for 15 hours, and then further stirred for 1 hour under reflux conditions. Thereafter, the reaction solution is cooled to 30 ° C. or lower, concentrated under reduced pressure, and the resulting residue is purified by distillation under reduced pressure at 85 ° C. and 1 mmHg to give colorless liquid 1- (2-bromo-1 , 1,2,2-tetrafluoroethyl) -4-iodooctahydropentalene (hereinafter referred to as “compound (a)”) 174 g was obtained.

Next, 174 g of compound (a) is dissolved in 500 ml of tetrahydrofuran, 85 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) is added and stirred at 5 ° C. for 30 minutes, and then at 60 ° C. The mixture was further stirred for 4 hours. Thereafter, the reaction solution was cooled to 5 ° C., and 3M hydrochloric acid was added to adjust the pH to 5-6. The resulting solution was concentrated under reduced pressure to remove most of the tetrahydrofuran and extracted three times with hexane. The obtained organic layer was washed successively with a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution 500, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was distilled under reduced pressure (80 to 84 ° C., 0.3 mmHg) to give 3- (2-bromo-1,1,2,2-tetrafluoro-ethyl) -1,2,3 as a colorless liquid. , 3a, 4,5-hexahydropentalene (hereinafter referred to as “compound (b)”) 103 g was obtained.

Next, a solution obtained by dissolving 103 g of compound (b) in 1 liter of ethyl acetate was placed in a 2 liter autoclave, 10 g of activated carbon containing 5% palladium was added, and the reaction system was replaced with hydrogen. Was stirred at room temperature for 3 hours. Thereafter, the reaction solution was suction filtered through a glass filter with celite, and the filtrate was concentrated under reduced pressure, and then evaporated under reduced pressure to give colorless liquid 1- (2-bromo-1,1,2,2-tetrafluoro). 92 g of (ethyl) -octahydropentalene (hereinafter referred to as “compound (c)”) was obtained.

Next, 500 ml of ion-exchanged water was placed in a 1000 ml three-necked flask that was sufficiently purged with nitrogen, thoroughly bubbled with nitrogen, and 50 g of sodium hydrogen carbonate and 69 g of sodium dithionite were sequentially added. Subsequently, a solution in which 92 g of compound (c) was dissolved in 500 ml of acetonitrile was sufficiently bubbled with nitrogen and then added dropwise at room temperature, followed by stirring at 60 ° C. for 3 hours in a nitrogen atmosphere. Thereafter, the reaction solution was cooled to 30 ° C. or lower, concentrated under reduced pressure to remove acetonitrile, the aqueous layer was extracted four times with ethyl acetate, and the organic layer was washed three times with saturated brine, and then under reduced pressure. 51 g of white solid sodium 1,1,2,2-tetrafluoro-2- (octahydro-pentalen-1-yl) ethanesulfinate (hereinafter referred to as “compound (d)”). Got.

Next, a solution obtained by dissolving 51 g of compound (d), 100 mg of sodium tungstate dihydrate and 1 g of disodium hydrogen phosphate in 300 ml of ion-exchanged water was placed in a 500 ml eggplant flask and cooled to 5 ° C. to react. While maintaining the pH of the solution, 11 ml of 30% aqueous hydrogen peroxide was carefully added dropwise at the same temperature, and the mixture was stirred at the same temperature for 5 minutes, and further stirred at 60 ° C. for 1 hour. Thereafter, the solution was concentrated under reduced pressure to remove water, and the residue was extracted twice with methanol, and then concentrated under reduced pressure to remove methanol, whereby sodium 1,1,2,2-tetrafluoro-2- (octahydro-pentalene- 56 g of 1-yl) ethanesulfonate (hereinafter referred to as “compound (e)”) was obtained.

Next, a solution obtained by dissolving 13 g of triphenylsulfonium bromide in 300 ml of ion-exchanged water was placed in a 1 liter eggplant flask, 7.5 g of compound (e) and 200 ml of methylene chloride were added at room temperature, and then at the same temperature for 1 hour. Stir. Thereafter, the organic layer was separated, washed 5 times with ion-exchanged water, and concentrated under reduced pressure to obtain white solid triphenylsulfonium 1,1,2,2-tetrafluoro-2- (octahydro-pentalene-1- Yl) 13 g of ethanesulfonate was obtained.
This compound is referred to as “acid generator (Ii)”.

As a result of mass analysis of the acid generator (Ii), the anion portion was m / z = 289 (M +).
Further, the result of ¹ H-NMR analysis (chemical shift δ (ppm)) of the acid generator (Ii) is as follows.
_{^{1 H-NMR σppm (CD 3}} Cl): 1.07~1.18 (2H, m, CH 2), 1.25~1.35 (2H, m, CH 2), 1.42~1.61 (4H, m, CH ₂ × 2), 1.82 to 2.04 (2H, m, CH ₂ ), 2.42 to 2.67 (3H, m, CH × 3), 7.26 to 7. 78 (15H, m, Ph)

Synthesis example 2
4 g of 1-n-butoxynaphthalene and 10.6 g of phosphorus pentoxide-methanesulfonic acid mixture were placed in a 300 ml eggplant flask and stirred for 15 minutes at room temperature. Then, 2.4 g of tetramethylene sulfoxide was added dropwise at 0 ° C. Stir for 20 minutes. Thereafter, the temperature is gradually raised to room temperature, and further stirred for 1 hour, then cooled again to 0 ° C., 100 ml of ion-exchanged water is added, pH is adjusted to 7.0 with 25% ammonia water, For 1 hour. Thereafter, the reaction solution was washed with ether, 3 g of compound (e) and 100 ml of methylene chloride were added at room temperature, and the mixture was stirred at the same temperature for 1 hour. Thereafter, the organic layer is separated, washed 5 times with ion-exchanged water, concentrated under reduced pressure, and the resulting concentrate is subjected to reprecipitation treatment in a methylene chloride / n-hexane system to give 1- (4 -N-Butoxynaphthalen-1-yl) tetrahydrothiophenium 1,1,2,2-tetrafluoro-2- (octahydro-pentalen-1-yl) ethanesulfonate was obtained.
This compound is referred to as “acid generator (I-ii)”.

As a result of mass spectrometry of the acid generator (I-ii), the anion portion was m / z = 289 (M +).
The results of ¹ H-NMR analysis (chemical shift δ (ppm)) of the acid generator (I-ii) are as follows.
¹ H-NMR σ ppm (CD ₃ Cl): 1.03 (3H, t, J = 7.3 Hz, CH ₃ ), 1.07 to 1.18 (2H, m, CH ₂ ), 1.25 to 1 .35 (2H, m, CH ₂ ), 1.42-1.67 (10H, m, CH ₂ × 5), 1.82-2.06 (4H, m, CH ₂ × 2), 2.42 ˜2.67 (5H, m, CH × 3, CH ₂ ), 3.61 to 3.71 (2H, m, CH ₂ ), 4.11 to 4.34 (4H, m, CH ₂ × 2) 7.04 (1H, d, J = 8.6 Hz, Ar), 6.64 (1H, t, J = 7.8 Hz, Ar), 7.75 (1H, t, J = 7.9 Hz), 7.95 (1H, d, J = 8.3 Hz, Ar), 8.27 (1H, d, J = 8.6 Hz, Ar), 8.38 (1H, d, J = 7.8 Hz, Ar)

Synthesis example 3
A solution of 20 g of diphenyliodonium chloride dissolved in 1 liter of water was placed in a 2 liter eggplant flask, 500 ml of an aqueous solution of 9.3 g of compound (e) was added dropwise at room temperature, and the mixture was stirred for 15 minutes. Thereafter, the precipitated crystals are filtered through a glass filter, sufficiently washed with water, dried under reduced pressure, and diphenyliodonium 1,1,2,2-tetrafluoro-2- (octahydro-pentalen-1-yl) ethane. 12 g of sulfonate was obtained.
This compound is referred to as “acid generator (I-iii)”.
As a result of mass spectrometry of the acid generator (I-iii), the anion portion was m / z = 289 (M +).
The results of ¹ H-NMR analysis (chemical shift δ (ppm)) of the acid generator (I-iii) are as follows.
_{^{1 H-NMR σppm (CD 3}} Cl): 1.07~1.18 (2H, m, CH 2), 1.25~1.35 (2H, m, CH 2), 1.42~1.61 (4H, m, CH ₂ × 2), 1.82 to 2.04 (2H, m, CH ₂ ), 2.42 to 2.67 (3H, m, CH × 3), 7.32 to 7. 56 (6H, m, Ph), 7.98 (4H, d, J = 7.8 Hz, Ph)

Synthesis example 4
A solution prepared by dissolving 80 g of compound (d) in 250 ml of water was placed in a 2-liter eggplant flask, and excess chlorine gas was bubbled for 15 minutes or more while stirring at room temperature. Thereafter, the oily substance accumulated at the bottom of the flask was extracted with methylene chloride, and the organic layer was washed with an aqueous sodium hydrogen carbonate solution and then dried over anhydrous magnesium sulfate. Thereafter, by distillation under reduced pressure to remove methylene chloride, 1,1,2,2-tetrafluoro-2- (octahydro-pentalen-1-yl) ethanesulfonyl chloride (hereinafter referred to as “compound (f)”) 68 g was obtained.

Next, 22 g of N-hydroxy-5-norbornene-2,3-dicarboximide was added to a solution of compound (f) in 150 g of tetrahydrofuran, and 29 g of triethylamine was added dropwise. Thereafter, the reaction vessel was stirred at room temperature for 10 minutes, and water was removed. Thereafter, the reaction solution was concentrated under reduced pressure, the residue was dissolved in methylene chloride, the resulting solution was transferred to a separatory funnel, shaken and allowed to stand, and then the aqueous layer was removed. Thereafter, the methylene chloride layer was washed successively with an aqueous sodium hydrogen carbonate solution, an aqueous oxalic acid solution and water. Thereafter, the methylene chloride solution was dried over anhydrous magnesium sulfate and filtered, and then the methylene chloride was distilled off from the methylene chloride solution using an evaporator. The obtained liquid was subjected to silica gel chromatography (developing solvent: ethyl acetate / hexane). Separation and purification were performed to obtain 1,1,2,2-tetrafluoro-2- (octahydro-pentalen-1-yl) ethanesulfonic acid 3,5-dioxo-4-aza-tricyclo [5.2.1]. .0 ^2,6] dec-8-ene-4 Niruesuteru (to the "acid generator and (I-iv).) was obtained 10g.

The result of mass spectrometry of the acid generator (I-iv) is m / z = 437 (M +), and the result of ¹ H-NMR analysis of the acid generator (I-iv) is as follows. is there.
¹ H-NMR analysis (chemical shift δ (ppm)):
_{^{1 H-NMR σppm (CD 3}} Cl): 1.07~1.18 (2H, m, CH 2), 1.25~1.35 (2H, m, CH 2), 1.42~1.61 (5H, m, CH ₂ × 2, CH ₂ ), 1.82 to 2.04 (3H, m, CH ₂ , CH ₂ ), 2.42 to 2.67 (3H, m, CH × 3), 3.38 (2H, s, CH × 2), 3.55 (2H, s, CH × 2), 6.20 (2H, s, CH × 2)

[Synthesis of acid-dissociable group-containing resin (B)]
Synthesis example 5
After dissolving 101 g of 4-acetoxystyrene, 5 g of styrene, 42 g of 4-t-butoxystyrene, 6 g of azobisisobutyronitrile (AIBN) and 1 g of t-dodecyl mercaptan in 160 g of propylene glycol monomethyl ether, the reaction was performed in a nitrogen atmosphere. Polymerization was carried out for 16 hours while maintaining the temperature at 70 ° C. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to coagulate and purify the resulting resin.
Next, 150 g of propylene glycol monomethyl ether was added to the purified resin, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting resin was dissolved in acetone, then dropped into a large amount of water to solidify, and the resulting white powder was filtered and dried at 50 ° C. under reduced pressure overnight. did.
The obtained resin had an Mw of 16,000 and an Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of 4-hydroxystyrene, styrene and 4-t-butoxystyrene was The copolymer was 72: 5: 23.
This resin is referred to as “resin (B-1)”.

Resin Measurement of Mw and Mn of (B-1) and the following resin-(B-2) ~ (B -11) are manufactured by Tosoh Corporation GPC column (G2000H _XL 2 present, one G3000H _XL, G4000H _XL 1 This was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of a flow rate of 1.0 ml / min, an elution solvent tetrahydrofuran, and a column temperature of 40 ° C.

Synthesis Example 6
100 g of 4-acetoxystyrene, 25 g of t-butyl acrylate, 18 g of styrene, 6 g of AIBN and 1 g of t-dodecyl mercaptan are dissolved in 230 g of propylene glycol monomethyl ether, and polymerization is performed for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. did. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to coagulate and purify the resulting resin.
Next, 150 g of propylene glycol monomethyl ether was added to the purified resin, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting resin was dissolved in acetone, then dropped into a large amount of water to solidify, and the resulting white powder was filtered and dried at 50 ° C. under reduced pressure overnight. did.
The obtained resin had Mw of 11,500 and Mw / Mn of 1.6. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of 4-hydroxystyrene, t-butyl acrylate and styrene was 61. : 19:20 copolymer.
This resin is referred to as “resin (B-2)”.

Synthesis example 7
176 g of 4-t-butoxystyrene was anionically polymerized in 500 ml of tetrahydrofuran at −78 ° C. using n-butyllithium as a catalyst. After polymerization, the reaction solution was coagulated in methanol to obtain 150 g of white poly (4-t-butoxystyrene).
Next, 150 g of this poly (4-t-butoxystyrene) was dissolved in 600 g of dioxane, diluted hydrochloric acid was added, and a hydrolysis reaction was performed at 70 ° C. for 2 hours. Thereafter, the reaction solution was dropped into a large amount of water to solidify the resin. Thereafter, the operation of dissolving the coagulated resin in acetone and coagulating in a large amount of water was repeated, and the produced white powder was filtered and dried overnight at 50 ° C. under reduced pressure.
The obtained resin had an Mw of 10,400 and an Mw / Mn of 1.10. As a result of ¹³ C-NMR analysis, only a part of the t-butyl group in poly (4-t-butoxystyrene) was obtained. It was a copolymer having a hydrolyzed structure and a copolymerization molar ratio of 4-t-butoxystyrene and 4-hydroxystyrene of 68:32.
This resin is referred to as “resin (B-3)”.

Synthesis example 8
25 g of 4-hydroxystyrene / 4-t-butoxystyrene copolymer having a copolymerization molar ratio of 90:10 was dissolved in 100 g of n-butyl acetate, bubbled with nitrogen gas for 30 minutes, and then ethyl vinyl ether 3 .3 g was added, 1 g of p-toluenesulfonic acid pyridinium salt was added as a catalyst, and the mixture was reacted at room temperature for 12 hours. Thereafter, the reaction solution was dropped into a 1% aqueous ammonia solution to solidify the resin, filtered, and dried overnight at 50 ° C. under reduced pressure.
The obtained resin had Mw of 13,000 and Mw / Mn of 1.01, and as a result of ¹³ C-NMR analysis, 23 mol% of hydrogen atoms of the phenolic hydroxyl group in poly (4-hydroxystyrene) was found to be The ethoxyethyl group had a structure in which 10 mol% was substituted with a t-butyl group.
This resin is referred to as “resin (B-4)”.

Synthesis Example 9
2-butanone (200 g) was obtained by adding 53.69 g of 5-oxo-4-oxatricyclo [4.2.1.0 ^{3, 7} ] nonan-2-yl methacrylate and 46.31 g of 2-methyladamantan-2-yl methacrylate. And a monomer solution charged with 4.04 g of dimethylazobisbutyrate was prepared.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the content was heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel, the start of dropping was taken as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, and then poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol, washed in a slurry state, filtered, and dried under reduced pressure at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has an Mw of 9,700 and an Mw / Mn of 2.14. As a result of ¹³ C-NMR analysis, 5-oxo-4-oxatricyclomethacrylate [4.2.1.0 ^{3, 7} It was a copolymer having a copolymerization molar ratio of nonane-2-yl and 2-methyladamantan-2-yl methacrylate of 59.6: 40.4.
This resin is referred to as “resin (B-5)”.

Synthesis Example 10
40.90 g of 2-methyladamantan-2-yl methacrylate, 15.47 g of 3-hydroxyadamantan-1-yl methacrylate and 5-oxo-4-oxatricyclo methacrylate [4.2.1.0 ^{3, 7} A monomer solution was prepared by dissolving 43.64 g of nonan-2-yl in 200 g of 2-butanone and adding 4.02 g of dimethylazobisbutyrate.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the content was heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel, the start of dropping was taken as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, and then poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol, washed in a slurry state, filtered, and dried under reduced pressure at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has Mw of 9,200 and Mw / Mn of 2.00. As a result of ¹³ C-NMR analysis, 2-methyladamantan-2-yl methacrylate and 3-hydroxyadamantan-1-yl methacrylate were obtained. methacrylic acid 5-oxo-4-oxa-tricyclo [4.2.1.0 ^{3, 7]} the copolymerization molar ratio of nonane-2-yl 36.2: 15.2: 48.6 of the copolymer Met.
This resin is referred to as “resin (B-6)”.

Synthesis Example 11
43.66 g of 1- (adamantan-1-yl) -1-methylethyl methacrylate, 14.74 g of 3-hydroxyadamantan-1-yl methacrylate and 5-oxo-4-oxatricyclomethacrylate [4.2. 1.0 ^{3, 7} ] 43.66 g of nonan-2-yl was dissolved in 200 g of 2-butanone, and a monomer solution charged with 3.83 g of dimethylazobisisobutyrate was prepared.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the content was heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel, the start of dropping was taken as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, and then poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol, washed in a slurry state, filtered, and dried under reduced pressure at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has Mw of 9,600 and Mw / Mn of 1.96, and as a result of ¹³ C-NMR analysis, 1- (adamantan-1-yl) -1-methylethyl methacrylate and 3-hydroxymethacrylate were obtained. The copolymer molar ratio of adamantane-1-yl and 5-oxo-4-oxatricyclo [4.2.1.0 ^{3, 7} ] nonan-2-yl methacrylate was 35.6: 15.1: 49 .3 copolymer.
This resin is referred to as “resin (B-7)”.

Synthesis Example 12
16.13 g of 2-ethyladamantan-2-yl methacrylate, 40.58 g of 2-methyladamantan-2-yl methacrylate and 5-oxo-4-oxatricyclomethacrylate [4.2.1.0 ^{3, 7} A monomer solution was prepared by dissolving 3.29 g of nonan-2-yl in 200 g of 2-butanone and adding 3.99 g of dimethylazobisisobutyrate.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the content was heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel, the start of dropping was taken as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, and then poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol, washed in a slurry state, filtered, and dried under reduced pressure at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has Mw of 8,900 and Mw / Mn of 2.00. As a result of ¹³ C-NMR analysis, 2-ethyladamantan-2-yl methacrylate and 2-methyladamantan-2-yl methacrylate were obtained. methacrylic acid 5-oxo-4-oxa-tricyclo [4.2.1.0 ^{3, 7]} the copolymerization molar ratio of nonane-2-yl 13.7: 38.2: 48.1 copolymers Met.
This resin is referred to as “resin (B-8)”.

Synthesis Example 13
42.44 g of 5-oxo-4-oxatricyclo [4.2.1.0 ^{3, 7} ] nonan-2-yl acrylate, 15.10 g of 3-hydroxyadamantan-1-yl acrylate and 2-acrylic acid 2- A monomer solution was prepared by dissolving 42.46 g of ethyladamantan-2-yl in 200 g of 2-butanone and adding 4.17 g of dimethylazobisbutyrate.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the content was heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel, the start of dropping was taken as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, and then poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol, washed in a slurry state, filtered, and dried under reduced pressure at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has an Mw of 10,200 and an Mw / Mn of 1.75. As a result of ¹³ C-NMR analysis, 5-oxo-4-oxatricycloacrylate [4.2.1.0 ^{3, 7} Copolymer with a copolymer molar ratio of 49.2: 15.3: 35.5 of nonan-2-yl, 3-hydroxyadamantan-1-yl acrylate and 2-ethyladamantan-2-yl acrylate Met.
This resin is referred to as “resin (B-9)”.

Synthesis Example 14
Methacrylic acid 5-oxo-4-oxa-tricyclo [4.2.1.0 ^{3, 7]} non-2-yl 55.00 g, methacrylic acid 3-hydroxy-adamantan-1-yl 11.70g and acrylic acid 1- A monomer solution was prepared by dissolving 33.31 g of ethylcyclopentyl in 200 g of 2-butanone and adding 4.56 g of dimethylazobisbutyrate.
Separately, a 1,000 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. Thereafter, the content was heated to 80 ° C. while stirring, and the monomer solution was added dropwise over 4 hours using a dropping funnel, the start of dropping was taken as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After the polymerization, the reaction solution was cooled with water and cooled to 30 ° C. or lower, and then poured into 2,000 g of methanol, and the precipitated white powder was filtered off. Thereafter, the obtained white powder was mixed twice with 400 g of methanol, washed in a slurry state, filtered, and dried under reduced pressure at 50 ° C. for 17 hours to obtain a white powder resin.
This resin has Mw of 8,500 and Mw / Mn of 1.75. As a result of ¹³ C-NMR analysis, 5-oxo-4-oxatricyclo methacrylate [4.2.1. ^{3, 7} ] A copolymer having a molar ratio of 53.7: 11.1: 35.2 of nonan-2-yl, 3-hydroxyadamantan-1-yl methacrylate and 1-ethylcyclopentyl acrylate. there were.
This resin is referred to as “resin (B-10)”.

Synthesis Example 15
In a three-necked flask, 1.52 g of a silane compound represented by the following formula (18-1), 1.57 g of a silane compound represented by the following formula (18-2), 1.91 g of methyltriethoxysilane, 4- After adding 15 g of methyl-2-pentanone and 1.31 g of 1.75% oxalic acid aqueous solution and reacting at 80 ° C. for 6 hours with stirring, the reaction vessel was ice-cooled to stop the reaction. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added and washed, and washing was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain a resin.
This resin has Mw of 2,500, and the molar ratio of the structural unit represented by the formula (12-2) to the structural unit represented by the formula (13-1) is 54.7: 45. 3 resin.
This resin is referred to as “resin (B-11)”.

The evaluation of each resist in Examples and Comparative Examples was performed as follows.
sensitivity:
The resist film formed on the silicon wafer is exposed to light, immediately subjected to PEB, alkali developed, washed with water and dried to form a resist pattern. When the exposure light source is other than an ArF excimer laser, the line width is 0. The optimum exposure dose is an exposure dose for forming a 22 μm line-and-space pattern (1L1S) with a one-to-one line width. When the exposure light source is an ArF excimer laser, the line-and-space pattern is 0.16 μm The exposure amount for forming the space pattern (1L1S) in a one-to-one line width was taken as the optimum exposure amount, and the sensitivity was evaluated based on this optimum exposure amount.
resolution:
The minimum dimension of the line-and-space pattern (1L1S) resolved when exposed at the optimum exposure amount was taken as the resolution.

Mask pattern dependency:
If the exposure light source is other than an ArF excimer laser, a 1L10S pattern with a design dimension of 0.22 μm (0.22 μm line / 2.2 μm space) is formed, and the exposure light source is an ArF excimer laser. When a 1L / 10S pattern (0.16 μm line / 1.6 μm space) with a design dimension of 0.16 μm is formed, the line width of the obtained line pattern exceeds 70% of the design dimension (0.22 μm). “Good” was defined as “bad” when 70% or less.

Mask pattern fidelity:
When exposure is performed at the optimum exposure amount, if the exposure light source is other than an ArF excimer laser, a 1L5S pattern (0.22 μm line / 1.1 μm space) with a design dimension of 0.22 μm is formed. If the exposure light source is an ArF excimer laser Forms a 1L5S pattern (0.16 μm line / 0.80 μm space) with a design dimension of 0.16 μm, and the difference (absolute value) between the line width of the obtained line pattern and the design dimension is determined as the mask pattern fidelity. It was.

Nano edge roughness:
When the exposure light source is other than an ArF excimer laser, a line and space pattern (1L1S) having a design dimension of 0.22 μm is formed, and the line pattern is observed with a scanning electron microscope. ) (However, the unevenness is exaggerated more than actually). The difference ΔCD (absolute value) between the line width and the design dimension d0.22 μm at the most remarkable unevenness generated along the lateral surface of the line pattern. ) Was measured, and the case where the ΔCD was less than 0.044 μm was judged as “good”, and the case where it was 0.044 μm or more was judged as “bad”.
When the exposure light source is an ArF excimer laser, a line and space pattern (1L1S) having a design dimension of 0.16 μm is formed, and the line pattern is observed with a scanning electron microscope. As shown in b), the difference ΔCD (absolute value) between the line width and the design dimension d 0.16 μm at the most conspicuous portion of the unevenness generated along the lateral surface of the line pattern is measured, and the ΔCD is 0.032 μm. The case of less than “32” was defined as “good”, and the case of 0.032 μm or more was defined as “bad”.

Examples 1-20 and Comparative Examples 1-5
Each component shown in Table 1 was mixed to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution. Then, after spin-coating each composition solution on the silicon wafer, PB was performed on the conditions shown in Table 2, and the resist film of the film thickness shown in Table 2 was formed.
Next, when the exposure light source is a KrF excimer laser (shown as “KrF” in Table 2), a Nikon stepper NSR2205 EX12B (numerical aperture 0.55) is used, and the exposure light source is an ArF excimer laser (Table 2). In the case of “ArF”, a Nikon ArF excimer laser exposure device (numerical aperture: 0.55) is used, and the exposure light source is an F ₂ excimer laser (shown as “F ₂ ” in Table 2). is used Ultratech Co. F ₂ excimer laser exposure apparatus XLS (numerical aperture 0.60), also when the exposure light source is an electron beam, Hitachi Ltd. straight描用electron beam lithography system HL700 (the acceleration voltage After exposure using an apparatus improved from 30 KeV to 50 KeV, PEB was performed under the conditions shown in Table 2. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was used and developed by the paddle method at 23 ° C. for 1 minute, followed by washing with pure water and drying to form a resist pattern. Table 3 shows the evaluation results of each resist.

In Table 1, components other than the acid generator (I) and the resins (B-1) to (B-11) are as follows.
Other acid generators a-1: N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide a-2: triphenylsulfonium nonafluoro-n- Butanesulfonate a-3: triphenylsulfonium perfluoro-n-octanesulfonate a-4: 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate a-5: 1 -(4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate a-6: bis (cyclohexylsulfonyl) diazomethane

Alkali-soluble resin C-1: 4-hydroxystyrene / styrene copolymer (copolymerization molar ratio = 78: 22, Mw = 3,100, Mw / Mn = 1.13)
Crosslinker D-1: N, N, N, N-tetra (methoxymethyl) glycoluril
Acid diffusion controller E-1: Tri-n-octylamine E-2: Triethanolamine E-3: 2-phenylbenzimidazole E-4: 1,2-dimethylimidazole E-5: Nt-butoxycarbonyl 2-Phenylbenzimidazole
Other additive F-1: t-butoxycarbonylmethyl deoxycholate
Solvent S-1: Ethyl lactate S-2: Ethyl 3-ethoxypropionate S-3: Propylene glycol monomethyl ether acetate S-4: 2-heptanone S-5: Cyclohexanone S-6: γ-Butyrolactone

From Table 3, the radiation-sensitive resin composition using the acid generator (I) of the present invention is excellent in mask pattern dependency or mask pattern fidelity, and also has good nano edge roughness, so that smoothness is also achieved. It is clear that it is excellent and has high sensitivity and high resolution.

The acid generator (I) of the present invention is very preferably used as a radiation-sensitive acid generator in positive-type radiation-sensitive resin compositions and negative-type radiation-sensitive resin compositions useful as chemically amplified resists. it can.
Since the sulfonic acid (IA) of the present invention has a strong fluorine-containing electron withdrawing group at the α-position of the sulfonic acid group, the acidity is high, and the boiling point is sufficiently high, so that it is difficult to volatilize in the photolithography process. In addition, the diffusion length in the resist film is moderately short, and the fluorine content is lower than that of higher perfluoroalkanesulfonic acid, so that it exhibits good flammability and low human body accumulation.
The sulfonyl halide compound (1B) of the present invention is particularly useful as a raw material or intermediate for synthesizing the acid generator (I).

The positive-type radiation-sensitive resin composition and negative-type radiation-sensitive resin composition of the present invention containing the acid generator (I) are active radiation, in particular, KrF excimer laser, ArF excimer laser, F ₂ excimer laser, or EUV. Effectively sensitive to deep ultraviolet rays and electron beams typified by the above, the sensitivity is high, the acid diffusion length in the resist film is moderately short, the resolution is excellent, and the mask pattern has a dependency on the sparse density. It is small and excellent in the smoothness of the surface and side walls of the resist pattern, and can be used very favorably in the field of microfabrication represented by the manufacture of integrated circuit elements that are expected to become increasingly finer in the future. .

It is a figure explaining the evaluation point of nano edge roughness.

Claims (13)

An acid generator comprising a sulfonic acid onium salt compound represented by the following general formula (1).

[In General Formula (1), R ¹ represents —OH, —CH ₃ , —OCH ₃ , —OCOCH ₃ , —COOCH ₃ , —SCH ₃ , —SOCH ₃ , —SO ₂ CH ₃ , or —SO ₂ (OCH ₃ ), a plurality of R ¹ may be the same or different from each other, m is an integer of 0 to 2, n is an integer of 1 to 5 , and M ⁺ represents a monovalent onium cation. ] In the general formula (1), M ⁺ is as defined in claim 1 is a iodonium cation represented by the following general formula (5A) or sulfonium cation represented by (5B) or the following general formula, (6A) Acid generator.

[In General Formula (5A), R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or a halogen atom, oxygen atom, nitrogen An atom, a sulfur atom, a phosphorus atom, or a group having 1 to 30 atoms including a silicon atom is shown]

[In the general formula (5B), R ′ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or silicon. Represents a group having 1 to 30 atoms including atoms]

[In General Formula (6A), R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or a halogen atom, oxygen atom, nitrogen atom, sulfur A 1-30 atom group containing an atom, phosphorus atom, or silicon atom] In the general formula (1), M ⁺ represents the following formulas (5-1), (5-2), (5-6), (5-8), (5-13), (5-19), A sulfonium cation represented by (5-25), (5-27), (5-29), (5-51) or (5-54), or the following formula (6-1) or (6-11) The acid generator according to claim 1 , which is an iodonium cation represented by the formula:

An acid generator comprising an N-sulfonyloxyimide compound represented by the following general formula (2).

[In General Formula (2), R ¹ represents —OH, —CH ₃ , —OCH ₃ , —OCOCH ₃ , —COOCH ₃ , —SCH ₃ , —SOCH ₃ , —SO ₂ CH ₃ , or —SO ₂ (OCH ₃ ), a plurality of R ¹ may be the same or different from each other, m is an integer of 0 to 2, n is an integer of 1 to 5 , and R is represented by the following formulas (7-1) to (7 The group represented by any of -9) is shown. ]

A halogen-containing bicyclooctene compound represented by the following general formula (3).

[In General Formula (3), R ¹ represents —OH, —CH ₃ , —OCH ₃ , —OCOCH ₃ , —COOCH ₃ , —SCH ₃ , —SOCH ₃ , —SO ₂ CH ₃ , or —SO ₂ (OCH ₃ ), a plurality of R ¹ may be the same or different from each other, m is an integer of 0 to 2, n is an integer of 1 to 5 , and X is a chlorine atom, a bromine atom or an iodine atom . Moreover, in General formula (3), a double bond can exist in arbitrary positions in a bicyclooctene structure. ] A halogen-containing bicyclooctane compound represented by the following general formula (4).

[In General Formula (4), R ¹ represents —OH, —CH ₃ , —OCH ₃ , —OCOCH ₃ , —COOCH ₃ , —SCH ₃ , —SOCH ₃ , —SO ₂ CH ₃ , or —SO ₂ (OCH ₃ ), a plurality of R ¹ may be the same or different from each other, m is an integer of 0 to 2, n is an integer of 1 to 5 , and X is a chlorine atom, a bromine atom or an iodine atom . ] A sulfonate represented by the following general formula (1C).

[In General Formula (1C), R ¹ represents —OH, —CH ₃ , —OCH ₃ , —OCOCH ₃ , —COOCH ₃ , —SCH ₃ , —SOCH ₃ , —SO ₂ CH ₃ , or —SO ₂ (OCH ₃ ), and a plurality of R ^{1 s} may be the same or different from each other, m is an integer of 0 to 2, n is an integer of 1 to 5 , and M represents Na, K, or Li. ] A sulfonic acid represented by the following general formula (IA).

[In General Formula (IA), R ¹ represents —OH, —CH ₃ , —OCH ₃ , —OCOCH ₃ , —COOCH ₃ , —SCH ₃ , —SOCH ₃ , —SO ₂ CH ₃ , or —SO ₂ (OCH ₃ ), and a plurality of R ¹ may be the same or different from each other, m is an integer of 0 to 2, and n is an integer of 1 to 5 . ] A sulfonyl halide compound represented by the following general formula (IB).

[In General Formula (IB), R ¹ represents —OH, —CH ₃ , —OCH ₃ , —OCOCH ₃ , —COOCH ₃ , —SCH ₃ , —SOCH ₃ , —SO ₂ CH ₃ , or —SO ₂ (OCH ₃ ), a plurality of R ¹ may be the same or different from each other, m is an integer of 0 to 2, n is an integer of 1 to 5 , and Hal represents a halogen atom. ]   (A) a radiation-sensitive acid generator comprising the acid generator according to claim 1 as an essential component, and (B) an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group, the acid-dissociable group A positive-type radiation-sensitive resin composition comprising a resin that becomes readily soluble in alkali when dissociated. The positive radiation sensitive resin composition according to claim 10 , wherein the component (A) contains the acid generator according to any one of claims 2 to 4 .   (A) A radiation-sensitive acid generator containing the acid generator according to claim 1 as an essential component, (C) an alkali-soluble resin, and (D) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid. A negative-type radiation-sensitive resin composition characterized by that. (A) Component contains the acid generator in any one of Claims 2-4, The negative radiation sensitive resin composition of Claim 12 characterized by the above-mentioned.

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