JP4946094B2 - Novel compound, radiation-sensitive acid generator and positive radiation-sensitive resin composition using the same - Google Patents

Description

  The present invention is a resist material suitably used in the field of microfabrication including the manufacture of integrated circuit elements, particularly an acid group having at least a part of the acid group protected by an acid dissociable group. A chemical amplification type utilizing a chemical amplification effect between an acid-dissociable group-modified alkali-soluble resin and a radiation-sensitive acid generator that generates acid upon irradiation with short-wavelength radiation such as deep ultraviolet rays, X-rays, and electron beams The present invention relates to a radiation sensitive resin composition. More specifically, the present invention relates to a compound capable of forming a resist pattern with high resolution when used as a radiation sensitive acid generator.

In recent years, in the field of microfabrication including the manufacture of integrated circuit elements, it is possible to perform microfabrication at a level of 0.1 μm or less (submicron order) in order to manufacture elements with higher integration. There is a need for lithographic techniques. In order to process a fine pattern, it is known that it is effective to draw a pattern using radiation having a shorter wavelength, and instead of the conventionally used visible light and ultraviolet light, far ultraviolet light is used. , X-ray, electron beam and other short wavelength radiation, more specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), EUV (Extreme Ultra-Violet) : Extreme ultraviolet rays, wavelength of 13 nm, etc.) or use of electron beams or the like has been studied.

  Lithographic techniques using short-wavelength radiation as described above include acid-dissociable group-modified alkali-soluble resins having an acid group and at least part of the acid group being protected by an acid-dissociable group, Chemical amplification type radiation-sensitive resin using chemical amplification effect between radiation-sensitive acid generator that generates acid upon irradiation (exposure) of wavelength radiation (simply referred to as “acid generator”) A technique for forming a resist pattern using a composition has been proposed.

  The chemically amplified radiation-sensitive resin composition generates an acid from an acid generator by exposure, dissociates an acid-dissociable group that protected the acidic group of the alkali-soluble resin by the action of the acid, and the alkali-soluble resin This is a composition for forming a resist pattern by exposing the acidic group of the material and making the exposed region easily soluble in an alkali developer.

  For example, a polymer having a carboxyl group (acidic group) protected with a t-butyl group (acid-dissociable group) or a polymer having a phenolic hydroxyl group (acidic group) protected with a t-butoxycarbonyl group (acid-dissociable group) A resist composition containing an acid generator such as a diaryl iodonium salt or a triaryl sulfonium salt is disclosed (for example, see Patent Document 1).

  A resist composition containing a compound in which an amide group or the like is introduced into the aryl group or the like of the triarylsulfonium salt as described above is also disclosed as an acid generator (see, for example, Patent Document 2).

JP 59-45439 A JP 2003-307839 A

  The resist composition described in Patent Document 1 generates an acid from a diaryliodonium salt or the like by exposure, dissociates a t-butyl group or the like that protected the carboxyl group of the alkali-soluble resin by the action of the acid, A resist pattern can be formed by exposing the carboxyl group of the soluble resin and making the exposed region easily soluble in an alkali developer. However, this resist composition has a problem of low sensitivity to short wavelength radiation.

  In addition, the resist composition described in Patent Document 2 introduces an amide group or the like into the aryl group or the like of the triarylsulfonium salt of the acid generator, thereby improving sensitivity, resolution, There is an advantage that the profile and the like are improved. However, in recent years, the high integration of integrated circuit elements has been progressing rapidly, so that in the field of microfabrication, a resist having excellent resolving power that can form a resist pattern with higher definition than before. There is a need for materials. Considering such a situation, the resist composition described in Patent Document 2 is still not fully satisfactory in terms of resolution, and further improvement has been demanded.

  As described above, at present, a resist material capable of obtaining a sufficiently high resolution, for example, a high resolution capable of forming a sufficient process margin in a resist pattern of less than 0.1 μm with an ArF excimer laser is available. Not yet disclosed. Therefore, in the field of microfabrication, especially lithography, it has become an important issue to create a resist material that can obtain a high resolution that can cope with the high definition of resist patterns in recent years.

  The present invention has been made to solve the above-described problems of the prior art, and uses a novel compound having a chemical structure different from that of the conventional one and a higher definition using the compound. The present invention relates to a radiation-sensitive acid generator and a radiation-sensitive resin composition capable of forming a resist pattern. The compound of the present invention is an onium salt and is used in a radiation-sensitive resin composition as a radiation-sensitive acid generator.

  As a result of intensive studies to solve the problems of the prior art as described above, the present inventors have an aromatic onium salt such as triphenylsulfonium salt as a basic skeleton, and the aromatic ring has an oxygen atom or a sulfur atom interposed therebetween. Thus, the inventors have conceived that the above problems can be solved by an aromatic onium salt having an amino group introduced therein, and thus completed the present invention. Specifically, according to the present invention, the following compounds, a radiation sensitive acid generator and a positive radiation sensitive resin composition using the following compounds are provided.

〔一般式（１）において、Ａは硫黄原子、Ａｒは各々が同一若しくは異なった、下記置換基によって置換されていてもよい炭素数６〜２０の芳香族炭化水素基、Ｂは各々が同一若しくは異なった下記一般式（２）で示される構造の官能基、Ｒ^１及びＲ^２は各々が同一若しくは異なった、水素原子、下記置換基によって置換されていてもよい炭素数１〜２０のアルキル基、Ｒ^３は各々が同一若しくは異なった、下記置換基によって置換されていてもよい芳香族炭化水素基、Ｙ⁻はＡ^＋の対イオン、Ｚは酸素原子、ｘは１〜３の整数を示す。ｍは１〜３の整数、ｎは０〜２の整数（但し、ｍ＋ｎ＝３）である。〕

〔一般式（２）において、Ｒ ^４ 及びＲ ^５ は各々が同一若しくは異なった、水素原子、下記置換基によって置換されていてもよい炭素数１〜２０のアルキル基、下記置換基によって置換されていてもよい炭素数３〜２０の脂環族基、炭素数２〜２０のアルケニル基、下記置換基によって置換されていてもよい芳香族炭化水素基又は下記置換基によって置換されていてもよい複素環式炭化水素基、ｐは１〜２０の整数を示す。〕
置換基：ヒドロキシル基、カルボキシル基、シアノ基、炭素数１〜４のヒドロキシアルキル基、炭素数１〜４のアルコキシル基、炭素数２〜５のシアノアルキル基、アルコキシカルボニル基、アルコキシカルボニルアルコキシ基、ハロゲン原子、フルオロアルキル基。 [1] A compound represented by the following general formula (1).

In [general formula (1), A is sulfur atom, Ar each have the same or different, aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted by the following substituents, each B is the same Alternatively, different functional groups having the structure represented by the following general formula (2) , R ¹ and R ² are the same or different, a hydrogen atom, and an alkyl having 1 to 20 carbon atoms which may be substituted by the following substituents group, R ³ each is the same or different, aromatic be substitution by the following optionally substituted hydrocarbon group, Y ^- is a ⁺ counterion, Z is acid MotoHara child, x is 1 to 3 Indicates an integer . m is an integer of 1 to 3, n represents an integer of 0 to 2 (provided, m + n = 3) Ru der. ]

[In General Formula (2), R ⁴ and R ⁵ are the same or different and each is substituted with a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with the following substituents, or the following substituents. May be an alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aromatic hydrocarbon group which may be substituted with the following substituents, or a heterocycle which may be substituted with the following substituents. A cyclic hydrocarbon group, p represents an integer of 1 to 20; ]
Substituent: hydroxyl group, carboxyl group, cyano group, hydroxyalkyl group having 1 to 4 carbon atoms, alkoxyl group having 1 to 4 carbon atoms, cyanoalkyl group having 2 to 5 carbon atoms, alkoxycarbonyl group, alkoxycarbonylalkoxy group, A halogen atom, a fluoroalkyl group;

[ 2 ] A radiation-sensitive acid generator containing at least one compound according to [1 ] .

[ 3 ] An acid-dissociable group-modified alkali-soluble resin (component A) having an acidic group and at least a part of the acidic group protected by an acid-dissociable group, and a radiation-sensitive acid generator (component B) A positive radiation sensitive resin composition containing at least one compound according to [1 ] as the B component.

[ 4 ] The positive radiation sensitive resin composition according to [ 3 ], further comprising an acid diffusion inhibitor (component C) as a constituent component.

  The novel compound, radiation-sensitive acid generator, and positive-type radiation-sensitive resin composition of the present invention can obtain sufficiently satisfactory high resolution. For example, it exhibits an excellent resolution that can form a high-definition resist pattern of less than 0.1 μm with an ArF excimer laser.

  Hereinafter, the best mode for carrying out the compound, radiation sensitive acid generator and positive radiation sensitive resin composition of the present invention will be specifically described. However, the present invention includes all embodiments including the invention-specific matters, and is not limited to the embodiments described below.

〔一般式（１）において、Ａは硫黄原子又はヨウ素原子、Ａｒは各々が同一若しくは異なった、置換されていてもよい炭素数６〜２０の芳香族炭化水素基又は置換されていてもよい炭素数４〜２０の複素環式炭化水素基、Ｂは各々が同一若しくは異なった２価の官能基、Ｒ^１及びＲ^２は各々が同一若しくは異なった、水素原子、置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよい炭素数３〜２０の脂環族基、置換されていてもよい芳香族炭化水素基又は置換されていてもよい複素環式炭化水素基、Ｒ^３は各々が同一若しくは異なった、置換されていてもよい炭素数１〜１０のアルキル基、置換されていてもよい炭素数３〜２０の脂環族基、置換されていてもよい芳香族炭化水素基又は置換されていてもよい複素環式炭化水素基、Ｙ⁻は非求核性対イオン、Ｚは各々が同一若しくは異なった、酸素原子又は硫黄原子、ｘは１〜３の整数を示す。Ａが硫黄原子の場合には、ｍは１〜３の整数、ｎは０〜２の整数（但し、ｍ＋ｎ＝３）であり、Ａがヨウ素原子の場合には、ｍは１又は２、ｎは０又は１（但し、ｍ＋ｎ＝２）である。Ｒ^１とＲ^２が単結合、２価の官能基又は２価の原子を介して結合され、構成原子数が５〜１０の環構造を形成していてもよい。〕 [1] Compound:
The compound of the present invention is represented by the following general formula (1).

[In General Formula (1), A is a sulfur atom or an iodine atom, Ar is the same or different, and each is an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted carbon. A heterocyclic hydrocarbon group of 4 to 20; B is the same or different divalent functional group; R ¹ and R ² are the same or different and each is a hydrogen atom or an optionally substituted carbon number; An alkyl group having 1 to 20 carbon atoms, an optionally substituted alicyclic group having 3 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group or an optionally substituted heterocyclic hydrocarbon group, R ³ is the same or different, each optionally substituted alkyl group having 1 to 10 carbon atoms, optionally substituted alicyclic group having 3 to 20 carbon atoms, optionally substituted aromatic carbon A hydrogen group or an optionally substituted heterocyclic group Hydrocarbon group, Y ^- is a non-nucleophilic counter ion, Z is each is the same or different, an oxygen atom or a sulfur atom, x is an integer of 1-3. When A is a sulfur atom, m is an integer of 1 to 3, n is an integer of 0 to 2 (provided that m + n = 3), and when A is an iodine atom, m is 1 or 2, n Is 0 or 1 (where m + n = 2). R ¹ and R ² may be bonded through a single bond, a divalent functional group, or a divalent atom to form a ring structure having 5 to 10 constituent atoms. ]

[1-A] Cation moiety:
In the general formula (1), “A” represents a sulfur atom or an iodine atom. That is, examples of the compound of the present invention include a sulfonium salt in which “A” is a sulfur atom and an iodonium salt in which “A” is an iodine atom. Among these, a sulfonium salt in which “A” is a sulfur atom is preferable because of its high effect of improving the storage stability as an onium salt.

  In the general formula (1), “Ar” represents the same or different, each optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or optionally substituted carbon atoms 4 ˜20 heterocyclic hydrocarbon groups.

  Examples of the “aromatic hydrocarbon group having 6 to 20 carbon atoms” include phenyl group, toluyl group, benzyl group, methylbenzyl group, xylyl group, mesityl group, naphthyl group and anthryl group.

  “C4-C20 heterocyclic hydrocarbon group” means a group containing one or more heteroatoms such as a sulfur atom, an oxygen atom, and a nitrogen atom in the above-mentioned “aromatic hydrocarbon group”. Specifically, a furanyl group, a thiophenyl group, a pyridyl group, an imidazolyl group, a morpholinyl group, a piperidinyl group, a pyrrolidinyl group, and the like can be given.

  Among the aromatic hydrocarbon group and the heterocyclic hydrocarbon group, a phenyl group, a naphthyl group, or an anthryl group is preferable because it has a high effect of improving the light absorbency with respect to irradiation light of a KrF or ArF excimer laser. More preferred is a phenyl group.

  The “aromatic hydrocarbon group having 6 to 20 carbon atoms” or the “heterocyclic hydrocarbon group having 4 to 20 carbon atoms” may be one in which some or all of the hydrogen atoms are substituted with substituents. . Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3 A hydroxyalkyl group having 1 to 4 carbon atoms such as a hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group; a methoxy group, an ethoxy group, and an n-propoxy group , I-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group and the like alkoxy groups having 1 to 4 carbon atoms; cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl A cyanoalkyl group having 2 to 5 carbon atoms such as a 4-cyanobutyl group; a methoxycarbonyl group; Alkoxycarbonyl groups such as tooxycarbonyl group and t-butoxycarbonyl group; alkoxycarbonylalkoxy groups such as methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group and t-butoxycarbonylmethoxy group; halogen atoms such as fluorine and chlorine; fluoromethyl group; And fluoroalkyl groups such as a trifluoromethyl group and a pentafluoroethyl group;

  The compound of the present invention has an aromatic hydrocarbon group or a heterocyclic hydrocarbon group as described above, and an amino group is introduced into the aromatic ring via an oxygen atom or a sulfur atom. By introducing an amino group, it is possible to obtain an acid diffusion suppressing effect (specifically, an effect of suppressing the problem of reduced resolution due to diffusion of the generated acid), and as a result, a sufficiently satisfactory high resolution can be obtained. be able to.

  In order to obtain the effect as described above, each Z may be an oxygen atom or a sulfur atom. However, it is preferable that all of Z are oxygen atoms because the effect of improving the storage stability of the compound is high.

  Further, the compound of the present invention does not directly bind an amino group to an oxygen atom or sulfur atom bonded to an aromatic ring, but between the oxygen atom or sulfur atom and the amino group, in the general formula (1), It has a structure in which a “divalent functional group” represented by “B” is interposed and an oxygen atom or the like and an amino group are bonded via this “B”. With such a structure, the amino group is difficult to decompose, so that the stability of the onium salt is improved. In addition, when a “divalent functional group” is interposed, the basicity of the amino group can be controlled by the type of atom or functional group, and a desired level of acid diffusion suppression effect can be obtained. .

In the general formula (1), examples of the “divalent functional group” represented by “B” include inorganic functional groups such as —SO ₂ — and —SO ₂ O—; —CO—, —COO—, — OCOO -, - NR '-, - NR'CO -, - OCH 2 CONR' -, - O (CH 2) 2 CONR '-, - SCH 2 CONR' -, - S (CH 2) 2 CONR'- like Organic functional groups of However, "R '" couple | bonded with a nitrogen atom in the said general formula is respectively the same or different, i) The linear or branched alkyl group (C1-C20) which may be substituted, ii) An optionally substituted monovalent alicyclic hydrocarbon group (3 to 20 carbon atoms) or iii) a linear or branched alkenyl group (2 to 20 carbon atoms).

  In the general formula (1), the “divalent functional group” represented by “B” is a divalent organic functional group, especially, because it has a high effect of improving the storage stability of the compound. Preferred is a divalent hydrocarbon group. Examples of the unsubstituted divalent hydrocarbon group include a methylene group; 1,1-ethylene group, 1,2-ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, and the like. An alkylene group having 2 to 8 carbon atoms; a cycloalkylene group having 3 to 10 carbon atoms such as 1,3-cyclopentylene group, 1,3-cyclohexylene group and 1,4-cyclohexylene group; 1,3-phenylene Group, an arylene group having 6 to 14 carbon atoms such as 1,4-phenylene group, methyl-1,4-phenylene group, 1,4-phenylenemethylene group, and the like.

  The divalent hydrocarbon group may be one in which some or all of the hydrogen atoms are substituted with substituents. Examples of the substituent of the methylene group or alkylene group include a hydroxyl group, a carboxyl group, a cyano group, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a 2-methylpropoxy group. An alkoxyl group having 1 to 4 carbon atoms such as 1-methylpropoxy group and t-butoxy group; an alkylcarbonyloxy group having 2 to 5 carbon atoms such as methylcarbonyloxy group, ethylcarbonyloxy group and t-butylcarbonyloxy group An alkoxycarbonyl group having 2 to 5 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a t-butoxycarbonyl group; a carbon atom having 3 to 6 carbon atoms such as a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group and a t-butoxycarbonylmethoxy group; Alkoxycarbonylalkoxy group; fluorine atom, chlorine Halogen atoms child like; and the like.

  Examples of the substituent of the cycloalkylene group or the arylene group include a hydroxyl group, a carboxyl group, a cyano group, an oxo group (═O), a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- C1-C4 alkyl group such as butyl group and t-butyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl Group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and other C1-C4 hydroxyalkyl groups; methoxy group, ethoxy group, n-propoxy group, i- 1 to 4 carbon atoms such as propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group Alkoxyl group; C2-C5 cyanoalkyl group such as cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group; methylcarbonyloxy group, ethylcarbonyloxy group, t-butylcarbonyloxy group, etc. An alkylcarbonyloxy group having 2 to 5 carbon atoms; an alkoxycarbonyl group having 2 to 5 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a t-butoxycarbonyl group; a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group and a t-butoxy An alkoxycarbonylalkoxy group having 3 to 6 carbon atoms such as a carbonylmethoxy group; a halogen atom such as a fluorine atom or a chlorine atom; a fluoroalkyl group having 1 to 4 carbon atoms such as a fluoromethyl group, a trifluoromethyl group or a pentafluoroethyl group And so on That.

  In the methylene group, alkylene group, cycloalkylene group or arylene group, part or all of the hydrogen atoms may be substituted with one kind of substituent, or may be substituted with two or more kinds of substituents. .

  As described above, in the general formula (1), the “divalent functional group” represented by “B” is preferably a “divalent hydrocarbon group”, but may be substituted. It is preferable that it is a C1-C20 alkylene group which may be contained or a C3-C20 alicyclic group which may be substituted. “It may contain a ring structure” means that a part of the carbon chain of the “alkylene group” is replaced with a ring structure such as an alicyclic group, and is included in the concept of the “alkylene group”. means.

〔一般式（２）において、Ｒ^４及びＲ^５は各々が同一若しくは異なった、水素原子、置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよい炭素数３〜２０の脂環族基、置換されていてもよい芳香族炭化水素基又は置換されていてもよい複素環式炭化水素基、ｐは１〜２０の整数を示す。Ｒ^４及びＲ^５は、Ｒ^１、Ｒ^２、Ｒ^４又はＲ^５のいずれかと、単結合、２価の官能基又は２価の原子を介して結合され、構成原子数が５〜１０の環構造を形成していてもよい。〕 In the general formula (1), B is more preferably a functional group having a structure represented by the following general formula (2).

[In General Formula (2), each of R ⁴ and R ⁵ is the same or different, a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, and an optionally substituted carbon atom having 3 to 20 carbon atoms. An alicyclic group, an optionally substituted aromatic hydrocarbon group or an optionally substituted heterocyclic hydrocarbon group, p represents an integer of 1 to 20. R ⁴ and R ⁵ are bonded to any one of R ¹ , R ² , R ⁴ or R ⁵ via a single bond, a divalent functional group or a divalent atom, and a ring having 5 to 10 constituent atoms A structure may be formed. ]

In the general formula (1), examples of the “alkyl group having 1 to 20 carbon atoms” represented by “R ⁴ ” to “R ⁵ ” include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, i-propyl group, i-butyl group, sec-butyl group, t-butyl group, Examples thereof include a t-dodecyl group.

  Examples of the “C3-C20 alicyclic group” include, for example, cyclopentyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, tricyclodecanyl group, tetracyclododecyl group, adamantyl group, methyladamantyl group A bridged alicyclic hydrocarbon group having 6 to 20 carbon atoms such as a group, an ethyladamantyl group, and a butyladamantyl group.

  Examples of the “aromatic hydrocarbon group” and “heterocyclic hydrocarbon group” include the groups already exemplified in the section “Ar”.

Each hydrocarbon group represented by “R ⁴ ” to “R ⁵ ” may be one in which part or all of the hydrogen atoms are substituted with a substituent. Examples of such a substituent include the groups already exemplified as the substituent constituting the substituted aromatic hydrocarbon group and the substituted heterocyclic hydrocarbon group in the “Ar” section. Among them, an alkyl group or a cycloalkyl group is preferable and an alkyl group is more preferable because the acid diffusion suppressing effect as a radiation sensitive acid generator is high.

“R ⁴ ” to “R ⁵ ” are methyl group, ethyl group, n-propyl group, i-propyl group, n group and the like because of the high effect of improving the crystallinity of the compound among the groups exemplified above. -Butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group, t-dodecyl group, n-hexadodecyl group, cyclopentyl group, cyclohexyl group , Camphoroyl group, norbornyl group, p-toluyl group, benzyl group, phenyl group, 1-naphthyl group, 2-naphthyl group, trifluoromethyl group, nonafluorobutyl group, perfluorooctyl group, methoxycarbonyldifluoromethyl group are preferable. .

  As described above, in the general formula (1), the “divalent functional group” represented by “B” has been described. Among these, for the reason that the effect of improving the crystallinity of the compound is high, the alkylene group is An ethylene group and a propylene group are more preferable.

In the general formula (1), “R ¹ ” and “R ² ” are the same or different from each other, a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, and a substituted group. An alicyclic group having 3 to 20 carbon atoms, an aromatic hydrocarbon group which may be substituted, or a heterocyclic hydrocarbon group which may be substituted. Specific examples of these substituents include the same substituents as those described in the sections of “R ⁴ ” and “R ⁵ ”, and the same applies to preferable substituents.

“R ¹ and R ² may be bonded through a single bond, a divalent functional group or a divalent atom to form a ring structure having 5 to 10 constituent atoms”. Each atom or functional group is dissociated from R ¹ and R ² to form a residue, and the residues are directly bonded by a single bond or via a divalent functional group or a divalent atom. It means that the compound of the present invention includes those in which a ring structure having 5 to 10 constituent atoms (that is, a 5-membered ring to 10-membered ring structure) is formed by indirectly bonding. Yes. However, this ring structure is not an essential structure for the compound of the present invention. That is, the compound of the present invention includes both those having no such ring structure and those having a ring structure formed between R ^{1 and} R ² . “R ⁴ and R ⁵ are bonded to any of R ¹ , R ² , R ⁴ or R ⁵ via a single bond, a divalent functional group or a divalent atom, and the number of constituent atoms is 5 to 10 “A ring structure may be formed” has the same meaning.

  Examples of the “divalent functional group” include a methylene group; a divalent alkylene group such as an ethylene group; and other divalent organic functional groups such as an arylene group. Among these, an alkylene group is preferable because it has a high effect of improving the transmittance of irradiation light of KrF, ArF excimer laser. The “divalent functional group” may include a hetero atom including a sulfur atom, an oxygen atom and a nitrogen atom in the main chain. Examples of the “divalent atom” include —O— and —S—.

In the general formula (1), “R ³ ” is the same or different, each having an optionally substituted alkyl group having 1 to 10 carbon atoms, and optionally having 3 to 20 carbon atoms. An alicyclic group, an optionally substituted aromatic hydrocarbon group or an optionally substituted heterocyclic hydrocarbon group. Specific examples of these substituents include the same substituents as those described in the sections of “R ⁴ ” and “R ⁵ ”, and the same applies to preferable substituents.

  Since “x” in the general formula (1) is an integer of 1 to 3, at least one amino group and at most three amino groups are introduced per one aromatic hydrocarbon group or the like. When “x” is 1 to 2, it is preferable because alkali developability of the radiation-sensitive resin composition is improved.

When “A” is a sulfur atom, “m” in the general formula (1) is an integer of 1 to 3, “n” is an integer of 0 to 2, and the sum of “m” and “n” is 3. is there. That is, the sulfonium salt in which “A” is a sulfur atom has three aromatic hydrocarbon groups or heterocyclic hydrocarbon groups, of which at least one aromatic hydrocarbon group has an oxygen atom. And an amino group may be introduced via a sulfur atom. In addition, when n = 2, R ³ may be bonded via an alkylene group having 2 to 10 carbon atoms which may be substituted with each other to form a ring structure together with the bonded sulfur atom.

  On the other hand, when “A” is an iodine atom, “m” in the general formula (1) is 1 or 2, “n” is 0 or 1, and the sum of “m” and “n” is 2. That is, the iodonium salt in which “A” is an iodine atom has two aromatic hydrocarbon groups or heterocyclic hydrocarbon groups, and at least one of the aromatic hydrocarbon groups has an oxygen atom. And an amino group may be introduced via a sulfur atom.

  The cation moiety of the compound of the present invention is preferably a cation having the structure of (K-1) to (K-6) exemplified in Table 1.

[1-B] Anion moiety (counter ion of A ⁺ ):
In the general formula (1), examples of the “non-nucleophilic counter ion” represented by “Y ⁻ ” include CH ₃ SO ₃ ⁻ , C ₄ H ₉ SO ₃ ⁻ , C ₈ H ₁₇ SO ₃ ⁻ and p. In addition to sulfonate anions such as —CH ₃ C ₆ H ₄ SO ₃ ^— , CF ₃ SO ₃ ^— , C ₄ F ₉ SO ₃ ^— , C ₈ F ₁₇ SO ₃ ^—, etc., the general formula (Y -1) to (Y-2), that is, sulfonate anions containing a norbornane skeleton or a norbornene skeleton.

The sulfonate anion having the structure of the general formulas (Y-1) to (Y-2) will be described more specifically. In the general formulas (Y-1) to (Y-2), R ^y is a monovalent or divalent substituent, D is a single bond, a divalent atom or a divalent functional group, and E ¹ and E ² are each Are the same or different, fluorine atom, linear or branched perfluoroalkyl group (1 to 10 carbon atoms), (Y-1) and (Y-2), k is an integer of 0 to 5, n is An integer of 0 to 5 is shown.

Examples of the “monovalent or divalent substituent” represented by “R ^y ” include an oxo group (═O), a hydroxyl group, a carboxyl group, a formyl group, an alkyl group (having 1 to 10 carbon atoms), and a vinylidene group. (C1-C10) monovalent cyclic organic group (C1-C12), C6-C20 aryl group, alkoxyl group (C1-C10), C6-C20 aryloxy group, Examples thereof include an alkylcarbonyl group (2 to 10 carbon atoms), an arylcarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group (1 to 10 carbon atoms), an aryloxycarbonyl group (7 to 20 carbon atoms), and the like. Of these groups, the alkyl group, vinylidene group, alkoxyl group, alkylcarbonyl group and alkoxycarbonyl group may be linear or branched.

  Examples of the “alkyl group” include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, C1-C10 alkyl groups, such as an n-octyl group, n-nonyl group, n-decyl group, can be mentioned. Examples of the “linear or branched vinylidene group” include a carbenyl group, a 1,1-ethylidenyl group, a propylidenyl group, a 1-methylpropylidenyl group, a 1-ethylpropylidenyl group, and the like. Mention may be made of vinylidene groups having 1 to 10 carbon atoms.

  Examples of the “monovalent cyclic organic group” include a cyclic organic group having 1 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a camproyl group. Examples of the “aryl group having 6 to 20 carbon atoms” include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a p-hydroxyphenyl group, a 1-naphthyl group, and a 1-anthracenyl group. And benzyl group.

  Examples of the “alkoxyl group” include an alkoxyl group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a t-butoxy group. Examples of the “C6-C20 aryloxy group” include phenoxy group, p-hydroxyphenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group and the like.

  Examples of the “alkylcarbonyl group” include alkyl having 2 to 10 carbon atoms such as methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, t-butylcarbonyl group and the like. A carbonyl group can be mentioned. Examples of the “arylcarbonyl group having 7 to 20 carbon atoms” include a phenylcarbonyl group and a benzylcarbonyl group.

  Examples of the “alkoxycarbonyl group” include alkoxy having 2 to 10 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group and the like. A carbonyl group can be mentioned. Examples of the “C 7-20 aryloxycarbonyl group” include a phenoxycarbonyl group and a benzyloxycarbonyl group.

The substituent represented by “R ^y ” may be further substituted with an arbitrary substituent. For example, it may be substituted with at least one of the substituents exemplified as “monovalent or divalent substituent”.

Since “k” in the general formulas (Y-1) to (Y-2) is an integer of 0 to 5, the carbon atom constituting the norbornane ring or the norbornene ring is completely substituted by the substituent represented by “R ^y ”. It may not be substituted, or a plurality may be substituted. When substituted by a substituent more carbon atoms is represented by "R ^y", each "R ^y" may be the same substituent, may be different substituents. However, it is preferable that “k” is 0 because the alkali developability of the radiation-sensitive resin composition is improved. That is, it is preferable that the carbon atom constituting the norbornane ring or the norbornene ring is not substituted at all by the substituent represented by “R ^y ”.

  Since “n” in the general formulas (Y-1) to (Y-2) is an integer of 0 to 5, the norbornane ring and the norbornene ring may be condensed or may not be condensed. However, it is preferable that “n” is 0 or 1, since the alkali developability of the radiation-sensitive resin composition is improved. That is, the norbornane skeleton or the norbornene skeleton is preferably one obtained by condensing two norbornane or norbornene rings, or a non-condensed norbornane or norbornene ring.

  Examples of the “divalent atom” represented by “D” include —O— and —S—, and examples of the “divalent functional group” include a carbonyl group, a sulfinyl group, and a sulfonyl group. Group, methylene group, 1,1-ethylene group, 1,2-ethylene group, propylene group, 1-methylpropylene group, 1-ethylpropylene group, trimethylene group, difluoromethylene group, tetrafluoro-1,2-ethylene group 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group and the like. Among the “divalent functional groups”, a carbonyl group, a methylene group, a difluoromethylene group, a tetrafluoro-1,2-ethylene group and the like are preferable. “D” is preferably a single bond, a methylene group or a carbonyl group.

Examples of the “linear or branched perfluoroalkyl group” represented by “E ¹ ” and “E ² ” include, for example, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, and a nonafluoro-n. -C1-C10 perfluoroalkyl groups, such as a butyl group, can be mentioned. As “E ¹ ” and “E ² ”, a fluorine atom or a trifluoromethyl group is preferable. “E ¹ ” and “E ² ” may be of the same type or different types.

  Examples of the sulfonate anion having the structure represented by the general formulas (Y-1) to (Y-2) include those represented by (Y-1a) to (Y-1f) in Table 3, and (Y- 1g) to (Y-1l), those shown in Table 5 (Y-2a) to (Y-2g), and those in Table 6 (Y-2h) to (Y-2m) The structure shown by these can be mentioned. The sulfonate anions exemplified in Tables 3 to 6 include various isomers. For example, the norbornane skeleton or the norbornene skeleton may be an exo type or an endo type.

The “non-nucleophilic counter ion” represented by “Y ⁻ ” is CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ or shown in Table 5 because of its high acidity (Y-2b) Or the structure shown by (Y-2d) is preferable.

〔前記反応式において、Ａ、Ａｒ、Ｂ、Ｒ^１、Ｒ^２、Ｒ^３、Ｙ⁻、Ｚ、ｍ、ｎ、ｘは前記の定義通りである。Ｘはヨウ素原子、臭素原子又は塩素原子を示す。〕 [1-C] Production method:
The compound (1) of the present invention includes, for example, a compound having a Z—H group represented by the following general formula (3) and an amine halide hydrochloride represented by the following general formula (4) (hereinafter referred to as “amine halogen”). Compound hydrochloride)) in the presence of a suitable base.

[In the above reaction formula, A, Ar, B, R ¹ , R ² , R ³ , Y ⁻ , Z, m, n, and x are as defined above]. X represents an iodine atom, a bromine atom or a chlorine atom. ]

  The molar ratio of amine halide hydrochloride (4) to compound (3) is usually from 1 to 100, preferably from 1.5 to 15.

  Examples of the base used for the reaction include triethylamine, pyridine, potassium hydroxide, sodium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate and the like. Among these, potassium carbonate is preferable because it has moderate basicity. The molar ratio of the base to the amine halide hydrochloride (4) is usually 1.0 to 10.0, preferably 1.5 to 4.0.

  This reaction is performed in an aprotic organic solvent such as toluene, tetrahydrofuran, methylene chloride, pyridine, DMF, DMSO, acetone or the like. Of these, the reaction is preferably carried out in DMF or acetone. The use ratio of the organic solvent is usually 5 to 100 parts by mass, preferably 10 to 100 parts by mass, and preferably 20 to 90 parts by mass with respect to 100 parts by mass in total of the organic solvent and water. Is more preferable.

  The reaction temperature is usually −40 to 100 ° C., preferably −20 to 80 ° C. Moreover, reaction time is 0.1 to 72 hours normally, and it is preferable to set it as 0.5 to 10 hours.

[2] Positive radiation sensitive resin composition:
The positive radiation sensitive resin composition of the present invention is a composition containing an acid dissociable group-modified alkali-soluble resin (component A) and a radiation sensitive acid generator (component B) as essential components.

[2-A] Acid-dissociable group-modified alkali-soluble resin (component A):
The “acid-dissociable group-modified alkali-soluble resin” is a resin having an acidic group and at least a part of the acidic group being protected by the acid-dissociable group. This resin exhibits alkali insolubility or alkali insolubility in a state where at least part of the acid groups in the resin is protected by the acid dissociable group. However, when the acid dissociable group is dissociated by the action of an acid, the acid group is It is a resin that is exposed and exhibits alkali solubility.

  Here, “alkali insoluble or hardly alkali soluble” is obtained by a radiation sensitive resin composition containing an acid dissociable group-modified alkali soluble resin (component A) and a radiation sensitive acid generator (component B). When a film obtained only with an acid-dissociable group-modified alkali-soluble resin is developed instead of the resist film under the alkali development conditions used when forming a resist pattern from the resist film formed, the initial film of the film It means that 50% or more of the thickness remains after development.

  The “acidic group” is not particularly limited as long as it is a functional group exhibiting acidity. For example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc. can be mentioned. Among these, a phenolic hydroxyl group and a carboxyl group are preferable because the effect of improving the solubility in alkali is high. Of these, the acid-dissociable group-modified alkali-soluble resin may have only one acidic group, or may have two or more acidic groups.

  Examples of the “acid-dissociable group” include substituted methyl group, 1-substituted ethyl group, 1-substituted n-propyl group, 1-branched alkyl group, silyl group, germyl group, alkoxycarbonyl group, acyl group and ring. Formula acid dissociable groups and the like can be mentioned.

  More specifically, examples of the “substituted methyl group” include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, and a 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-nitrobenzyl group, 4-methoxybenzyl group, 4-methylthiobenzyl group, 4-ethoxybenzyl group, 4-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group I-propoxycarbonyl me Le group, n- butoxycarbonyl methyl group, and 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-diethyl Ethoxyethyl 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 group 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, etc. That.

  Examples of the “1-substituted-n-propyl group” include 1-methoxy-n-propyl group and 1-ethoxy-n-propyl group, and the “1-branched alkyl group” includes, for example, i-propyl. Group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group and the like.

  Examples of the “silyl group” include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, t Examples thereof include -butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group and the like.

  Examples of the “germyl group” include trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, i-propyldimethylgermyl group, methyldi-i-propylgermyl group, tri- List i-propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group, etc. Can do.

  Examples of the “alkoxycarbonyl group” include methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, t-butoxycarbonyl group and the like.

  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, camphoroyl group, Benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydroatropoyl, atropoyl, cinnamoyl, furoyl, thenoyl, nicotinoyl, Nicotinoyl 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 tetrahydrothio group. Examples include furanyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene-1,1-dioxide group.

  Among these “acid-dissociable groups”, benzyl group, t-butoxycarbonylmethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 1-ethoxy-n-propyl group, A t-butyl group, 1,1-dimethylpropyl group, trimethylsilyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group and the like are preferable.

  The acid-dissociable group-modified alkali-soluble resin may have an acidic group protected by only one acid-dissociable group among the acid-dissociable groups, or two or more acid-dissociable groups acidic. It may be protected by a group.

  In the acid-dissociable group-modified alkali-soluble resin, it is sufficient that at least a part of the acidic group is protected by the acid-dissociable group, and it is not necessary that all of the acidic groups are protected by the acid-dissociable group. The rate of introduction of acid dissociable groups (ratio of the number of acid dissociable groups to the total number of acid groups and acid dissociable groups in the acid dissociable group-modified alkali-soluble resin) It depends on the type of resin. However, the introduction rate is preferably in the range of 5 to 100%, and more preferably in the range of 10 to 100%.

  The structure of the acid-dissociable group-modified alkali-soluble resin is not particularly limited as long as it has the above-described properties, and various structures can be used as necessary. For example, a resin in which part or all of the hydrogen atoms of the phenolic hydroxyl group in poly (p-hydroxystyrene) are substituted with the acid dissociable group, p-hydroxystyrene and / or p-hydroxy-α-methylstyrene ( Resins in which part or all of the hydrogen atoms of the phenolic hydroxyl group and / or the carboxyl group in the copolymer with (meth) acrylic acid have been substituted with the acid dissociable groups, and the branched structure described later in these resins. The introduced resin or the like can be suitably used.

  In addition, the structure of the acid-dissociable group-modified alkali-soluble resin can be various structures depending on the type of radiation used. For example, when a KrF excimer laser is used, the phenolic hydroxyl group contained in the repeating unit represented by the following general formula (5) and the repeating unit represented by the following general formula (5) is protected with the acid dissociable group. An alkali-insoluble (hard) soluble resin (hereinafter, also referred to as “resin (A1)”) containing the above repeating unit is preferable. The resin (A1) can also be suitably used for a radiation sensitive resin composition using EUV, electron beam or the like.

〔一般式（５）において、Ｒ^６は水素原子又は一価の有機官能基を示す。ａ及びｂは１〜３の整数を示す。〕

[In General Formula (5), R ⁶ represents a hydrogen atom or a monovalent organic functional group. a and b show the integer of 1-3. ]

  Examples of the repeating unit represented by the general formula (5) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methylhydroxystyrene, 3-methyl-4-hydroxystyrene, 2-methyl-4- Non-aromatic double such as hydroxy styrene, 2-methyl 3-hydroxy styrene, 4-methyl 3-hydroxy styrene, 5-methyl 3-hydroxy styrene, 3,4-dihydroxy styrene, 2,4,6-trihydroxy styrene Mention may be made of units in which the bond is cleaved. Among these, a unit in which a non-aromatic double bond is cleaved, such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methylhydroxystyrene and the like is preferable.

  Examples of the repeating unit containing an acid dissociable group include a repeating unit in which the phenolic hydroxyl group of the repeating unit represented by the general formula (5) is protected with the acid dissociable group.

  The resin (A1) may further contain other repeating units. Examples of such other repeating units include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4 -T-butoxystyrene, 4-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethyloxystyrene, 4- (2'-t-butoxycarbonylethyloxy) styrene, 4-tetrahydrofuranyloxystyrene, 4-tetrahydro Vinyl aromatic compounds such as pyranyloxystyrene;

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, Sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2- (meth) acrylic acid 2- Ethylhexyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Norbornyl acid, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate (Meth) acrylic acid dicyclopentenyl, (meth) acrylic acid adamantyl (meth) acrylic acid 2-methyladamantyl, (meth) acrylic acid tetrahydrofuranyl, (meth) acrylic acid tetrahydropyranyl, (meth) acrylic acid phenyl, Benzyl (meth) acrylate, phenethyl (meth) acrylate,

  Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid; (meth) acrylic acid 2-carboxyethyl, (meth) acrylic acid 2-carboxypropyl, (meth) acrylic acid Carboxyalkyl esters of unsaturated carboxylic acids such as 3-carboxypropyl; unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile; (meth) acrylamide, N, N-dimethyl Unsaturated amide compounds such as (meth) acrylamide, crotonamide, maleamide, and fumaramide; unsaturated imide compounds such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; N-vinyl-ε-caprolactam, N-vinylpyrrolidone, 2- Examples include units in which a polymerizable unsaturated bond such as vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, 2-vinyl imidazole, and 4-vinyl imidazole and other nitrogen-containing vinyl compounds are cleaved.

  Among the other repeating units, styrene, α-methylstyrene, 4-t-butoxystyrene, 4-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethyloxystyrene, 4- (2′-t- Polymerizable unsaturated bonds such as butoxycarbonylethyloxy) styrene, t-butyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-methyladamantyl (meth) acrylate Cleaved units are preferred.

In the case of using an ArF excimer laser, an alkali-insoluble (hard) soluble resin (hereinafter also referred to as “resin (A2)”) having a repeating unit represented by the following general formula (6) is preferable. The resin (A2) can also be suitably used for a radiation sensitive resin composition using an F ₂ excimer laser, an electron beam, or the like.

〔一般式（６）において、Ｒ^７は水素原子又はメチル基を示す。また、各Ｒ^８は各々が同一若しくは異なった、直鎖状若しくは分岐状のアルキル基（炭素数１〜４）、置換されていてもよい１価の脂環式炭化水素基（炭素数４〜２０）又はいずれか２つのＲ^８が互いに結合して、それぞれが結合している炭素原子と共に置換されてもよい炭素数４〜２０の２価の脂環式炭化水素基を形成し、残りのＲ^８が炭素数１〜４の直鎖状若しくは分岐状のアルキル基又は置換されていてもよい１価の脂環式炭化水素基（炭素数４〜２０）である。〕

[In General Formula (6), R ⁷ represents a hydrogen atom or a methyl group. Each R ⁸ is the same or different and is a linear or branched alkyl group (1 to 4 carbon atoms), an optionally substituted monovalent alicyclic hydrocarbon group (4 to 4 carbon atoms). 20) or any two of R ⁸ are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms which may be substituted together with the carbon atom to which each is bonded, and the remaining R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms or an optionally substituted monovalent alicyclic hydrocarbon group (4 to 20 carbon atoms). ]

〔前記一般式において、Ｒ^７は水素原子又はメチル基である。〕 Moreover, as a repeating unit represented by the said General formula (6), the repeating unit derived from t-butoxycarbonyl (meth) acrylate and the repeating unit represented by the following general formula are preferable, for example.

[In the above general formula, R ⁷ represents a hydrogen atom or a methyl group. ]

  The resin (A2) may further contain other repeating units. Examples of such other repeating units include norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo. [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-fluorobicyclo [2.2.1] hept-2-ene, tetracyclo [4 4.0.12, 5.17,10] dodec-3-ene, 8-methyltetracyclo [4.4.0.12, 5.17,10] dodec-3-ene, 8-ethyltetracyclo [4.4.0.12, 5.17,10] dodec-3-ene, 8-hydroxytetracyclo [4.4.0.12,5.17,10] dodec-3-ene, 8-fluoro Tetracyclo [4.4.0.12,5.17,10] do Monomers having a norbornene skeleton of mosquito-3-ene;

〔一般式（７）において、Ｒ^７は水素原子又はメチル基である。〕 Acid anhydrides such as maleic anhydride and itaconic anhydride; (meth) acrylic acid represented by the following general formula (7) in addition to the (meth) acrylic acid ester described as the other repeating unit in the resin (A1) Examples include units in which a polymerizable unsaturated bond such as an ester is cleaved.

In [Formula ^(7), R 7 is a hydrogen atom or a methyl group. ]

  There is no particular limitation on the molecular weight range of the acid-dissociable group-modified alkali-soluble resin, and various molecular weight ranges can be used as necessary. The polystyrene-reduced mass molecular weight (may be referred to as “Mw”) measured by gel permeation chromatography (GPC) is usually 1000 to 500,000, preferably 2000 to 400,000, and preferably 3000 to 300,000. Is more preferable. Moreover, in the case of resin which does not have a branched structure, it is more preferable that it is 1000-150,000, and it is especially preferable that it is 3000-100000. In the case of a resin having a branched structure, it is more preferably 5,000 to 500,000, and particularly preferably 8,000 to 300,000. By setting it as such a range, the development characteristic of the resist obtained will be excellent.

  There is no particular limitation on the method for producing the acid dissociable group-modified alkali-soluble resin. For example, in addition to the method of introducing one or more acid-dissociable groups into the acid group in an alkali-soluble resin produced in advance, one or more polymerizable compounds having the acid group protected by the acid-dissociable group A method of polymerizing an unsaturated monomer or one or more polymerizable unsaturated monomers thereof and one or more other polymerizable unsaturated monomers, or the acidic group protected with the acid dissociable group Or a polycondensation of one or more polycondensation components and one or more other polycondensation components.

  Here, the one or more polymerizable unsaturated monomers having the acidic group protected by the acid dissociable group, or the one or more polymerizable unsaturated monomers and one or more other polymerizable monomers. In the method of polymerizing with an unsaturated monomer, a polymerization initiator such as a radical polymerization initiator, an anionic polymerization catalyst, a coordination anionic polymerization catalyst, a cationic polymerization catalyst, or a polymerization depending on the type of monomer or reaction medium. The catalyst can be selected appropriately and can be carried out by an appropriate polymerization method such as bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, bulk-suspension polymerization. In the method of polycondensing one or more polycondensation components having the acidic group protected by the acid dissociable group or the one or more polycondensation components and one or more other polycondensation components, (Co) polycondensation can be carried out in an aqueous medium or in a mixed medium of water and a hydrophilic solvent in the presence of an acidic catalyst.

[2-B] Radiation sensitive acid generator (component B):
The positive radiation sensitive resin composition of the present invention needs to contain at least one compound of the present invention as a radiation sensitive acid generator. Such a composition can provide sufficiently satisfactory high resolution, for example, high resolution capable of forming a resist pattern of less than 0.1 μm with an ArF excimer laser.

  In addition, the positive radiation sensitive resin composition of the present invention may contain a radiation sensitive acid generator (B ′ component) other than the compound of the present invention together with the compound of the present invention. Examples of such an acid generator include onium salts and sulfonimide compounds other than the compound of the present invention.

  Examples of the “onium salt” include bis (4-t-butylphenyl) iodonium nonafluorobutanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, and bis (4-t-butylphenyl) iodonium perfluoro. Octanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, 4-trifluoromethylbenzenesulfonate,

  Bis (4-t-butylphenyl) iodonium perfluorobenzenesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium perfluorooctanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10 -Camphorsulfonate, diphenyliodonium 4-trifluoromethylbenzenesulfonate, diphenyliodonium perfluorobenzenesulfonate,

  Bis (p-fluorophenyl) iodonium trifluoromethanesulfonate, bis (p-fluorophenyl) iodonium nonafluoromethanesulfonate, bis (p-fluorophenyl) iodonium camphorsulfonate, (p-fluorophenyl) (phenyl) iodonium trifluoromethanesulfonate,

  Triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium-2-bicyclo [2.2.1] hept-2-yl-1,1-difluoroethanesulfonate, Triphenylsulfonium-2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium 4-trifluoromethylbenzenesulfonate,

  Triphenylsulfonium perfluorobenzenesulfonate, 4-hydroxyphenyl diphenylsulfonium trifluoromethanesulfonate, tri (p-methoxyphenyl) sulfonium nonafluorobutanesulfonate, tri (p-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (p-methoxyphenyl) ) Sulfonium perfluorooctane sulfonate, tri (p-methoxyphenyl) sulfonium p-toluenesulfonate, tri (p-methoxyphenyl) sulfonium benzene sulfonate, tri (p-methoxyphenyl) sulfonium 10-camphor sulfonate, tris (p-fluorophenyl) ) Sulfonium trifluoromethanesulfonate, tris (p-fluorophenyl) sulfoniu p- toluenesulfonate, may be mentioned (p- fluorophenyl) diphenyl sulfonium trifluoromethanesulfonate, and the like.

Examples of the “sulfonimide compound” include compounds represented by the following general formula (8).

  In the general formula (8), V represents a divalent organic functional group such as an alkylene group, an arylene group, or an alkoxylene group. Specifically, a methylene group, an alkylene group having 2 to 20 carbon atoms, an aralkylene group having 2 to 20 carbon atoms, a difluoromethylene group, a perfluoroalkylene group having 2 to 20 carbon atoms, a cyclohexylene group, or a substituted group. Examples thereof include a group having a good norbornane skeleton, a phenylene group, and a group in which an aromatic hydrocarbon group having 2 or more carbon atoms or an alkoxyl group is introduced into these groups as a substituent.

In the general formula (8), R ¹⁰ represents a monovalent organic functional group such as an alkyl group, an aromatic hydrocarbon group, a halogen-substituted alkyl group, and a halogen-substituted aromatic hydrocarbon group. Specifically, an alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, a perfluorocycloalkyl group having 3 to 10 carbon atoms, a bicyclo ring-containing hydrocarbon group having 7 to 15 carbon atoms, A C6-C12 aromatic hydrocarbon group etc. can be mentioned. Specifically, alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group and n-decyl group; Perfluoroalkyl group such as trifluoromethyl group, pentafluoroethyl group, nonafluoro-n-butyl group, perfluoro-n-octyl group; perfluorocycloalkyl group such as pentafluorocyclohexyl group; alkyl group, alkoxyl group, alkoxy A bicyclo ring-containing hydrocarbon group such as a group having a norbornane skeleton which may be substituted with a carbonyl group, an alkylalkoxycarbonyl group, etc .; a phenyl group, a perfluorophenyl group, a methylphenyl group, a trifluoromethylphenyl group, a tolyl group, An aromatic hydrocarbon group such as a naphthyl group can be exemplified.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) ) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) bicyclo [2] 2.1] hept-5-ene-2,3-dicarboximide, N- (4-trifluoro) Methylbenzenesulfonyl) succinimide, N-(4-trifluoromethyl benzenesulfonyl oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,

  N- (perfluorobenzenesulfonyloxy) succinimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluorobutylsulfonyloxy) ) Succinimide, N- (nonafluorobutylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluorooctanesulfonyloxy) succinimide, N- (perfluoro Octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) succinimide, N- (benzenesulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- ( Nzensulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-{(5-methyl-5-carboxymethanebicyclo [2.2.1] And hept-2-yl) sulfonyloxy} succinimide.

  Among the sulfonimide compounds, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) succinimide, N- (nonafluorobutylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N-{(5-methyl-5-carboxymethanebicyclo [2.2.1] hept-2-yl) sulfonyloxy} Succinimide is preferred.

  The mixing ratio of the other acid generator can be appropriately selected according to the type of each acid generator. The mixing ratio of the other acid generator is usually 95 parts by mass or less and 90 parts by mass or less with respect to 100 parts by mass in total of the radiation-sensitive acid generator of the present invention and the other acid generator. It is preferable that the content is 80 parts by mass or less. The blending ratio of the other acid generator is preferably 95 parts by mass or less because the effect (high resolution) of the compound of the present invention can be sufficiently exhibited. In addition, the said other acid generator may also be used individually by 1 type, and may use 2 or more types together.

  The blending ratio of each component constituting the positive radiation-sensitive resin composition of the present invention can be set in various ranges depending on the characteristics desired to be imparted to the resist. The compounding amount of the radiation sensitive acid generator is usually 0.001 to 70 parts by mass and preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the acid dissociable group-modified alkali-soluble resin. More preferably, the content is 0.1 to 20 parts by mass. When the blending amount of the radiation sensitive acid generator is 0.001 part by mass or more, it is preferable because a decrease in sensitivity and resolution can be suppressed. Moreover, it is preferable to set it as 70 mass parts or less, since it can suppress the resist coating property and the deterioration of the pattern shape.

[2-C] Acid diffusion inhibitor (C component):
In addition to the essential components, an acid diffusion inhibitor may be blended in the positive radiation sensitive resin composition of the present invention. The acid diffusion inhibitor is an additive having an action of controlling a diffusion phenomenon of an acid generated from an acid generator or the like by exposure in a resist film and suppressing an undesirable chemical reaction in a non-exposed region. By blending an acid diffusion inhibitor, the storage stability of the radiation sensitive resin composition can be improved. In addition, by adding an acid diffusion inhibitor, it is possible to improve the resolution of the resist and to suppress changes in the line width of the resist pattern due to fluctuations in the holding time (PED) from exposure to development processing. As a result, there is an advantage that a radiation sensitive resin composition having extremely excellent process stability can be obtained.

  The acid diffusion inhibitor is preferably a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment during the resist pattern formation step. Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (9) (hereinafter referred to as “nitrogen-containing compound (I)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (I)”). , “Nitrogen-containing compound (II)”), amide group-containing compounds, nitrogen-containing heterocyclic compounds, and the like. Among these nitrogen-containing organic compounds, the nitrogen-containing compound (I), the nitrogen-containing compound (II), the nitrogen-containing heterocyclic compound, and the like are preferable. These acid diffusion inhibitors may be used alone or in combination of two or more.

〔一般式（９）において、Ｒ^１２、Ｒ^１４及びＲ^１６は各々が同一若しくは異なった、水素原子、置換されていてもよいアルキル基、置換されていてもよい芳香族炭化水素基又は置換されていてもよいアラルキル基を示す。〕

[In the general formula (9), R ¹² , R ¹⁴ and R ¹⁶ are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group or a substituted group. An aralkyl group which may be present is shown. ]

  In the general formula (9), the linear, branched or cyclic alkyl group which may be substituted is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, such as a methyl group, Ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n -Heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, n-decyl group and the like can be mentioned.

  Examples of the optionally substituted aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group. Can do. Furthermore, examples of the aralkyl group which may be substituted include an aralkyl group having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, such as benzyl group, α-methylbenzyl group, phenethyl group, naphthylmethyl group and the like. it can.

  Examples of the nitrogen-containing compound (I) 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 , Tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, etc. Amines; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3 Methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, aromatic amines such as 1-naphthylamine; ethanolamine, diethanolamine, can be exemplified alkanolamines such as triethanolamine and the like. Among these, tri-n-octylamine is preferable because it has an appropriate boiling point height.

  Examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, N, N, N ′, N′-tetrakis (2- Hydroxyethyl) 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- Loxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and the like. Can be mentioned.

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

  Moreover, the nitrogen-containing compound which has an acid dissociable group can also be used as said nitrogen-containing organic compound. Examples of the nitrogen-containing 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) dioctylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl) diphenylamine Etc.

  The amount of the acid diffusion inhibitor is usually 15 parts by mass or less, preferably 0.001 to 10 parts by mass, with respect to 100 parts by mass of the acid dissociable group-modified alkali-soluble resin. It is still more preferable to set it as -5 mass parts. The amount of the acid diffusion inhibitor is preferably 15 parts by mass or less because the sensitivity as a resist and the developability of an exposed part can be improved. Moreover, when the compounding quantity of the said acid diffusion inhibitor shall be 0.001 mass part or more, since it can suppress that the pattern shape and dimensional fidelity as a resist fall with process conditions, it is preferable.

[2-D] Dissolution control agent (component D):
The positive radiation sensitive resin composition of the present invention may contain a dissolution control agent in addition to the essential components. The dissolution control agent is an additive that has the effect of adjusting the solubility of the resin during alkali development. By adding a dissolution control agent, the dissolution contrast and dissolution rate of the resist are more appropriately controlled. It is possible to obtain a preferable effect. Examples of the dissolution control agent include t-butyl deoxycholate.

  The amount of the dissolution control agent is usually 0 to 20 parts by mass, preferably 0 to 10 parts by mass, and preferably 0 to 5 parts by mass with respect to 100 parts by mass of the acid dissociable group-modified alkali-soluble resin. More preferably. If the blending amount exceeds 20 parts by mass, the resolution tends to decrease, which is not preferable. On the other hand, it is preferable to add an acid diffusion inhibitor in the range of 0 to 5 parts by mass because an effect of improving LER (Line Edge Roughness, fluctuations and rattling of the resist pattern) can be obtained.

[2-E] Solvent (E component):
In addition to the above essential components, a solvent may be blended in the positive radiation sensitive resin composition of the present invention. Examples of the solvent include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, lactones, (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, acetate esters, Hydroxyacetic acid esters, lactic acid esters, alkoxyacetic acid esters, (non) cyclic ketones, acetoacetic acid esters, pyruvate esters, propionate esters, N, N-dialkylformamides, N, N-dialkyl Acetamides, N-alkylpyrrolidones, γ-lactones, (halogenated) aliphatic hydrocarbons, (halogenated) aromatic hydrocarbons and the like can be mentioned.

  More specifically, for example, 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, isopropenyl acetate, isopropenyl propionate,

  Toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 3-methylbutyrate, methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Methyl acid, 3 Ethyl ethoxypropionate, N- methylpyrrolidone, N, N- dimethylformamide, N, N- dimethylacetamide may be mentioned γ- butyrolactone.

  Among these, when using propylene glycol monoalkyl ether acetates (such as propylene glycol monomethyl ether acetate), 2-heptanone, lactic acid esters, 2-hydroxypropionic acid esters, 3-alkoxypropionic acid esters, etc. This is preferable because in-plane uniformity is improved. Propylene glycol monomethyl ether acetate, cyclohexanone, and γ-butyrolactone are preferred because of high resin solubility. In preparing the radiation sensitive resin composition, the solvent may be used alone or in combination of two or more.

  In addition, the solvent may include other solvents (hereinafter referred to as “other solvents”) as necessary. Examples of the other solvent include benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, and benzyl. Examples thereof include high-boiling solvents such as alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate. Among these, γ-butyrolactone is preferable because of the high solubility of the resin. One of these other solvents may be used alone, or two or more thereof may be mixed and used.

  The amount of the solvent used is usually 5 to 50% by mass, preferably 10 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 10 to 30% by mass in the total solid content in the homogeneous solution. The amount is particularly preferably 10 to 25% by mass. By setting it as this range, since the uniformity in a film surface at the time of application | coating becomes favorable, it is preferable. Moreover, when the said solvent contains the said other solvent, the usage-amount of the said other solvent is 50 mass% or less normally with respect to all the solvents, and it is preferable to set it as 30 mass% or less, 25 mass% More preferably, it is as follows.

[2-F] Other components:
The positive-type radiation-sensitive resin composition of the present invention may contain additives other than the above-described components, for example, a surfactant.

  As the surfactant, any of an anionic, cationic, nonionic or amphoteric surfactant can be used, but a nonionic surfactant is preferably used. Nonionic surfactants include, for example, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, etc., and all of the following trade names: “KP” (Shin-Etsu) "Chemical Industry Co., Ltd.", "Polyflow" (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), "F Top" (manufactured by Tochem Products), "Megafuck" (manufactured by Dainippon Ink and Chemicals), "Fluorard" (Sumitomo 3M) ), “Asahi Guard” and “Surflon” (Asahi Glass Co., Ltd.). One of these surfactants may be used alone, or two or more thereof may be mixed and used.

  The said surfactant which can be added to the radiation sensitive resin composition of this invention shows the effect | action which improves the applicability | paintability, striation, developability, etc. of a radiation sensitive resin composition. When the surfactant is blended, the blending amount is usually 2 parts by mass or less, preferably 1. as an active ingredient of the surfactant with respect to 100 parts by mass of the total resin components in the radiation-sensitive resin composition. 5 parts by mass or less, more preferably 1 part by mass or less.

[2-G] Preparation of radiation-sensitive resin composition:
The radiation-sensitive resin composition of the present invention is usually prepared by dissolving each component in a solvent at the time of use to make a uniform solution, and then filtering by, for example, a filter having a pore size of about 0.2 μm as necessary. Is done.

[2-H] Formation of resist pattern:
When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the radiation-sensitive resin composition solution prepared by the above method or the like is prepared by means such as spin coating, cast coating, roll coating, etc. A resist film is formed by coating on a substrate such as a silicon wafer or a wafer coated with aluminum. In some cases, a heat treatment (hereinafter referred to as “PB”) is performed in advance, and then the resist film is exposed through a predetermined mask pattern.

  The radiation that can be used for exposure includes the emission line spectrum of a mercury lamp (wavelength 254 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), etc., depending on the type of acid generator used. Far ultraviolet rays, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. Among these, far ultraviolet rays and charged particle beams are preferable, and KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) and electron beam are particularly preferable. In addition, exposure conditions such as radiation dose are appropriately selected according to the composition of the radiation-sensitive resin composition of the present invention, the type of additive, and the like.

  Further, when a resist pattern is formed from the radiation-sensitive resin composition of the present invention, the apparent sensitivity of the resist can be improved by performing a heat treatment after exposure (hereinafter, this heat treatment is referred to as “PEB”). It is preferable because it is possible. The heating conditions for the PEB vary depending on the composition of the radiation-sensitive resin composition of the present invention, the type of additive, etc., but are usually 30 to 200 ° C., preferably 50 to 150 ° C.

  Then, a predetermined resist pattern is formed by developing the exposed resist film with an alkaline developer. 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 other alkaline compounds in which one or more alkaline compounds are dissolved are used. A particularly preferred alkaline developer is an aqueous solution of tetraalkylammonium hydroxides. The concentration of the alkaline aqueous solution is usually 10% by mass or less, preferably 1 to 10% by mass, and more preferably 2 to 5% by mass. The concentration of the alkaline aqueous solution is preferably 10% by mass or less because it is possible to suppress the dissolution of the non-exposed portion in the developer.

  An appropriate amount of a surfactant or the like can be added to the developer composed of the alkaline aqueous solution. This is preferable because the wettability of the developer with respect to the resist can be improved. 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 compound of the present invention, the radiation-sensitive acid generator and the positive radiation-sensitive resin composition will be described more specifically with reference to examples. However, these examples merely show some embodiments of the present invention. That is, the present invention should not be interpreted as being limited to these examples.

[Reference Examples 1-3]:
An acid dissociable group-modified alkali-soluble resin (component A), which is an essential component of the positive radiation sensitive resin composition of the present invention, was synthesized by the following method. As the monomer, any of the four types of monomers having the structures shown by (M-1) to (M-4) in Table 7 was used. For the synthesized resin, GPC columns (trade names: G2000HXL (× 2), G3000HXL (× 1), G4000HXL (× 1)) were used, flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column Temperature: Polystyrene-converted weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analysis conditions of 40 ° C.

[Reference Example 1]:
(M-1) 5 g, (M-2) 25 g, and (M-3) 20 g were uniformly dissolved in 150 g of methyl ethyl ketone, and bubbled with nitrogen gas for 30 minutes. Next, 2 g of azobisisobutyronitrile (AIBN) was added to this solution as a polymerization initiator and heated to 80 ° C. The polymerization reaction was carried out with stirring at this temperature for 6 hours.

  After completion of the polymerization reaction, 50 g of methyl ethyl ketone was added for dilution, and then the reaction solution was cooled to room temperature, poured into 1000 ml of methanol, and the precipitated white powder was filtered and dried to dry the acid-dissociable group-modified alkali-soluble. A resin was obtained.

The obtained resin had Mw of 6000. As a result of analysis using ¹³ C-NMR, the molar ratio of (M-1) unit: (M-2) unit: (M-3) unit in the copolymer was 15:50:35. . This resin is referred to as “A-1 component”.

[Reference Example 2]:
(M-1) 5 g, (M-2) 25 g, and (M-3) 20 g were uniformly dissolved in 150 g of methyl ethyl ketone, and bubbled with nitrogen gas for 30 minutes. Next, 2 g of dimethyl 2,2′-azobis (2-methylpropionate) was added to this solution as a polymerization initiator and heated to 80 ° C. The polymerization reaction was carried out with stirring at this temperature for 6 hours. After completion of the polymerization reaction, an acid-dissociable group-modified alkali-soluble resin was obtained in the same manner as in Reference Example 1.

The obtained resin had Mw of 13000. Further, as a result of analysis using ¹³ C-NMR, the copolymer had a molar ratio of (M-1) unit: (M-2) unit: (M-3) unit in the copolymer of 13:50:37. It was a coalescence. This resin is referred to as “A-2 component”.

[Reference Example 3]:
18 g of (M-1), 27 g of (M-2), and 5 g of (M-4) were uniformly dissolved in 150 g of methyl ethyl ketone, and bubbled with nitrogen gas for 30 minutes. Next, 2 g of AIBN was added to this solution as a polymerization initiator and heated to 80 ° C. The polymerization reaction was carried out with stirring at this temperature for 6 hours. After completion of the polymerization reaction, an acid-dissociable group-modified alkali-soluble resin was obtained in the same manner as in Reference Example 1.

The obtained resin had Mw of 5000. Further, as a result of analysis using ¹³ C-NMR, the copolymer had a molar ratio of (M-1) unit: (M-2) unit: (M-4) unit in the copolymer of 39: 50: 9. It was a coalescence. This resin is referred to as “A-3 component”.

[Example 1]:
An onium salt represented by the following general formula (10), 4- (N, N-dimethylaminopropoxyphenyldiphenylsulfonium perfluoro-n-butanesulfonate) was synthesized by the following method.

  In the reaction flask, 5.8 g of 4-hydroxyphenyldiphenylsulfonium perfluoro-n-butanesulfonate was dissolved in 30 g of acetone, and nitrogen was passed to perform nitrogen substitution. Then, 6.9 g of potassium carbonate was added, and after stirring for 30 minutes, 7.0 g of 3-dimethylaminopropyl chloride hydrochloride was added, and 1.1 g of potassium iodide was further added, followed by stirring at 65 ° C. for 6 hours.

  Subsequently, this reaction solution was put into 150 ml of ion exchange water, and 200 ml of ethyl acid acid was added. The mixed solution was transferred to a separatory funnel, shaken, allowed to stand, and the aqueous layer was removed. Further, 150 ml of distilled water was added and shaken, allowed to stand, and then the aqueous layer was removed. Thereafter, ethyl acetate is distilled off from the ethyl acetate layer using an evaporator, and purified by column chromatography, followed by drying under reduced pressure to give 4- (N, N-dimethylaminopropoxyphenyldiphenylsulfonium perfluoro-n-butanesulfonate). This compound is referred to as “component B-1”.

Incidentally, for this ^compound, 1 H-NMR (trade name: JNM-EX270, manufactured by JEOL Ltd.) using a result of analyzing the measurement solvent as deuterated chloroform, the resulting chemical ^shift, 1 H-NMR [ σppm (CD ₃ Cl): 2.11 (m, 2H), 2.67 (s, 6H), 2.89 (m, 2H), 3.69 (m, 2H), 7.11-7.86 (M, 14H)] and was confirmed to be the target compound.

  In addition, as a result of analysis using a mass spectrometer (trade name: JMS-AX505W, manufactured by JEOL Ltd.) under the conditions described in Table 8, 364 parent ion peaks were detected and confirmed to be the target compound. .

[Examples 2-8, Comparative Examples 1-2]:
A positive radiation sensitive resin composition was prepared using the onium salt of Example 1 as a radiation sensitive acid generator. Specifically, the acid-dissociable group-modified alkali-soluble resin shown in Table 9 (referred to as “resin” and “component A” in the table), the radiation-sensitive acid generator of the present invention (referred to as “acid generator” in the table) ”,“ B component ”), other radiation sensitive acid generator (in the table,“ acid generator ”,“ B ′ component ”), acid diffusion inhibitor (in the table,“ inhibitor ”, Mixing each component of “C component”), dissolution control agent (in the table, “control agent”, “D component”) and solvent (in the table, “E component”) to obtain a uniform solution Then, the radiation sensitive resin composition solutions of Examples 2 to 8 and Comparative Examples 1 and 2 were prepared by filtering using a membrane filter having a pore size of 0.2 μm. Details of the B ′ component, C component, D component, and E component used in the examples and comparative examples are shown in Table 10.

[Evaluation methods]
About the radiation sensitive resin composition of Examples 2-8 and Comparative Examples 1-2, the substrate which formed the 770A ARC29A (brand name, the product made by Nissan Chemical Industries) film | membrane on the wafer surface was used, and each composition was carried out on a board | substrate. The resist film having a thickness of 0.15 μm formed by spin coating and applying PB on a hot plate under the conditions shown in Table 9 was used to evaluate sensitivity, resolution, and pattern shape.

(1) Sensitivity (mJ / cm ² ):
The resist film was exposed using a full-field reduced projection exposure apparatus S306C (trade name, manufactured by Nikon Corporation, numerical aperture of 0.75) while solving the mask pattern. Thereafter, PEB was performed under the conditions shown in Table 9, followed by development with a 2.38 mass% TMAH aqueous solution at 25 ° C. for 60 seconds, washing with water, and drying to form a positive resist pattern. At this time, an exposure amount formed in a one-to-one line-and-space with a line width of 100 nm is defined as an optimum exposure amount, and the optimum exposure amount is set as a line width formed through a one-to-one line-and-space mask having a dimension of 100 nm. “Sensitivity”.

(2) Resolution (nm):
The minimum dimension (nm) of the resist pattern resolved when exposed at the optimum exposure amount was determined as the resolution.

(3) Pattern shape:
The lower side dimension La and the upper side dimension Lb of the rectangular cross section of the line-and-space pattern (1L1S) having a line width of 100 nm formed on the silicon wafer were measured using a scanning electron microscope and evaluated according to the following criteria. did.
A: satisfying the condition of 0.85 ≦ Lb / La ≦ 1 (good),
X: Not satisfying the condition of 0.85 ≦ Lb / La ≦ 1 (defect).

[Evaluation results]:
As is apparent from the data in Table 9, the positive-type radiation-sensitive resin compositions of Examples using the compounds of the present invention as acid generators were compared with Comparative Examples not using the compounds of the present invention as acid generators. In comparison, the resolution was remarkably improved, and extremely good results were shown. Also, the sensitivity value was small and the sensitivity was high. Furthermore, good results were also shown for the pattern shape.

  The compound of the present invention, the radiation sensitive acid generator and the radiation sensitive resin composition can obtain a sufficiently satisfactory high resolution. For example, it exhibits excellent resolving power that can form a high-definition resist pattern of less than 0.13 μm with a KrF excimer laser and less than 0.1 μm with an ArF excimer laser. Therefore, it can be suitably used in the field of microfabrication, particularly in the manufacture of integrated circuit elements such as semiconductor devices in which miniaturization, high definition, and high integration are rapidly progressing.

Claims (4)

A compound represented by the following general formula (1).

In [general formula (1), A is sulfur atom, Ar each have the same or different, aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted by the following substituents, each B is the same Alternatively, different functional groups having the structure represented by the following general formula (2) , R ¹ and R ² are the same or different, a hydrogen atom, and an alkyl having 1 to 20 carbon atoms which may be substituted by the following substituents group, R ³ each is the same or different, aromatic be substitution by the following optionally substituted hydrocarbon group, Y ^- is a ⁺ counterion, Z is acid MotoHara child, x is 1 to 3 Indicates an integer . m is an integer of 1 to 3, n represents an integer of 0 to 2 (provided, m + n = 3) Ru der. ]

[In General Formula (2), R ⁴ and R ⁵ are the same or different and each is substituted with a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with the following substituents, or the following substituents. May be an alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aromatic hydrocarbon group which may be substituted with the following substituents, or a heterocycle which may be substituted with the following substituents. A cyclic hydrocarbon group, p represents an integer of 1 to 20; ]
Substituent: hydroxyl group, carboxyl group, cyano group, hydroxyalkyl group having 1 to 4 carbon atoms, alkoxyl group having 1 to 4 carbon atoms, cyanoalkyl group having 2 to 5 carbon atoms, alkoxycarbonyl group, alkoxycarbonylalkoxy group, A halogen atom, a fluoroalkyl group; A radiation-sensitive acid generator containing at least one compound according to claim 1 . An acid-dissociable group-modified alkali-soluble resin (component A) having an acidic group and at least part of the acidic group protected by an acid-dissociable group and a radiation-sensitive acid generator (component B) are essential. A positive-type radiation-sensitive resin composition contained as a component,
A positive radiation sensitive resin composition containing at least one compound according to claim 1 as the component B. Furthermore, the positive radiation sensitive resin composition of Claim 3 which contains an acid diffusion inhibitor (C component) as a structural component.