TW200914991A - Resist composition, method of forming resist pattern, compound and acid generator - Google Patents

Abstract

A compound represented by general formula (b-14); and acid generator consisting of the compound; and a resist composition including a base component (A) which exhibits changed solubility in an alkali developing solution under action of acid and an acid-generator component (B) which generates acid upon exposure, the acid-generator component (B) including an acid generator (B1) consisting of a compound represented by general formula (b1-14): wherein R7" to R9" each independently represents an aryl group or an alkyl group, wherein two of R7" to R9" may be bonded to each other to form a ring with the sulfur atom, and at least one of R7" to R9" represents a substituted aryl group in which a portion or all of the hydrogen atoms are substituted with an alkoxyalkyloxy group or an alkoxycarbonylalkyloxy group; and X- represents an anion.

Description

200914991 IX. Description of the Invention [Technical Field] The present invention relates to a photoresist composition for forming a photoresist pattern using the photoresist composition, a compound suitable as an acid generator for a photoresist composition, and An acid generator formed by the compound. This case is based on the special wish 2007-156556 proposed by the Japan Patent Office on June 13, 2007, and the priority of 2007-294429, which was proposed by the Japan Patent Office on November 13, 2007. The contents are used in the manual. [Prior Art] In the lithography technique, for example, a photoresist film obtained from a photoresist material is formed on a substrate, and for the photoresist film, a mask of a specific pattern is formed by radiation such as light or electron lines. The selective exposure is carried out by applying a development treatment to form the photoresist film into a photoresist pattern having a specific shape. The portion of the exposure which is changed to have a characteristic of being dissolved in the developer is referred to as a positive type, and the portion of the photoresist which is exposed to have a property of not being dissolved in the developer is referred to as a negative type. In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, with the advancement of the lithography technique, the pattern has been rapidly refined. The method of miniaturization is generally carried out in such a manner as to shorten the wavelength of the exposure light source. Specifically, ultraviolet rays which are represented by g-line and i-line are conventionally used. However, KrF excimer lasers or ArF excimer lasers are now being used for mass production of semiconductor components. Further, F2 excimer lasers, electron beams, EUV (ultraviolet rays) or X-rays having shorter wavelengths have been studied for the above-mentioned quasi-minutes -6-200914991 sub-lasers. The photoresist material is sought to have sensitivity to the aforementioned exposure light source, and has lithographic etching characteristics such as reproducibility of reproducible fine-size patterns. The photoresist material which satisfies the above requirements is generally used as a base resin containing a change in alkali solubility based on an acid action, and a chemically amplified photoresist which generates an acid generator by exposure. For example, a positive type chemically amplified photoresist is a resin containing an acid-based action as a base resin to increase alkali solubility, and an acid generator component which is formed by exposure to an acid when formed in a photoresist pattern. The agent generates an acid and causes the exposed portion to form an alkali solubility. The base resin of the chemically amplified photoresist is a polyhydroxystyrene (PHS) highly transparent to KrF excimer laser (248 nm) or a resin which is protected by an acid-dissociable dissolution inhibiting group (PHS). Resin). However, since the PHS-based resin has an aromatic ring such as a benzene ring, transparency to a shorter wavelength of 24 8 nm, for example, light of 193 nm is still insufficient. Therefore, a chemically amplified photoresist using a PHS resin as a base resin component has disadvantages such as low resolution for a process using a 93 nm light. Therefore, at present, for the base resin of the photoresist used in the ArF excimer laser lithography etching, in order to have excellent transparency near 193 nm, it is generally used to have a (meth)acrylic acid in the main chain. A resin (acrylic resin) of a structural unit derived from an ester. In the case of a positive type, the above-mentioned resin is mainly a structural unit derived from a (meth) acrylate containing a tertiary alkyl ester type acid dissociable dissolution inhibiting group containing an aliphatic polycyclic group, 200914991, for example, mainly used 2 A resin having a structural unit derived from an alkyl-2-adamantyl (meth) acrylate or the like (for example, Patent Document 1). Further, '(acrylic acid ester) means an acrylate having a hydrogen atom bonded to the α-position, and one or both of the methacrylate of the methyl group; meaning. "(Meth)acrylate" means an acrylate having a hydrogen atom bonded to the α-position and one or both of a methyl methacrylate bonded to the α-position. "(Meth)acrylic acid" means an acrylic acid having a hydrogen atom bonded to the α-position, and one or both of the methacrylic acid having a methyl group bonded to the α-position. Further, various acid generators have been proposed for use in chemically amplified photoresists, such as a gun salt acid generator such as an iodine salt or a phosphonium salt, and an oxime sulfonate acid generator. A variety of known compounds such as a diazomethane acid generator, a nitrobenzyl sulfonate acid generator, an imidosulfonate acid generator, and a diterpenoid acid generator. At present, an acid generator containing a triphenylsulfonium skeleton, a dinaphthylmonophenylphosphonium skeleton or the like has been used as the acid generator. (Patent Document 2). [Patent Document 1] Japanese Patent Publication No. 2 0 0 3 - 2 4 1 3 8 5 [Patent Document 2] JP-A-2000-A-37-8 No. 8 [Invention] In recent years, along with a photoresist pattern The miniaturization of the type has further expectations for high resolution, and further improvements in various lithographic etching characteristics have been sought. For example, when a photoresist pattern is formed, its pattern shape or mask reproducibility, etc., will be more important as the pattern is refined. Mask error

200914991 Sub-(MEF) is one of the indicators indicating the above characteristics. Under the condition of guarding the fixed pitch, the mask size (line width of the line and the diameter of the through hole in the contact pattern) is changed. How to faithfully reproduce the mask pattern (mask reproducibility) For the purpose of improving the lithography etching characteristics, etc., it is an important factor to improve the above-mentioned pattern and the like, and the purpose is described when a novel acid generator is used. The present invention has been made in view of the above circumstances, that is, a novel compound which is an acid generator for a photoresist composition, an acid generator formed, and a photoresist containing the acid generator to constitute a photoresist of the photoresist composition. The method of forming the pattern is for the purpose. A first embodiment of the present invention which solves the above problems, a composition comprising a substrate component (A) which is changed by an action of an acid to an alkali developing solution, and a photoresist which generates an acid component (B) by exposure. In the composition, the acid (B) is a compound generating agent (B 1 ) represented by the following formula (bl-14), and is a compound (B 1 - 1 4). "~R9" each independently represents an aryl group or an alkyl group; meaning that two groups may be bonded to each other to form a sulfur atom in the formula. 'At least one of the hydrogen atoms is partially or wholly the same exposure space pattern. There are different parameters in the middle. In the case of Yuzhen or MEF, an acid "'~R9" which is suitable for the compound and which is used as a resistive acid generator generator component; R7"~R9 'Oxygenyloxy-9-200914991 or a substituted aryl group substituted by an alkoxycarbonylalkyloxy group; χ· is an anion]. Further, a second embodiment of the present invention includes the use of the above-described invention The step of forming a photoresist film on the support by the photoresist composition of the embodiment, the step of exposing the photoresist film, and the photoresist pattern of the step of forming the photoresist pattern by alkali development of the photoresist film Further, the third embodiment of the present invention is a compound represented by the above formula (b 1 -1 4 ). Further, in addition, the fourth embodiment of the present invention is the above formula (b 1 -1 4 ) An acid generator formed by the compound shown. In the specification and the patent application, "structural unit" means a monomer unit constituting a resin component (polymer). "Exposure" is a tribute to the full illumination of radiation. The "alkyl group" is not particularly limited, and includes a linear, branched, and cyclic monovalent saturated hydrocarbon group. The "lower alkyl group" means an alkyl group having 1 to 5 carbon atoms. The "acid dissociable group" means an organic group which is dissociated by the action of an acid. The present invention provides a photoresist composition using a photoresist pattern of the photoresist composition, a novel compound as an acid generator for the photoresist composition, and an acid generator formed of the compound. Hereinafter, the present invention will be described in more detail. <<Compound of Third Embodiment>> First, a compound of the third embodiment of the present invention will be described - -10-200914991. The compound of the second embodiment of the present invention is as shown in the above formula (b 1 14 ). In the above formula (bl-14), R alkyl group. Wherein, at least a part of R7''~R9" is independently substituted by a oxy group or a oxyalkyl group to R, each independently representing an aryl group or a part of a hydrogen atom or a substitution of a whole hospital oxygen s The aryl group of the aryl group R7''~R9'' is not particularly limited. For example, in the aryl group having 6 to 2 Å, the aryl group is a part or all of the hydrogen atom. The substituent other than the oxy group and the oxycarbonyl fluorenyloxy group may be substituted, for example, a compound such as a siloxane, an alkoxy group, a halogen atom or a hydroxy group, and may be substituted. The aryl group may be inexpensive. From the viewpoint of synthesis and the like, an aryl group having 6 to 1 carbon atoms is preferred. Specifically, for example, a phenyl group, a naphthyl group, etc. may be substituted for the base of the atom of the atom, and the number of carbon atoms is 1 to 5 The base is preferably 'methyl, ethyl, propyl, η-butyl, tert-butyl is the alkoxy group which can replace the hydrogen atom of the above aryl group, and the alkyl group having a carbon number of 1 to 5 Preferably, methoxy, ethoxy, η-propoxy, iso-propoxy, η-butoxy, tert-butoxy are preferred. Halogen which can replace the hydrogen atom of the aforementioned aryl group atom, The alkyl group having a fluorine atom of preferably R7'' to R9'' is not particularly limited, and for example, it may be a linear, branched or cyclic alkyl group having a carbon number of 1 to 10, etc., and has excellent resolution. The viewpoint is preferably a carbon number of 1 to 5. Specifically, for example, a methyl group, an ethyl group, a η-propyl group, an isopropyl group, an η-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, -11 - 200914991 A hexyl group, a cyclohexyl group, a fluorenyl group, a fluorenyl group, etc., which have excellent resolution and can be synthesized inexpensively, for example, a methyl group, etc. At least one of R7 to R9 is a hydrogen atom of the above aryl group. a part or all of J is k虱: ί: a substituted aryl group substituted by a mercaptooxy group or an alkoxycarbonylalkyloxy group. Two or more of R7 to R9 may be the above substituted aryl group, and Any one of R7'' to R9" is preferably the above substituted aryl group. The alkoxyalkyloxy group in which the hydrogen atom in the above substituted aryl group may be substituted, for example, is represented by the following formula (bl4-l). [Chemical 2]

[wherein R47 and R4 8 are each independently a hydrogen atom or a linear or branched alkyl group, R49 is an alkyl group, and R48 and R49 may be bonded to each other to form a ring structure. Wherein at least one of 'R47 and R48 is a hydrogen atom>. In the formula, each of R47 and R48 is independently a hydrogen atom or a linear or branched alkyl group, and at least one of R47 and R48 is a hydrogen atom. In R47 and R48, the carbon number of the alkyl group is preferably from 1 to 5, more preferably ethyl or methyl, and most preferably methyl. Further, it is preferred that one of R47 and R48 is a hydrogen atom, and the other is a hydrogen atom or a methyl group, and any of R47 and R48 is preferably a hydrogen atom. The alkyl group of R49 is preferably a carbon number of 1 to 15, and may be any of a linear chain, a branched chain, and a cyclic chain. The linear or branched alkyl group in R4 9 is preferably -12-200914991 having a carbon number of 1 to 5, for example, methyl, ethyl, propyl, η-butyl, tert-butyl. Wait. The cyclic alkyl group in R49 is preferably a carbon number of 4 to 15, and more preferably a carbon number of 4 to 12, and most preferably a carbon number of 5 to 10. Specifically, for example, it may be substituted by an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, or a monocyclic alkane or a bicycloalkane 'tricycloalkane which may be unsubstituted. A polycyclic alkane such as a tetracycloalkane is removed from a group of one or more hydrogen atoms. A monocyclic alkane such as cyclopentane, cyclohexane or the like. Polycyclic alkanes are exemplified by adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like. Among them, it is preferred that adamantane is used to remove one or more hydrogen atoms. R48 and R49 may be bonded to each other to form a ring structure. In this case, R48 and R49 may form a cyclic group with an oxygen atom bonded to R49 and a carbon atom bonded to the oxygen atom and R48. The ring base is preferably a 4 to 7 member ring, and a 4 to 6 member ring is preferred. In the above substituted aryl group, the alkoxycarbonylalkyloxy group in which the hydrogen atom is substituted is, for example, a content represented by the following formula (bl4-2). [化3]

[wherein, R5° is a linear or branched alkyl group, and R51 is an acid dissociable group]. A linear or branched alkyl group in R5Q, preferably having a carbon number of 1 to 5, for example, a methyl group, an ethyl group, a trisyl group, a tetramethyl group, a 1,1 -2 group. Methyl extended ethyl and the like. -13- 200914991 The acid-dissociable group in R51 is not particularly limited as long as it is dissociated by the action of an acid. It may be a cyclic or chain-like tertiary-grade vinegar-type acid dissociable group; An acetal type acid dissociable group such as an alkyl group, and the like, and a third-stage alkyl ester type acid dissociable group is preferred. Specifically, for example, 2-methyl-2-goldenyl, 2-ethyl-2-goldenyl, i-methyl-1-cyclopentyl, ethyl-1-cyclopentyl, 1-methyl 1-cyclohexyl, 1-ethyl-1-cyclohexyl, 丨-(1-adamantyl)-1-methylethyl, 1-(1-adamantyl)-1-methylpropyl, 1-(1-adamantyl)-1-methylbutyl, 1-(1-adamantyl)-1-methylpentyl; 1-(1-cyclopentyl)-1-methylethyl , 1-(1-cyclopentyl)-:ι-methylpropyl, 1-(l-cyclopentyl)-l-methylbutyl, 1-(l-cyclopentyl)-1-methyl Butyl; 1-(1-cyclohexyl)-1-methylethyl, 1-(1-cyclohexyl)-1-methylpropyl, 1-(1-cyclohexyl)-1-methylbutyl , cyclohexyl)-1-methylpentyl, tert-butyl, tert-pentyl, tert-hexyl, and the like. The number of the alkoxyalkyloxy group or the alkoxycarbonylalkyloxy group in which the hydrogen atom in the substituted aryl group is substituted is preferably 2 or less, and more preferably one. R7" to R9'' other than the substituted aryl group is preferably a phenyl group or a naphthyl group, and preferably a phenyl group. r7''~R9", wherein any two of them are bonded to each other The sulfur atoms in the form together form a ring. In this case, it is preferable to form a 3 to 10 member ring containing a sulfur atom, and it is more preferable to form a 5 to 7 member ring. In the above formula (bl-14), X- is an anion. The anion portion of X- is not particularly limited, and those known as an anion portion of the key salt acid generator can be suitably used. For example, an anion represented by the formula "r14s〇3_(R14 is a linear, branched or cyclic alkyl group, a halogenated alkyl group, an aryl group, or an alkenyl group) j can be used. The formula "Ri-OY^SOsIR1 is a monovalent aliphatic hydrocarbon group, a monovalent aromatic organic group, or a monovalent hydroxyalkyl group; Y1 is an alkyl group having 1 to 4 carbon atoms which may be substituted by fluorine" Show anion. In the above formula "R14S03-", R14 is a linear, branched or ring-shaped yard base, a dentifrice base, an aryl group, or a suspect base. The linear or branched alkyl group of the above R14 is preferably one having a carbon number of 1 or less, more preferably having a carbon number of 1 to 8, and most preferably having a carbon number of 1 to 4. The cyclic alkyl group of R14 is preferably a carbon number of 4 to 15, more preferably a carbon number of 4 to 10, and most preferably a carbon number of 6 to 10. The above halogenated alkyl group of R14, that is, a part or all of a hydrogen atom in the alkyl group is substituted by a halogen atom. Wherein, the alkyl group is preferably a lower alkyl group having 1 to 5 carbon atoms, wherein a linear or branched alkyl group is more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. More preferably, η-butyl, tert-butyl, tert-pentyl or isopentyl. A halogen atom which may be substituted for a hydrogen atom, such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom. In the halogenated alkyl group, 50 to 100% of the total number of hydrogen atoms is preferably substituted by a halogen atom, and more preferably all of them are substituted. Among them, the halogenated alkyl group is preferably a fluorinated alkyl group. The fluorinated alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. Further, the fluorination ratio of the fluorinated alkyl group (the ratio of the number of fluorine atoms substituted by fluorination to the total number of hydrogen atoms in the fluorinated alkyl group is the same as the following) is preferably 10 to 100%. More preferably, it is 50 to 100%, and it is particularly preferred that all of the hydrogen atoms are replaced by fluorine atoms, and the strength of the acid is enhanced to be the best -15-200914991. The above preferred fluorinated alkyl group is specifically, for example, a trifluoromethyl group, a heptafluoro-η-propyl group, a nonafluoro-n-butyl group or the like. The aryl group of R14 may have a substituent, and preferably an aryl group having 6 to 20 carbon atoms. There may be a substituent such as a halogen atom, a hetero atom, a fluorenyl group or the like. The substituents may have a plurality of substituents. The above alkenyl group of R14 may have a substituent, and is preferably an alkenyl group having 2 to 1 carbon atoms. There may be a substituent such as a halogen atom, a hetero atom, a hospital base or the like. The substituents may have a plurality of substituents. Among them, it is better to say that R 1 4 is a halogenated hospital base. In the above formula "R^OY^SOr", R1 is a monovalent aliphatic hydrocarbon group, a monovalent aromatic organic group, or a monovalent hydroxyalkyl group; and Y1 is a carbon number 1 to 4 which may be substituted by fluorine. Alkyl. The monovalent aliphatic hydrocarbon group of R1, for example, a linear, branched or cyclic monovalent saturated hydrocarbon group having 1 to 15 carbon atoms, or a linear or branched carbon number of 2 to 5 A monovalent aliphatic unsaturated hydrocarbon group or the like. A linear monovalent saturated hydrocarbon group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or the like. Branched monovalent saturated hydrocarbon group, such as '1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methyl Butyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and the like. The cyclic monovalent saturated hydrocarbon group may be any of a polycyclic group or a monocyclic group, for example, a polycyclic ring such as a monocyclic alkane 'bicycloalkane, a tricycloalkane or a tetracycloalkane. The base obtained by removing one hydrogen atom from the alkane. More specifically,-16-200914991, for example, a monocyclic alkane such as cyclopentane, cyclohexane 'cycloheptane, cyclooctane, or the like, or a diamond plant, a noodle house, an ice sculpture, a three-ring brothel, The base obtained by removing one hydrogen atom from a multi-ring chain such as the Fourth Ring and the Fourth House. A linear monovalent unsaturated hydrocarbon group such as a 'vinyl' propylene group (allyl), a butenyl group or the like. A branched monovalent unsaturated hydrocarbon group 'e.g., a 1-methylpropenyl group, a 2-methacryl group, or the like. The carbon number of the monovalent aliphatic hydrocarbon group of R is preferably 2 to 4, and more preferably 3. Aromatic organic group of a valence of R1, for example, a ring of an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyi group, a naphthyl group, an anthryl group or a phenanthroline group; a heteroaryl group obtained by substituting a hydrogen atom or a part of a carbon atom constituting the ring of the aryl group with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, benzyl, phenethyl or fluorene-naphthalene An aralkyl group such as a methyl group, a 2-naphthylmethyl group, a naphthylethyl group or a 2-naphthylethyl group. The carbon number of the chain in the aforementioned square yard is preferably from 1 to 4, more preferably from 1 to 2, and most preferably from 1. The aryl group, heteroaryl group or aralkyl group may have a substituent such as an alkyl group having a carbon number of i 〜1 〇, a halogenated alkyl group, an alkoxy group, a hydroxyl group or a halogen atom. The alkyl group or the halogenated alkyl group in the substituent is preferably a carbon number of 1 to 8 and more preferably a carbon number of 1 to 4. Further, the halogenated alkyl group is preferably a fluorinated alkyl group. The halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, a bromine atom or the like is preferably a gas atom.

The monovalent hydroxyalkyl group of R1 is a linear, branched or cyclic monovalent saturated hydrocarbon group in which at least one hydrogen atom is replaced by a hydroxyl group. Further, one or two hydrogen atoms of a linear or -17-200914991 branched monovalent saturated hydrocarbon group are preferably replaced by a hydroxyl group. Specifically, for example, hydroxymethyl, hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 2,3-dihydroxypropyl and the like. The carbon number of the monovalent hydroxyalkyl group of R1 is preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 3. Alkyl group of 1 to 4 carbon atoms which may be substituted by fluorine, such as -CF2-'-CF2CF2-, -CF2CF2CF2-'-CF(CF3)CF2-, -CF(CF2CF3)-, -c(cf3) 2-, -cf2cf2cf2cf2-, -cf(cf3)cf2cf2-, -CF2CF(CF3)CF2-, -CF(CF3)CF(CF3)-, -C(CF3)2CF2-, -cf(cf2cf3)cf2-, -cf(cf2cf2cf3)-, -C(CF3)(CF2CF3)-; -CHF- 'CH2CF2- ' -CH2CH2CF2- ' -CH2CF2CF2- ' -CH(CF3)CH2-, -CH(CF2CF3)-, -C( CH3)(CF3)·, -CH2CH2CH2CF2-, -CH2CH2CF2CF2-, -CH(CF3)CH2CH2-, -ch2ch(cf3)ch2-, -ch(cf3)ch(cf3)-, -c(cf3)2ch2-; -ch2-, -ch2ch2-, -ch2ch2ch2-, -ch(ch3)ch2-, -CH(CH2CH3)-, -C(CH3)2---CH2CH2CH2CH2-, -CH(CH3)CH2CH2-, -CH2CH( CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -CH(CH2CH2CH3)-, -C(CH3)(CH2CH3)-, and the like. Further, the alkyl group of Y1 which may be substituted by fluorine and has a carbon number of 1 to 4 is preferably a fluorine atom bonded to the carbon atom of S, and the above-mentioned fluorinated alkyl group, for example, -CF2-, -CF2CF2-' -CF2CF2CF2- ' -CF(CF3)CF2- ' •CF2CF2CF2CF2-, -CF(CF3)CF2CF2-, -CF2CF(CF3)CF2-, -CF(CF3)CF(CF3)-, -C(CF3)2CF2- -CF(CF2CF3)CF2-; -18- 200914991 -CH2CF2- '-CH2CH2CF2- '-CH2CF2CF2-; -CH2CH2CH2CF2-, -CH2CH2CF2CF2-, -CH2CF2CF2CF2-, etc. Further, -CF2CF2-, -CF2CF2CF2., or CH2CF2CF2- is preferred, and -CF2CF2. or -CF2CF2CF2- is more preferred, and -CF2CF2- is preferred. In the above formula (bl-14), an anion represented by the following formula (b-3), an anion represented by the following formula (b-4), or the like can be used as X. 【化4】

...(b-3) 〇2S—Y&quot;

-••(b-4) [wherein, X" is an alkylene group having 2 to 6 carbon atoms substituted with at least one hydrogen atom by a fluorine atom; Y", 2;" each independently is at least one hydrogen atom a carbon atom substituted by a fluorine atom to an alkyl group of 1 ]]. In the formula (b-3), X" is a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the extension The alkyl group preferably has 2 to 6 carbon atoms, more preferably 3 to 5 carbon atoms, most preferably 3 carbon atoms. In the formula (b-4), Y" and Z" are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the alkyl group preferably has 1 to 10 carbon atoms. More preferably, the carbon number is from 1 to 7, and the most preferred carbon number is from 1 to 3. When the carbon number of the alkyl group of X" or the carbon number of the alkyl group of Y" or Z" is in the above range, it is preferably as small as possible based on the solubility of the resist solvent, etc. Further, X '' In the alkyl group of the alkyl group or the Y", Z" group, which is replaced by a fluorine atom, the cylinder of the hydrogen atom is extended to 90 3 groups or in the middle, and the more the number of the following sub-numbers, the stronger the strength of the acid Further, it is preferable to increase the transparency with respect to an energy light or an electron beam of 200 nm or less. The fluorination rate in the alkyl group or the alkyl group is preferably 70 to 100%, more preferably E 1 00. % is preferably a perfluoroalkylene perfluorocarbon group in which all hydrogen atoms are replaced by fluorine atoms. Further, in the above formula (bl-14), X- may be a halogen anion. Its halogen anion such as fluoride ion or chlorine The compound ion, the bromide ion iodide ion, etc. The compound of the third embodiment of the present invention is preferably exemplified by a specific example. -20- 200914991

[Chemical 5 I

-21 - 200914991 [Chem. 6]

CH2OCF2CF2CF2SO3 (b 1 -1 4-20 1)

(b 1 - 1 4-2 0 2)

-22- 200914991 【化7】

-23- 200914991 【化8】

-24- 200914991

-25- 200914991 【化1 0】

-26- 200914991

Ch2ocf2cf2cf2so;

(b 1 — 1 4 — 3 1 6)

-27- 200914991 【化1 2】

Among them, compounds represented by the aforementioned chemical formulas (bl-14-101), (bl-14-201), (bl-14-301), (bl-14-401) and (bl-14-402) are preferred. . -28-200914991 &lt;Production Method of Compound of Third Embodiment&gt; The compound (b) of the third embodiment of the present invention can be produced, for example, in the following manner. That is, in the solution of the organic acid H + B- (for example, 'methanesulfonate ion, etc., indicating an anion portion of the organic acid), 'the following formula (bl-14-Ol) and (bl-14-〇2) are added. After the compound is reacted, pure water and an organic solvent (for example, dichloromethane, tetrahydrofuran, etc.) are added, and the organic layer is recovered, and the following formula (bl-14-03) is obtained from the organic layer. The compound shown. Next, the compound represented by the formula (bl-14-03) is dissolved in a mixed solvent of an organic solvent (for example, dichloromethane, tetrahydrofuran, etc.) and water, and then the alkali metal salt L of the desired anion X_ is added. + X_ (L+, for example, 'alkali metal cation represented by lithium ion, potassium ion, sodium ion, etc.) is allowed to react. After liquid separation and water washing, the following formula (bl-l4-) is obtained from the organic layer. 〇4) The compound shown. Next, 'the compound represented by the formula (bl-14-04) is dissolved in an organic solvent (for example, 'dichloromethane, tetrahydrofuran, etc.), and after water cooling, an addition test (for example, sodium hydride, etc.) is added to the desired a halide of an alkoxyalkyl or alkoxy group (for example, the formula "C1-C ( R47 ) ( R48 ) - 〇 - r49", "c 1-R5 〇 - C ( = 0 ) - 〇 - R51 "Br-R50-C (= 〇)-0-R51", etc., wherein r47 to r51 are the same as described above) - "-R1C" - the hydrogen atom of the -OH group of -OH and the alkoxy group described above The alkyl or alkoxycarbonylalkyl group is substituted to give the compound (b丨_丨4). -29- 200914991 【化1 3】 Ο t r8,-s-r9&quot;

H-R10-〇H (b 1 - 1 4-0 1 ) (b 1 - 1 4-0 2) OHR10&quot; H+B' R8-S+ B' (b 1 — 1 4-0 3)

OH D10&quot; R8'2 S+ X-(b 1 - 1 4) L+X- x* ^ R9&quot; (b 1 - 1 4-0 4) [wherein R8" and R9, with the above formula (b) 厌 中 8 and R are the same content; the aryl group obtained by removing one hydrogen atom from the ulnar 7 of the aryl group in the above formula (w-14); Β is an anion of an organic acid The moiety 'L+ is an alkali metal cation; the X. system is the same as I in the above formula (bl_14).) Further, in the anion exchange of the compound (bl-14-03), the system can be reacted by L + X. The hydrogen atom of the -H group of -R1(&gt;"-〇H of the compound (bl-14-03) is previously substituted with the alkoxyalkyl or alkoxycarbonylalkyl group to carry out anion exchange. The compound (b) can be obtained. The acid generator of the fourth embodiment of the present invention (hereinafter, also referred to as an acid generator (B1)) is composed of The compound represented by the above formula (bl-14) is formed. In the formula, the compounds listed in the formulas of 'R7'' to R9'', X-series and the above-mentioned third embodiment of the present invention -30-200914991 For the same content. A photoresist composition of the present invention: "The photoresist composition of the first embodiment of the present invention will be described. The photoresist composition of the first embodiment of the present invention contains a base for the action of an acid. The substrate component (A) (hereinafter referred to as (A) component) which changes the solubility of the developer, and the acid generator component (B) which generates an acid by exposure (hereinafter, also referred to as (B) component) Further, the component (B) is an acid generator (B 1 ) containing a compound represented by the above formula (bl-14). In the photoresist composition of the present invention, the component (A) can be used via an acid. As the polymer material which changes the solubility of the alkali developing solution, it is also possible to use a low molecular material which changes the solubility of the alkali developing solution by the action of an acid. Further, the photoresist composition of the present invention may be The negative photoresist composition or the positive photoresist composition. When the photoresist composition of the present invention is a negative photoresist composition, for example, the component (A) is an alkali-soluble resin, and the negative photoresist composition A crosslinking agent (C) is added to the material. The negative photoresist composition is in the form In the case of the resist pattern, when the acid is generated by the exposure of the component (B) by exposure, the exposed portion forms a crosslink between the alkali-soluble resin and the crosslinking agent via the action of the acid, and changes to alkali-insoluble. The soluble resin' can be formed by a resin having at least one -31 - 200914991 units selected from ct-(hydroxyalkyl)acrylic acid, or lower alkyl ester of -(hydroxyalkyl)acrylic acid It is better to have a good photoresist pattern of less swelling. Further, "-(hydroxyalkyl)acrylic acid' is bonded to the carboxyl group (the carbon atom at the X position is bonded to the hydrogen atom)丨 __ 'The meaning of one or both of the α-hydroxyalkyl acrylates bonded to the carbon atom of the α-position bonded to the hydroxyalkyl group (preferably the carbonic acid number 1 to 5) ° Crosslinking agent (c), for example, when an amine-based crosslinking agent having a methylol group or a methoxymethyl group such as glycoluril is usually used, a good photoresist pattern with less swelling can be formed, and good. The amount of the crosslinking agent (c) to be added is preferably 1 to 50 parts by mass based on 1 part by mass of the alkali-soluble resin. When the photoresist composition of the present invention is a positive photoresist composition, the component (A) is insoluble to the alkali developer before exposure, and the acid generated by the component (B) is formed by exposure when the photoresist pattern is formed. In the case of the action, the acid dissociable dissolution inhibiting group is dissociated, and the solubility of the alkali developing solution of the whole (A) component is increased to change from alkali insoluble to alkali soluble. Therefore, in the formation of the photoresist pattern, when the photoresist film obtained by applying the positive-type photoresist composition on the substrate is selectively exposed, the exposed portion is converted into alkali-soluble, and the unexposed portion is It is an alkali-insoluble, unaltered state, and alkali development is possible. In the resist composition of the present invention, the component (A) is preferably a substrate component which increases the solubility in an alkali developing solution by the action of an acid. That is, the photoresist composition of the present invention is preferably a positive photoresist composition. Further, the component (A) is preferably a resin component (A 1 ) (hereinafter also referred to as (A1) component) which increases the alkali solubility by the action of an acid. -32- 200914991 &lt; (A 1 ) Component&gt; The (A 1 ) component which is preferably used in the positive resist composition is a structural unit derived from an acrylate having an acid dissociable dissolution inhibiting group (a) 1) is better. Further, the component (A1) is preferably a structural unit (a2) derived from an acrylate having a cyclic group containing a lactone. Further, the component (A1) is preferably a structural unit (a3) derived from an acrylate further having an aliphatic hydrocarbon group having a polar group. In the present specification and the scope of the patent application, "the structural unit derived from acrylate" means the structural unit constituted by the cracking of the ethylenic double bond of the acrylate. The "acrylate" means a carbon atom of the α-position, in addition to an acrylate having a hydrogen atom bonded thereto, and a compound in which a carbon atom at the α-position is bonded with a substituent (atom or a group other than a hydrogen atom). The substituent is, for example, a lower alkyl group, a halogenated lower alkyl group or the like. Further, the ct position (carbon atom of the α-position) of the structural unit derived from the acrylate means a carbon atom bonded to the carbonyl group unless otherwise specified. In the acrylate, a lower alkyl group of the substituent at the α-position, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isoprene group A linear or branched lower alkyl group such as a benzyl group or a neopentyl group. Further, the halogenated lower-grade base group is specifically a group obtained by substituting a part or all of a hydrogen atom in the above-mentioned "lower alkyl group of the α-substituted substituent" with a halogen atom. The halogen atom 'e.g., a fluorine atom, a chlorine atom, a bromine atom -33-200914991, a sulfo atom or the like is particularly preferably a fluorine atom. In the present invention, the α-position of the acrylate is preferably a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and more preferably a hydrogen atom, a lower alkyl group or a fluorinated lower alkyl group. It is easy to obtain a viewpoint such as a hydrogen atom or a methyl group. • Structural unit (a 1 ) The structural unit (a 1 ) is a structural unit derived from an acrylate containing an acid dissociable dissolution inhibiting group. The acid dissociable dissolution inhibiting group in the structural unit (a 1 ) is such that, as long as the (A 1 ) component has an alkali-insoluble alkali dissolution inhibiting property before dissociation, the (A 1 ) component is obtained by dissociation of the acid. It is sufficient to increase the solubility in the alkali developing solution, and it is possible to use an acid dissociable dissolution inhibiting group which has been proposed as a base resin for a chemically amplified resist composition. In general, for example, a carboxyl group in (meth)acrylic acid may form a cyclic or chain tertiary alkyl ester group, or an acetal acid dissociable dissolution inhibiting group such as an alkoxyalkyl group. Further, "(meth) acrylate" means one or both of a acrylate having a hydrogen atom bonded to the α-position and a methyl acrylate having a methyl group bonded to the α-position. Here, the "trialkyl ester", for example, a hydrogen atom of a carboxyl group is substituted with a chain or a cyclic alkyl group to form an ester, and an oxygen atom at the terminal of the carbonyloxy group (-C(0)-0-) is bonded. A structure obtained by the tertiary carbon atom of the above-mentioned chain or cyclic alkyl group. In the above tertiary alkyl ester, the bond between the oxygen atom and the tertiary carbon atom can be interrupted by the action of an acid. Further, the chain or cyclic alkyl group may have a substituent. Hereinafter, the acid dissociable group composed of a carboxyl group and a tertiary alkyl ester is conveniently referred to as a "triester alkyl ester type acid dissociable dissolution inhibiting group". The tertiary alkyl ester type acid dissociable dissolution inhibiting group, for example, an aliphatic branched acid dissociable dissolution inhibiting group, an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, and the like. Here, the term "aliphatic" as used in the scope of the present application and the specification refers to the relative complication with respect to aromatics, that is, the meaning of a group or a compound having no aromaticity. "Aliphatic branched" means a branched structure having no aromaticity. The structure of the "aliphatic branched acid dissociable dissolution inhibiting group" is not limited to a group (hydrocarbon group) formed of carbon and ammonia, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and it is generally preferred to saturate. The aliphatic branched acid dissociable dissolution inhibiting group is preferably a tertiary alkyl group having 4 to 8 carbon atoms. Specifically, for example, tert-butyl, tert-pentyl, tert-heptyl or the like. The "aliphatic cyclic group" means a monocyclic or polycyclic group having no aromaticity. The "aliphatic cyclic group" in the structural unit (a 1 ) may have a substituent or may not have a substituent. The substituent is, for example, a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkane having a carbon number of 1 to 5 substituted by a fluorine atom, and an oxygen atom. "The fat is not limited by carbon, and the "hydrocarbon group" is preferably . "A fatty aliphatic or fluorinated alkylalkane, a monocyclic alkane or a cyclododecane obtained by a tricyclic atom, and the like, are contained in a cyclic alkyl group, for example, 2 or, for example, bonded to a carbonyloxantane as described below. a group of a ring or a cyclododecyl atom (=〇), etc. a group consisting of a hydrogen group and a hydrogen group (which may be a saturated or unsaturated ring group) is a polycyclic ring group. Specific examples, the substituted, or a group such as an alkane or a tetracycloalkane, etc., more specifically, an adamantane or a norbornane polycyclic alkane is removed from the ring skeleton having an aliphatic cyclic group. a radical having a -methyl-2-adamantyl formula (al"-l)-yl (-C-(O)-0.hexyl, cyclopentyl, descending aliphatic cyclic alkyl group Etc. The basic ring structure of the substituent, and a hydrocarbon group), but preferably a hydrocarbon group. Alternatively, it is preferred to use a saturated group as a base. For example, it can be substituted by a lower alkyl group or a fluorine atom. One or more hydrogens are removed from a monocyclic alkane or a bicyclic polycyclic alkane, for example, an alkane such as cyclopentane or cyclohexane, iso-araconine, tricyclodecane, or more than four hydrogen atoms. An acid dissociable dissolution inhibiting group, for example, a group of a tertiary carbon atom, or the like, or a 2-ethyl-2-adamantyl group or the like. In the structural unit represented by (a 1 ′ - 6 ), The base of the oxygen atom is 'having a gold borneol, a tricyclodecyl group, a tetra, and a triple carbon bonded thereto-36-200914991 [Chem. 1 4]

Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R1&quot; and R16 are alkyl groups (may be linear or branched, preferably 'carbon number 1 to 5)]° In the general formula (al,, -l)~(al, '-6), the lower alkyl group of R or the halogenated lower alkyl group, for example, is lower than the above-mentioned lower-grade or low-toothed base which can be bonded to the α-position of the acrylate. The alkyl group is the same content. The "acetal type acid dissociable dissolution inhibiting group" is generally an oxygen atom bonded to a hydrogen atom at the terminal of an alkali-soluble group which substitutes a carboxyl group or a hydroxyl group. Therefore, when an acid is generated by exposure, the bond between the acetal type acid dissociable dissolution inhibiting group and the oxygen atom to which the acetal type acid dissociable dissolution inhibiting group is bonded is cut by the action of the acid. The acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (Ρ 1 ). -37- 200914991 [Chem. 1 5]

—C-〇-fcH2)-Y

[wherein, R1' and R2' are each independently a hydrogen atom or a lower alkyl group, n is an integer of 0 to 3, and hydrazine is a lower alkyl group or an aliphatic cyclic group]. In the above formula, η is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 〇. The lower alkyl group of R1' and R2' is, for example, the same as the lower alkyl group of the above R, and preferably a methyl group or an ethyl group, and a methyl group is most preferable. In the present invention, it is preferred that at least one of R1' and R2' is a hydrogen atom. Namely, the acid dissociable dissolution inhibiting group (ρ 1 ) is preferably a group represented by the following formula (ρ 1 -1 ). 【化1 6】

• ( ρ 1 — 1 ) [wherein, R1', η, and Υ are the same as the above. The lower alkyl group of hydrazine is, for example, the same as the lower alkyl group of the above R. The aliphatic cyclic group of hydrazine can be appropriately selected from the monocyclic or polycyclic aliphatic cyclic group which has been proposed many times in the conventional ArF photoresist, for example, and the above-mentioned "aliphatic ring type". The base is the same content. Further, the acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (p2). [Chemical Formula 1] r -C-Ο-R19 r18 · * (p 2) [wherein, R17 and R18 are each independently a linear or branched alkyl group or a hydrogen atom, and R19 is a linear chain or a branch. A chain or a cyclic alkyl group, or R17 and R19 are each independently a linear or branched alkyl group, and the terminal of R17 is bonded to the end of R19 to form a ring]. In R17 and R18, the alkyl group preferably has 1 to 15 carbon atoms, and may be linear or branched, preferably ethyl or methyl, and most preferably methyl. In particular, it is preferred that either of R17 and R18 is a hydrogen atom and the other is a methyl group. When R19 is a linear, branched or cyclic alkyl group, the number of carbon atoms is preferably from 1 to 15, and it may be any of a linear chain, a branched chain or a cyclic chain. When R19 is linear or branched, the carbon number is preferably from 1 to 5, more preferably ethyl or methyl, and most preferably ethyl. When R19 is a ring, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, it may be substituted by a fluorine atom or a fluorinated alkyl group, or may be removed by a polycyclic alkane such as a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane which is not substituted. More than one hydrogen atom or the like. Specifically, for example, a monocyclic chain such as cyclopentane or cyclohexane, or adamantane, norbornane, isopentane, a tricyclic brothel, a four-ring, twelve-yard, etc. -39-200914991 polycyclic alkane The base of one or more hydrogen atoms is removed. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferred. Further, in the above formula, R17 and R18 are each independently a linear or branched alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and the terminal of R19 may be bonded to the end of R17. Also. At this time, R17 and R19 are bonded to the oxygen atom bonded to R19, and the oxygen atom forms a cyclic group with the carbon atom bonded to R17. The ring base is preferably a 4 to 7 member ring, and a 4 to 6 member ring is preferred. Specific examples of the cyclic group include, for example, a tetrahydropyranyl group, a tetrahydrofuranyl group and the like. The structural unit (a 1 ) is one selected from the group consisting of the structural unit represented by the following formula (a 1 - 0 -1 ) and the structural unit represented by the following formula (al-0-2 ). The above is better.

[In the formula, R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; and X1 is an acid dissociable dissolution inhibiting group]. -40- 200914991

[In the formula, R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; X2 is an acid dissociable dissolution inhibiting group; and Y2 is an alkylene group or an aliphatic cyclic group]. In the formula (al-0-l), the halogen atom of R, the lower-grade or the halogenated lower alkyl group is the same as the above-mentioned halogen atom, lower alkyl group, or halogenated lower alkyl group which may be bonded to the α-position of the acrylate. The meaning. X1 is not particularly limited as long as it is an acid dissociable dissolution inhibiting group, and may be, for example, a tertiary alkyl ester type acid dissociable dissolution inhibiting group or an acetal type acid dissociating dissolution inhibiting group, and a tertiary alkyl group. The ester-type acid dissociable dissolution inhibiting group is preferred. In the formula (al-0_2), R has the same meaning as described above. X2 is the same as X1 in the formula (al-0-1). Y2 is preferably an alkylene group having a carbon number of 1 to 1 Torr or a divalent aliphatic ring group. In the case of the aliphatic cyclic group, the same as the above description of the "aliphatic cyclic group" can be used, except for the use of a group in which two or more hydrogen atoms are removed. -41 - 200914991 In the structural unit (al), more specifically, for example, the structural unit represented by the following general formula (al-Ι) to (al-4). [化2 0]

[In the above formula, 'X' is a tertiary alkyl ester type acid dissociable dissolution inhibiting group; Y is a lower fluorenyl group having a carbon number of 1 to 5, or an aliphatic cyclic group; η is an integer of 〇 to 3; Υ 2 is The excipient or aliphatic cyclic group; R has the same meaning as above; R1', R2' are each independently a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms]. It is preferable that at least one of R1' and R2' is a hydrogen atom, and more preferably a hydrogen atom. η is preferably 0 or 1. X' is the same as the cyclic tertiary alkyl ester type acid dissociable dissolution inhibiting group exemplified in the above X 1 . The aliphatic cyclic group of hydrazine is, for example, the same as those exemplified in the description of the above "aliphatic cyclic group". Υ2 is preferably an alkylene group having a carbon number of 1 to 10 or a divalent aliphatic cyclic group-42-200914991 'The aliphatic cyclic group may be used in addition to the group obtained by removing two or more hydrogen atoms, and may also be used. The above "aliphatic cyclic group" is illustrated as the same group. When γ2 is an alkylene group having 1 to 1 carbon atoms, it is more preferably 1 to 6 carbon atoms, most preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. When Y2 is a divalent aliphatic ring-based group, two or more hydrogen atoms are removed from cyclopentanium, cyclohexyl, norbornene, isoborn, adamantane, tricyclodecane, and tetracyclododecane. The basis obtained is the best. The following are specific examples of the structural unit represented by the above formula (al-Ι) to (al-4), -43- 200914991 lit 2 1 ch3 -fcH2 - C-V. Heart ' 0=1 © &lt; ch2-ch

CH

(a1-1-2)

^h2-chV ,

CH

Cat-1-8) (CH2)3CH3 (a1-1-7)

(a1-1-9) CHf (al-1-10) ch3

CH3 &quot;CH2—c-A- -ch2—c-^~ 0==\ CH3 〇,^

(a1-1-13)

(a 1-1-14) 〇4 〇2h50, CH2—ch} °=( C2H5 -44 - 200914991 [Chem. 2 2]

(a1-1-21) (a1-1-22) (a1-1-23)

3 (al+27) (a1 10 28) (a1~1~25) (a 1 —Ή26)

(a1-1-31) (a1-1-32) -45- 200914991 [Chem. 2 3]

-ch2—chV -/-CHr-Q_L

CH2—CH^~

(a1—1-41)

. 4 i. 4

〇=A mr :ir 【化2 4】

Ch3 ~(ch2-c-)-

(a1-2-4)

(a1-2-5)

-46- 200914991 [Chemical 2 5 ch3 10 2 | 0=&lt; 〇, (a 1-2*7) -fcH2-CHV-〇4^ (a1'2-10) ch3 —(ch2-c-)- O^- (a1-2-13) -(ch2-ch)- &gt;=k ch3 —(ch2-c4- 〇4 〇= 〇.

Cal-2-16) —fcH2-c)— 〇~ (al-2-19) o 〇· (a1-2-9) ch3 —f〇H2-c)— ΊΘ 〇4° ° -fcH2-CHV- 〇一(a1-2-12) , 0 -^CH2-ch)-Name (:::3⁄4

,0

O- (al-2-14)f3 -(ch2-〒十-o 〇4 (a1-2-17), i2Z .〇Ow (a1-2-20) ch3 —(-ch2-c^- 〇, (a 1-2-15) f3 —(ch2-c-)- 〇,

p (a1—2-18) :°3⁄4 -47- 200914991 【化2 6 ch3 / ί \ —(ch2-c-)- 0=^〇ν〇ΤΊ (a1-2-21) -(ch2-ch ) - -{ch2—ch)〇4 0, (a1-2-22) ch3 I, ch2-c4—〇4 0, ~T&gt; (a 1-2-24) (a1 -2-25) —( Ch2-c-)—fly, Γ3—(ch2-c4-. .4X) °- (a 1 -2-27) (a 1-2-28) 〇

Ch3 -(ch2-c·)- (a1-2-31) ch3 〇~ (a1-2-23) -(ch2-ch 卜 T). 4. ~ \^___/ (31-2-26) cf3 —(-ch2-c^— 0=l &quot;O (.~

;O •0 -48- 200914991 [Chem. 2 7]

(al-2-32) (a1-2-33) (a1-2-34)

(a1-2-35) (a1-2-36)

-49- 200914991 [Chem. 2 8]

Cal-3-1) (a1-3-2) Ca 1-3-3)

Cat-3~5)

Cal-3-β)

Ca1-3-1〇) (at-3-Jl) (ai-3-t2)

50- 200914991 [Chem. 2 9]

-51 - 200914991

[化3 Ο] CH ch3 ?H3 ch3 -(CH2-C-)- ~(CH2^h)- -f cH2-C-)- -(-CH2-Ch)- -(*CH2-^f 〇10 , ° / ° 0 - ° gas.% gas is O Guang 0, Q Γ °

ο Ο Ο )ο

ο ; Q (a1-4~1) (at-4-2)

Ca 1-4-4) ?η3

Ca1-4-3)

Ca 1-4-5) CH 9Η3 -^-CH2-CH}- -^CH2-C-)--(-CH2-C^--(CH2-C-3--(-CH2-CH)- iiiiii (a 1-4-0) t δ (a1-4-7) (a 1-4-8) (al-4-9) (a1-4-10) (al-4-11)

• CH ch3 ch3 l2&quot;*cH]h -(-ch2-ch) (-ch2-c-)— &quot;f ch2—9 two r\ one. °&gt;〇=&lt;〇〇&gt;°&gt; 〇, ό ο

,0

.〇 〇 。. .0

-CH;ο

CH3 .〇 P

Q〇 〇&gt;〇

Ca 1-4-12) Ca1-4'13) (at-4-14) 0. 0 (al-4-15) h (a1-4-16) (al-4-17) 52- 200914991 3 1 CH.H0 ten ^ ten H 咩 咩 f ten + ten? ? \ \ °\. 4

0) 〇 Ο 0 &gt; 〇 ) U) (al-4-18) (al-4^19) (al-4-20) (a1-4-21) (al-4-22)

-CH2. ·^ Ten H. ^子十卡 H士卡Η ^Word f CH^_ _/° P P ρ 〇 〇 (al-4-24)

Ο \

〇 ;=0 〇v 0,

〇

Ο ο ο

(8l'4'2S) (8, '4&quot;2W (a,+27)(4)-4-2« Cat-4-29) (al-4-30) ., H3C ten ch2 h3c o =〇

Cal-4-31) 1Θ (at-4-33) (a1-4-32) , . H3? 0=\ °\ 0==^ (Material 34) ________ (el-4-35)

Cat-4-36) 才 f f CH才 + f CH 念 ffCH by H+ f CH Hf f CH"- /° / p °&gt; 〇 b 〇Λ S 彳 S ( S 〇 b

(al-4-37) (at-4-39) (at-4-38) Cal-4-40) (4)-4-41)

Cat-4-42) The structural unit (a 1 ) ' may be used singly or in combination of two or more. -53- 200914991 Among them, the structural unit represented by the formula (a 1 -1 ) is preferred. Specifically, at least one selected from the group consisting of the formulae (al-1-l) to (al-1-6) and the formula (al-1-35) to (a 1 -1 - 4 1 ) One is the best. Further, the structural unit (al) is, in particular, a unit ' or a formula (al-1) represented by the following general formula (31_b 01) containing structural units of the formula (al-ll) to (al_; !_4) The following formula (al_l-02) of the structural unit of -35) to (al-:l-41) is preferred. [化3 2]

Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and R11 is a lower alkyl group] [Chemical 3 3]

c=o

-54- 200914991 [wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and R12 is a lower-grade hospital group, and h is an integer of 1 to 3]. In the formula (al-1-Ol), R has the same content as described above. The lower alkyl group of R11 is the same as the lower alkyl group represented by R, and a methyl group or an ethyl group is preferred. In the formula (al-l-〇2), R has the same content as described above. The lower-grade yard base of R12 is the same as the lower-grade yard base shown by R above, and is preferably methyl or ethyl, and ethyl is preferred. h is preferably 1 or 2, and 2 is the best. In (A 1 ), the ratio of the structural unit (a 1 ) is from 10 to 80 mol with respect to the entire structural unit constituting the component (A1). /. Preferably, it is preferably from 20 to 70% by mole, and preferably from 25 to 50% by mole. When the lower limit is 値 or more, the pattern can be easily formed when it is a positive resist composition, and it can be balanced with other structural units when it is below the upper limit 値. • Structural unit (a2) In the present invention, the structural unit (a2) is a structural unit derived from an acrylate having a cyclic group containing a lactone. Here, the cyclic group containing a lactone is a cyclic group containing one ring (lactone ring) of the -O-C(O)- structure. The lactone ring is counted as a ring unit, and the monocyclic group is only a lactone ring. If the ring has other ring structures, regardless of its structure, it is called a polycyclic group. The lactone ring group of the structural unit (a2) can effectively improve the adhesion of the photoresist film to the substrate in the case where the (A1) component is used to form the photoresist film, and can effectively improve Affinity with a developer containing water. Among them, the structural unit (a2) can be used in any unit without any limitation. Specifically, a lactone-containing monocyclic group such as butyrolactone is obtained by removing one hydrogen atom. Further, the polycyclic group having a lactone is, for example, a group obtained by removing one hydrogen atom from a bicycloalkane having a lactone ring, a tricycloalkane or a tetracycloalkane. In the exemplification of the structural unit (a2), 'more specifically' is, for example, a structural unit represented by the following general formulas (a2-l) to (a2-5). [化3 4]

Wherein R is a hydrogen atom, a lower-grade or a halogenated lower-grade, R is a hydrogen atom, a lower alkyl group, or an alkoxy group having a carbon number of 1 to 5, and „! is an integer of 〇 or 1, and A is The alkyl group having 1 to 5 carbon atoms or the oxygen atom]. In the formulae (a2-l) to (a2-5), 'R has the same content as R in the above structural unit (al). Lower alkyl group of R' 'having the same content as the lower alkyl group of R in the above structural unit (a 1 ). The alkyl group having a carbon number of 1 to 5', specifically, for example, methyl group, ethyl group, η-extension In the formulae (a2-l) to (a2-5), R' is preferably a hydrogen atom from the viewpoint of industrial availability. An example of a specific structural unit of (a2-l) to (a2-5). [Chemical 3 5]

-57- 200914991 [Chemical 3 6] ch3 TMfCH2-C·)-〇4 -(ch2-ch)-°=\ ch3 ch3 -fCH2-c-)- -(CH2-C·)- ' o o.

(a2-2-1) 〇

(a2-2-2) ch3 B〇〆0 (a2-2-6) (a2-2-3)

O ch3

O (32-2-4) CH3

O (a2-2-7) O, ch3

(32-2-10) 58 200914991 [Chemical 3 7] ch3 -(cH2-c)- -(cHj-CH, 〇, a ^ 0.

(9) Column 〇 (32^-2) 0 ch3 -{ch2-c·)- -{ch2-ch〇&lt; 〇4 o, o

o.

Ch3 O ch3 0 (a2-3-4) (a2-W)

(a2-3-6) ch3 -(ch2-c^- -(ch2-ch^- 0==( 0=

~(ch2-ch}- 0=4

0 (a2-3-1〇)

-59- 200914991 [Chem. 3 8]

(a2-4-7) (a2*4-8) (a2-4-9) -{ch2-ch&gt;- ch3 p H3C, - H3C (32-4-11) (a2-4-12). ^. Speaking secret -60- 200914991 [Chemical 3 9]

H3C (a2·*-5) (aZ-5-6) wherein, at least one selected from the structural units represented by the formulas (a2-l) to (a2-3) is preferred, and It is more preferable that at least one or more selected from (a2-l) to (a2-3). Specifically, the equations (a2-1 -1), (a2-1-2), (a2-2- 1 ), (a2-2-2), (a2-3-1), (a2) are used. One or more selected from -3-2), (a2-3-9) and (a2-3-10) are preferred. In the component (A1), the structural unit (a2) may be used singly or in combination of two or more. The ratio of the structural unit (a2) in the component (A1) is preferably 5 to 60 mol%, and 10 to 50 mol%, based on the total of the structural units constituting the component (-61 - 200914991 A1). % is preferred, preferably 20 to 50% by mole. When it is more than the lower limit 値, the effect can be sufficiently obtained when the structural unit (a2) is contained, and when it is less than the upper limit 値, the balance with other structural units can be obtained. • Structural unit (a3) The structural unit (a3) is a structural unit derived from an acrylate having an aliphatic hydrocarbon group containing a polar group. When the component (A3) has a structural unit (a3), the hydrophilicity of the component (A) can be improved, and the affinity with the developer can be improved, and the alkali solubility of the exposed portion can be improved, and the resolution can be expected to be improved. A polar group such as a hydroxyl group, a cyano group, a carboxyl group, a hydroxyalkyl group in which a part of hydrogen atoms in the alkyl group is substituted by a fluorine atom, and the like are preferably a hydroxyl group. The aliphatic hydrocarbon group 'e.e., a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group), or a polycyclic aliphatic hydrocarbon group (polycyclic group) or the like. The polycyclic group is, for example, a resin which can be used for a composition for a photoresist for an ArF excimer laser, and is appropriately selected from the contents of most proposals. The polycyclic group preferably has a carbon number of from 7 to 30. Further, a structural unit derived from an acrylate having a hydroxyl group, a cyano group, a carboxyl group, or an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms in the alkyl group is substituted by a fluorine atom is more preferable. The polycyclic group is, for example, a base temple obtained by removing two or more hydrogen atoms from a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, it is solidified by, for example, a multi-ring chain such as the King Kong Institute, the Nori Institute, the Weak House, the Third Ring Hospital, and the Fourth Ring and the 12th Institute, and the base obtained by removing two or more hydrogen atoms - 62 - 200914991 atoms. In the polycyclic group, it is more suitable for industrially to remove two or more hydrogen atoms from adamantane, to remove two or more hydrogen atoms from norbornane, and to remove two or more hydrogen atoms from tetracyclododecane. use. In the structural unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group having a polar group is a linear or branched hydrocarbon group having 1 to 1 carbon atoms, the structural unit derived from hydroxyethyl acrylate of acrylic acid is When the hydrocarbon group is a polycyclic group, for example, a structural unit represented by the following formula (a 3 -1 ), a structural unit represented by (a 3 · 2 ), and a structural unit represented by (a3-3) are preferable. [化4 0]

OH (a3-3) [wherein R has the same meaning as described above, j is an integer from 丨 to 3, k is an integer from 1 to 3, t' is an integer from 1 to 3, and 1 is an integer from 1 to 5. , S is an integer from 1 to 3.]. In the formula (a3-l), 'j is preferably 2 or more and more preferably 1 is used. In the case where j is 2, it is more preferable that the base group is bonded to the 3 and 5 positions of the diamond base. In the case where j is 1, 'especially hydroxy-bonded to the base of the King Kong Institute -63-200914991 3 is the best. It is also preferable that j is 1 and it is preferable that the hydroxyl group is bonded to the base of the King Kong. In the formula (a3-2), it is preferred that k is one. Further, it is preferred that the cyano group is bonded to the 5- or 6-position of the norbornyl group. In the formula (a3-3), it is preferable that t' is one, and that one is one, and it is preferable that s is one. It is preferred that the terminal of the carboxyl group of the above-mentioned acrylic acid is bonded to the compound of the 2 -norborn or 3-norborn. Preferably, the fluorinated alcohol is bonded to the 5 or 6 position of the norbornyl group. In the component (A 1 ), the structural unit (a3) may be used singly or in combination of two or more. The ratio of the structural unit (a3) in the component (A 1 ) is preferably from 5 to 50 mol%, more preferably from 5 to 40 mol%, based on the entire structural unit constituting the component (A 1 ). The best is 5 to 25 mol%. When the lower limit is 値 or more, the effect of containing the structural unit (a3) can be sufficiently obtained, and when it is less than the upper limit 値, the balance with other structural units can be obtained. • Structural unit (a4) (A1) component 'in the range not impairing the effects of the present invention, may further contain other structural units (a4) 〇 structural unit (a4) other than the above structural units (a 1 ) to (a3) It is not particularly limited as long as it is a structural unit that is not classified into the above structural units (a!) to (a3). It is possible to use a conventionally known plurality of structural units used for a photoresist composition such as an ArF excimer laser or a KrF excimer laser (preferably for ArF sub-fraction -64 - 200914991 sub-laser). The structural unit (a4), for example, a structural unit derived from an acrylate having a non-acid dissociable aliphatic polycyclic group is preferred. The polycyclic group is, for example, the same as exemplified in the above structural unit (a 1 ), and can be used for ArF excimer laser or KrF excimer laser (preferably for ArF excimer laser). Most of the conventionally known structural units used for the resin component of the photoresist composition. In particular, when at least one selected from the group consisting of a tricyclodecylalkyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is industrially preferable, it is preferably obtained. The polycyclic group may be substituted by a linear or branched alkyl group having 1 to 5 carbon atoms. The structural unit (a4) is specifically, for example, a structural unit represented by the following general formulae (a4-l) to (a4-5). [化4 1]

[wherein R has the same content as described above]. When the structural unit (a4) is contained in the (A丨) component, the ratio of the structural unit (a4) to the total structure of the constituents of the (A1) component is -65 to 200914991, to 1 to 3 0% by mole is preferred, and more preferably 1% to 20% by mole. In the present invention, the (Α1) component is a resin component (polymer) which increases the solubility to the alkali developer based on the action of an acid, and is suitable as a unit of the resin component (polymer), for example, having a structural unit (a 1 ). , structural unit (a2), and copolymer of structural unit (a3) 'the aforementioned copolymer, for example, a copolymer obtained from structural units (a 1 ), ( a2 ), and (a3 ), structural unit (a 1 ) And the copolymer obtained by (a2), (a3) and (a4). (A1) The component ' can be used alone or in combination of two or more. In the present invention, the component (A1) is, in particular, a copolymer (A1-1) to (A1) containing a combination of structural units represented by the following formula (A 1 -1 ) to (A 1 - 3 ). 3) is better.

-66- 200914991 [wherein R has the same content as described above, and the plural R may be the same or different. R20 is a lower alkyl group]. In the formula, R has the same content as described above. Among them, hydrogen atom or methyl group is preferred. Wherein 'R2Q is a lower alkyl group, of which methyl or ethyl is preferred. The copolymers (A1-1) to (A1-3) in the component (A) may be used singly or in combination of two or more. Further, when two or more of the 'copolymers (A1-1) to (A1-3) are used in combination, it is preferable to use a combination of copolymers such as a copolymer (A 1 - 2 ) and (A 1). - 3) combinations, etc. The content of the copolymer (A1-1) to (A1-3) in the component (A) is preferably 70% by mass or more, and more preferably 80% by mass or more, and may be 100% by mass. It is also preferably 100% by mass. When the lower limit 値 or more of the range is used, when the positive resist composition is used, the lithographic microetching characteristics can be further improved. (A1) component, for example, a monomer derived from each structural unit, for example, an azo-based radical polymerization initiator such as azo-isobutyronitrile (AIBN) can be produced by a polymerization reaction such as radical polymerization. Got it. Further, in the above-mentioned polymerization, the (A 1 ) component may be, for example, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH, and -c(cf3)2- may be introduced at the end. Oh base. Thus, a copolymer having a hydroxyalkyl group in which one of the hydrogen atoms in the alkyl group is substituted with a fluorine atom can be obtained, whereby the defect can be effectively reduced or the LER (Line Edge Roughness) can be effectively reduced. -67- 200914991 (A1) The mass average molecular weight (Mw) of the component (polystyrene equivalent amount of gel permeation chromatography) is not particularly limited, and is generally preferably 2,000 to 50,000, and more preferably 3,000 to 30,000. Good, 4,000 to 20,000 is the best, and 5,000 to 20,000 is the best. In the above range, when used as a photoresist, sufficient solubility is obtained for the resist solvent, and a good dry etching resistance or a resist pattern cross-sectional shape can be obtained. Further, the degree of dispersion (Mw / Μη) is preferably in the range of 1 · 0 to 5 · 0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5. Further, Μη is a number average molecular weight. Further, as the (A 1 ) component, in addition to the alkali-soluble resin component other than the copolymer (A 1 -1 ) to (A 1 - 3 ), for example, other polymer compounds used in the conventional positive-type resist composition can be used. . In the positive resist composition of the present invention, the content of the (A 1 ) component may be appropriately prepared in accordance with the thickness of the photoresist film to be formed. &lt; (B) Component&gt; In the photoresist composition of the present invention, the component (B) is an acid generator (B 1 ) containing a compound represented by the above formula (b 1 - 14 ) (hereinafter, Also known as (B1) ingredients. In the formula, 'R7' to R9' and X_ are the same as those listed in the above-mentioned third embodiment of the present invention, and the content of the component (B) is formed when the (B 1 ) component is contained. The photoresist pattern can improve the reproducibility of the mask, for example, when forming the connection hole (C / Η) pattern, the roundness and diameter (CD) uniformity of the through hole can be improved (-68- 200914991) CDU) 'Improve the mask error factor (MEF), have excellent C/H pattern pick-up, etc., and improve the lithography etching characteristics. Further, when the line and space resist pattern (L/S pattern) is formed, the MEF is improved, and the lithography residual characteristics can be improved. Subsequently, the photoresist composition of the present invention is excellently used as a photoresist composition for immersion exposure in a photoresist pattern forming method including an immersion exposure step, and good lithographic etching characteristics can be obtained. In the photoresist pattern forming method including the step of forming a three-layer photoresist layer, it is also suitable as a positive-type photoresist composition for forming an upper photoresist film, and good lithographic etching characteristics can be obtained. In the component (B1), the anion moiety is an anion represented by the above formula "R14S〇T" or "R^oY^sor", or the above formula (b-3) or (b-4) The anion is better. Further, it is more preferable to use an anion represented by the formula "R14S03_" or "Ri-O-Y^SOr". (B) The components may be used alone or in combination of two or more. In the photoresist composition of the present invention, the content of the component (B1) in the entire component (B) is preferably 40% by mass or more, more preferably 60% by mass or more, and may be 100% by mass. When the lower limit of the range is above ,, a good photoresist pattern shape can be obtained. In particular, when the photoresist composition for immersion exposure or the photoresist composition for forming an upper photoresist film is used to form a photoresist pattern, the lithography characteristics can be improved. When the three-layer photoresist layer is formed, it is preferable because it has good adhesion to the underlayer film of the photoresist, and it is possible to suppress edge curling of the photoresist pattern. Further, in the photoresist composition of the present invention, the content of the component (B1), phase -69 to 200914991 is preferably from 1 to 30 parts by mass, based on 100 parts by mass of the above component (A), and is from 3 to 18 parts by mass. For better, it is particularly good for 5 to 16 parts by mass. When the lower limit of the range is 値 or more, in particular, when the photoresist composition for immersion exposure or the photoresist composition for forming an upper photoresist film is used to form a photoresist pattern, the lithography characteristics can be improved. Also, when the upper limit is less than 値, good preservation stability can be obtained. In the component (B), the acid generator (B 2 ) other than the component (B 1 ) (hereinafter also referred to as the component (B2)) may be the same as the component (B 1 ). The component (B2) is not particularly limited as long as it is a component other than the component (B1), and a component which has been proposed as an acid generator for a chemically amplified photoresist has been used. The acid generator is, for example, a gun salt acid generator such as an iodine salt or a phosphonium salt, an oxime sulfonate acid generator, a dialkyl or bisarylsulfonyldiazomethane, or a polysulfonate. Hydrazine-based diazomethane-based acid generator, nitrobenzyl sulfonate-based acid generator, iminosulfonate-based acid generator, diterpenoid acid generator, etc. Compound. As the key salt acid generator, for example, a compound represented by the following formula (b-1) or (b-2) can be used. [化4 3]

Rif r4,.s〇-3 (4) /l+ R4S〇3 — (b-2) R6&quot; [wherein 'R1' to R3'', R5'' to R6", each independently being an aryl or alkyl group; -70- 200914991 In the formula (b1), R to R3'', any two of them may be bonded to each other and form a ring together with a sulfur atom in the formula; R4" is linear, branched or cyclic. At least one of the alkyl group or the fluorinated alkyl group 'R1'' to R3,' is an aryl group, and at least one of R5" to R6" is an aryl group. In the formula (bl), 1^'' to R3 The same applies to the formulas R7'' to R9" in the formula (b-14) except that the alkoxyalkylcarbonyl group or the alkoxycarbonylalkoxy group is not a substituent which is substituted as a hydrogen atom. Among R1" to R3", at least one of them is an aryl group. Among R1" to R3", it is preferable to use two or more aryl groups, and it is preferable that all of R1" to R3" are aryl groups. It is preferred that R1'' to R3'' are respectively phenyl or naphthyl. R4 is a linear, branched or cyclic group, or a fluorinated base. The aforementioned linear or branched chain Alkyl group, preferably with carbon number 1-10 to 10, with carbon number 1 to 8 being more Preferably, the cyclic alkyl group is a cyclic group represented by the above R 1 ", and preferably has a carbon number of 4 to 15 and a carbon number of 4 to 1 Å. For better, the best carbon number is 6 to 1 。. The above-mentioned fluorinated alkyl group is preferably one having a carbon number of 1 to 1 Torr, more preferably having a carbon number of 1 to 8 and preferably having a carbon number of 1 to 4. Further, the fluorination ratio of the fluorinated alkyl group (the ratio of the fluorine atom in the alkyl group) is preferably from 1 Torr to 1% by weight, more preferably from 50 to 100%. In particular, all of the hydrogen atoms are replaced by fluorine atoms. The winner is better because the strength of the acid is stronger. R4 'is linear or ring-based, or gasification yard base is best -71 - 200914991 Formula (b-2) 'R5" to R6" are each independently aryl or alkyl; R5' At least one of R6'' is an aryl group, and all of R5" to R6" are preferably an aryl group. The aryl group of R5'' to R6" is, for example, the same as the aryl group of R1" to R3". The alkyl group of R5" to R6" is, for example, the same as the group of R1" to R3". It is also preferred that both of R5'' to R6" are phenyl groups at the same time. R4" in the above formula (b-2) and R4" in (b-Ι) are the same contents. Specific examples of the gun salt acid generators represented by the formulae (b-1) and (b-2), such as 'diphenyliodide trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert) -butylphenyl) iodine gun trifluoromethane sulfonate or nonafluorobutane sulfonate, triphenyl sulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluoro 1 butyl sulfonate 5 Bayeine vinegar, bis(4-methylphenyl) mirror of digastric sulfonic acid vinegar, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, dimethyl (4-hydroxynaphthyl) anthracene Trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, triphenylmethanesulfonate monophenyldimethylhydrazine, its heptafluoropropane sulfonate or its nonafluorobutane sulfonic acid Ethyl ester, triphenylmethanesulfonate of diphenylmonomethylhydrazine, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, trifluoromethanesulfonic acid of (4-methylphenyl)diphenylphosphonium Ester, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluoro Butane sulfonate, three (4-tert- Phenylhydrazine trifluoromethanesulfonate, heptafluoro-72- 200914991 propane sulfonate or its nonafluorobutane sulfonate, diphenyl (1-(4-methoxy)naphthyl) Trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, di(1-naphthyl)phenylphosphonium trifluoromethanesulfonate, heptafluoropropane sulfonate or its nine Fluorobutane sulfonate, 1-phenyltetrahydrothiophene key trifluoromethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-(4-methylphenyl)tetrahydrogen Thiophene iron trifluoromethane sulfonate's heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene-trifluoromethane a sulfonate, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof, a trifluoromethanesulfonate of 1-(4.methoxynaphthalen-1-yl)tetrahydrothiophene, and a heptafluoropropane sulfonate thereof Or a nonafluorobutane sulfonate, a trifluoromethanesulfonate of 1-(4-ethoxynaphthalen-1-yl)tetrahydrothiophene, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof , l-(4-n-butoxynaphthalene-buyl) tetrahydrothiophene Methanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-phenyltetrahydrothienyl trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonic acid Ester, 1-(4-hydroxyphenyl)tetrahydrothienyl trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-(3,5-dimethyl- 4-hydroxyphenyl) tetrahydrothiopyranium trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 4-(4-phenylphenyl)tetrahydrothiopyran Trifluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate thereof. Further, a key salt in which the anion portion of the iron salt is replaced by a methanesulfonate, η-propanesulfonate, η-butanesulfonate or η-octanesulfonate can be used. Further, in the above formula (b-Ι) or (b-2), the anion portion may be substituted with an anion portion represented by the following formula (b-3) or (b-4) to obtain an iron salt-73-200914991. The acid generator may also be (the cationic moiety is the same as the above formula (b_}) or (b_2)). Further, a sulfonium salt having a cation portion represented by the following formula (b-5) or (b-6) may be used as a gun salt acid generator. [4 4]

Wherein R41 to R40 are each independently an alkyl group, an ethyl sulfonyl group, an alkoxy group, a carboxyl group, a hydroxy group or a hydroxyalkyl group; and ~ ns are independent integers of 33, and n6 is an integer of 0 to 2 ]. In R41 to R46, the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a linear or branched alkyl group, and a methyl group, an ethyl group, a propyl group, an isopropyl group, or the like. Η-butyl or tert-butyl is particularly preferred. The oxy group is preferably a methoxy group having 1 to 5 carbon atoms, more preferably a linear or branched decyloxy group, and particularly preferably a methoxy group or an ethoxy group. It is preferred that the base of the hospital is substituted with a hydrogen atom of one or more of the above-mentioned bases, such as a hydroxymethyl 'hydroxyethyl group, a hydroxypropyl group or the like. When the symbols ηι to n6 to be added to R41 to R46 are integers of 2 or more, the plural numbers R41 to R46 may be the same or different. -74- 200914991 ηι is preferably 〇~2, more preferably 〇 or 1, preferably 〇. Preferably, Π2 and η3 are independently 〇 or 1, more preferably 〇. Η4 is preferably 〇~2, more preferably 〇 or 1. Η5 is preferably 0 or 1, more preferably 0. Η6 is preferably 〇 or 1, more preferably 1. The anion portion having the sulfonium salt of the cation portion represented by the formula (b-5) or (b-6) is not particularly limited, and it can be used in the same manner as the anion portion currently proposed as the key salt acid generator. Anion part. The anion portion is, for example, a fluorinated alkylsulfonic acid ion such as an anion portion (R4''S03·) of a gun salt acid generator represented by the above formula (b-Ι) or (b-2); An anion portion or the like represented by (b-3) or (b-4). Among them, a fluorinated alkylsulfonic acid ion is preferred, and a fluorinated alkylsulfonic acid ion having a carbon number of 1 to 4 is more preferred, and a linear perfluoroalkylsulfonate ion having a carbon number of 1 to 4 is used. For the best. Specifically, for example, a trifluoromethanesulfonic acid ion, a heptafluoro-?-propylsulfonic acid ion, a nonafluoro-?-butylsulfonic acid ion or the like. In the present specification, an oxime sulfonate-based acid generator, for example, a compound having at least one group represented by the following formula (Β -1 ) has a property of generating an acid via radiation irradiation. The above-mentioned oxime sulfonate-based acid generator is commonly used in the chemically amplified photoresist composition. The present invention can be optionally used. [Chemical 4 5] -C=N—Ο—S〇2—R31 p32 1 · * (Β - 1 ) [In the formula (Β-!), R3L r32 is independently an organic group]. -75- 200914991 The organic group of R31 and R3 2 is a group containing a carbon atom, but it may also contain an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom). and many more). The organic group of R31 is preferably a linear, branched or cyclic alkyl or aryl group. The aforementioned alkyl group or aryl group may have a substituent. The substituent is not particularly limited and may, for example, be a fluorine atom, a linear one having a carbon number of 1 to 6, a branched or a cyclic alkyl group or the like. Wherein "having a substituent" means that at least one of the hydrogen atoms of the alkyl group or the aryl group is substituted with a substituent. The alkyl group is preferably a carbon number of 1 to 20, preferably a carbon number of 1 to 1 Torr, a carbon number of 1 to 8 or more, preferably a carbon number of 6 to 6 and a carbon number of 1 to 4. good. The 'alkyl group' is particularly preferably a hospital base (hereinafter also referred to as a halogenated alkyl group) obtained by partial or complete halogenation. Further, the partially halogenated alkyl group means an alkyl group in which a part of a hydrogen atom is substituted by a halogen atom, and a wholly halogenated group means an alkyl group in which a hydrogen atom is entirely substituted by a halogen atom. The halogen atom "e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc." is particularly preferably a fluorine atom. Namely, the halogenated alkyl group is preferably a fluorinated alkyl group. The aryl group is preferably a carbon number of 4 to 20, preferably a carbon number of 4 to 10, and more preferably a carbon number of 6 to 1 Å. The aryl group is particularly preferably a square group which is partially or wholly halogenated. Further, the "partially halogenated aryl group" means an aryl group which is completely halogenated by an aryl group in which a part of a hydrogen atom is replaced by a halogen atom, and means an aryl group in which all hydrogen atoms are replaced by a halogen atom. R31 is particularly preferably an alkyl group having 1 to 4 carbon atoms which has no substituent, or a fluorinated alkyl group having 1 to 4 carbon atoms. -76- 200914991 The organic group of R32 is preferably a linear, branched or cyclic alkyl, aryl or cyano group. The base group and the square group of R 3 2 are, for example, the same as those of the alkyl group and the aryl group exemplified in the above R3 1 . R32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms which has no substituent, or a fluorinated group having 1 to 8 carbon atoms. The oxime sulfonate-based acid generator is more preferably a compound represented by the following formula (B-2) or (B-3). [Chemical 4 6] R34—C==N—Ο-S02—R35 R33 · · · · (B-2) [In the formula (B-2), R33 is a cyano group, an alkyl group having no substituent or halogenation An alkyl group; R34 is an aryl group; R35 is an alkyl group having no substituent or a halogenated alkyl group [Chemical 4 7]

[In the formula (B-3), R36 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group; R3 7 is a 2 or 3 valent aromatic hydrocarbon group; and R3 8 is an alkyl group having no substituent or halogenation. The alkyl group, P" is 2 or 3]. In the above formula (B-2), the alkyl group or the halogenated alkyl group having no substituent of R33 is preferably a carbon number of 1 to 10 and a carbon number of 1 to 8. More preferably, the carbon number is preferably from 1 to 6. -77- 200914991 R3 3 is preferably a halogenated alkyl group, and more preferably a fluorinated group. The fluorinated alkyl group in R33 has a hydrogen atom in the alkyl group. It is preferably 5% or more of fluorinated, more preferably 70% or more, and more preferably 90% or more of fluorinated. R34 aryl, such as phenyl or biphenyl, fluorenyl a ring of an aromatic hydrocarbon such as a fluorenyl group, a naphthyl group, an anthyl group or an phenanthroline group, which removes one hydrogen atom, and a part of a carbon atom constituting the ring of the above group is an oxygen atom, The heteroaryl group such as a sulfur atom or a nitrogen atom is substituted with a heteroaryl group or the like, and a fluorenyl group is more preferable. The aryl group of R34 may have an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. Base group. The substituent The base or halogenated yard base preferably has a carbon number of 1 to 8, preferably a carbon number of 1 to 4. Further, the halogenated alkyl group is more preferably a fluorinated alkyl group. The alkyl group or the halogenated alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 6. R3 5 is preferably a halogenated alkyl group or a fluorinated alkyl group. More preferably, the fluorinated alkyl group in R35 is preferably one in which the hydrogen atom in the alkyl group is fluorinated by 50% or more, more preferably 70% or more, and more preferably 90% or more. More preferably, it is a perfluorinated alkyl group in which 100% of hydrogen atoms are substituted by fluorine. In the above formula (B-3), an alkyl group or a halogenated alkyl group having no substituent of R36, for example It is the same as the alkyl group or the halogenated alkyl group having no substituent represented by the above R33. The 2 or 3 valent aromatic hydrocarbon group of R37 is, for example, 1 or 2 removed from the aryl-78-200914991 group of the above R34. The group obtained by the amino atom, etc. R. The alkyl group or the halogenated alkyl group having no substituent, for example, the same as the alkyl group or the halogenated alkyl group having no substituent represented by R35, preferably 2 . Specific examples of the sulfonate-based acid generator, such as α-(ρ-toluenesulfonyl)·cyanide, α-(ρ-chlorophenylsulfonimido)-benzyl cyanide Compound, α-(4-nitrophenylsulfonyloxyimido: cyano cyanide, α-(4-nitro-2·trifluoromethylbenzenesulfonyloxyimido: phenyl cyanide, α-( Phenylsulfonyloxyimido)-4-chlorobenzyl cyanated α-(phenylsulfonyloxyimino)-2,4-dichlorobenzyl cyanide, α-sulfonyloxyimido) -2,6-dichlorobenzyl cyanide, α-(phenylsulfonimido)-4-methoxybenzyl cyanide, α-(2-chlorophenylsulfonylamino)-4- Alkyl cyano cyanide, α-(phenylsulfonyloxyimido group: um-2-ylacetonitrile, α-(4-dodecylbenzenesulfonyloxyimino)-benzylate, hydrazine: -[ (ρ-toluenesulfonyloxyimido)-4-methoxyphenyl], hydrazine: -[(dodecylbenzenesulfonyloxyimino)-4-methoxyphenyl], α - (p-toluenesulfonyloxyimido)-4-thienyl cyanide, "·sulfonyloxyimino]-1-cyclopentenylacetonitrile, α_(methylsulfonylamino)-1- Cyclohexenylacetonitrile, α-(methylsulfonyloxyimido - heptyl acetonitrile, α-(methylsulfonyloxyimino)-1-cyclooctyl, 〇:-(trifluoromethylsulfonyloxyimido)-bucyclopentenylacetonitrile, Trifluoromethylsulfonyloxyimido)-cyclohexylacetonitrile, ethylsulfonimido)-ethylacetonitrile, α-(propylsulfonyloxyimino)-propyl, the above content, oxygen, oxygen -benzyl)-benzyl, (benzophenoxyoxy)&gt;-thylthioacetonitrile acetonitrile (methoxy- 1 -cycloacetonitrile τ-(glycolic acetonitrile-79-200914991, α-(cyclohexylsulfonate) -cyclopentylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(B Alkylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α-(isopropylsulfonyloxyimino)-1 -cyclopentenylacetonitrile, a - (η_butylsulfonyloxy) Amino)-1-cyclopentenylacetonitrile, a-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclo Hexenylacetonitrile, α-(η-butylsulfonyloxyimido)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-phenylacetonitrile, α -( Alkylsulfonyloxyimido)-fluorene-methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino) )-Ρ-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimido)-fluorene-methoxyphenylacetonitrile, hydrazine:-(propylsulfonyloxyimino)-indole-A Phenyl phenyl acetonitrile, α-(methylsulfonyloxyimido)-fluorene-bromophenylacetonitrile, etc. Further, Japanese Laid-Open Patent Publication No. Hei 9-20 8 5 54 (paragraphs [0012] to [0014] The oxime sulfonate-based acid generator disclosed in WO 8/A to [Chem. 19], W02004/074242A2 (Examples 1 to 40 of pages 65 to 85) may also be used. Need to use with the cooperation. Further, for example, a compound shown below or the like is suitable. [化4 8]

H3° A?=N-~os〇2-(ch2)3ch3

HsC C=N-〇s〇2-(CH2)3CH3 -80- 200914991 [化4 9]ch3O~ C*=N一Ο—S〇2—CF3 |cF2)6—Η

C=N—O—S02—CF3 C3F7

Ch3o C*=N-O-S〇2—CF3 (CF2)6-H

C—N一Ο—S〇2—CF3 C2F6

C3F7 C=N—〇—S〇2~C4F9 (CF2)6—H

&lt;CF2&gt; 4-H The above four compounds are preferably the following four compounds. -81 - 200914991 【化5 0】

H3C—C=N—〇s〇2-(CH2)3CH3 h3c-C=N-OS02-(〇Η2)3〇Η3

C-=N—O—S〇2—C4F9 (CF2}6-H

Specific examples of the dialkyl or bisarylsulfonyldiazomethane in the C=N—O—S02—C4F9 (CF2)4-H diazomethane acid generator, such as bis(isopropylsulfonate) Diazomethane, bis(P-toluenesulfonyl)diazomethane, bis(ι,ι-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, Bis(2,4-dimethylphenylsulfonyl)diazomethane or the like. Further, it is also suitable to use the diazomethane disclosed in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. 1 1 -03 5 5 5 No. 1 and JP-A No. 1 1 - 0 3 5 5 5 2 An acid generator. Further, poly(disulfonyl)diazomethane, for example, 1,3-bis(phenylsulfonyldiazomethylsulfonyl)propane disclosed in JP-A No. 11-3 22 07 07, , 4-bis(phenylsulfonyldiazomethylsulfonyl)butane, 1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane, 1,10-bis(benzene Sulfhydrazinyldiazomethylsulfonyl)decane, 1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane, 1,3 -bis(cyclohexylsulfonyldiazo Methylsulfonyl)propane, 1,6-bis(cyclohexylsulfonyldiazomethylsulfonyl)hexane, 1,1 fluorene-bis(cyclohexylsulfonyldiazomethylsulfonyl) Decane and so on. (B2) The component may be used alone or in combination of two or more kinds of -82 - 200914991 or more. The content of the component (B) in the photoresist composition of the present invention is from 0.5 to 30 parts by mass, preferably from 1 to 20 parts by mass, per part by mass of the component (A). In the above range, the pattern can be sufficiently formed. A uniform solution is obtained with good preservation stability. &lt; (D) Component&gt; In the photoresist composition of the present invention, in the case of post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer, Any other component of the nitrogen-containing organic compound (D) (hereinafter also referred to as (D) component) may be further added. As the component (D), there have been proposals for various compounds, and any of the known components may be used, and among them, an aliphatic amine, particularly a secondary aliphatic amine or a tertiary aliphatic amine is preferred. In the specification and the scope of the patent application, the "aliphatic" is a concept related to aromaticity, that is, it is defined as a group or a compound having no aromaticity. The "aliphatic cyclic group" is defined as a monocyclic group or a polycyclic group having no aromaticity. The aliphatic amine means an amine having one or more aliphatic groups, and the aliphatic group preferably has a carbon number of from 1 to 12. An aliphatic amine such as an amine (alkylamine or alkanolamine) or a cyclic amine obtained by substituting at least one hydrogen atom of ammonia NH3 with an alkyl group having 1 or less carbon atoms or a hydroxyalkyl group. Specific alkylamines and alkanolamines such as η-hexylamine, η-heptylamine, n--83-200914991 octylamine, η-decylamine, n-decylamine, etc.; N-propylamine, di-η-heptylamine, di-n-octylamine, dicyclohexylamine amine; trimethylamine, triethylamine 'tri-n-propylamine, diamine , tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, diamine, di-n-decylamine, tri-n-decylamine, tri-n-anthracene Alkenylamine, such as diethanolamine, triethanolamine, diisopropanolamine, triisopropyldi-n-octanolamine, tri-n-octanolamine. Which is carbon again! The trialkylamine is preferably a tri-n-pentylamine or a tri-n-octylamine, and the tri-n-pentylamine is most preferred. The cyclic amine is, for example, a heterocyclic ring containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic amine), or a polycyclic compound (aliphatic polycyclic amine) or an aliphatic monocyclic amine, specifically, for example, piperazine, piperazine )Wait. Aliphatic polycyclic amines, preferably having a carbon number of 6 to 1 ,, such as 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diaza [5.4. 0]-7--(-carbene, hexamethylenetetramine, hydrazine, 4 diaza [2.2.2] octane, etc., which may be used singly or in combination of two or more. The component (A) component is in the range of generally 0.01 to 5.0 parts by mass. <Optional component> [(E) component] Further, the photoresist composition of the present invention is for preventing sensitivity amine, - a trialkanolamine such as an amine such as di-η-butyl-η-octyl, or a compound of a monocyclic pyridazine which is a better compound (the heterobicyclic heterobicycle is degraded in use) (-84- 200914991

Deterioration in sensitivity), or the purpose of improving the resistive shape of the latent image formed by the pattern-wise exposure of the resist layer, etc. At least one compound (E) (hereinafter also referred to as (E) component) selected from the group consisting of acid or phosphorus oxyacids or derivatives thereof. An organic carboxylic acid such as acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like is preferred. Phosphorus oxyacids such as phosphoric acid, Phosphonic acid, Phosphinic acid, etc., of which phosphonic acid is preferred. The oxo acid derivative of phosphoric acid, for example, an ester group obtained by substituting a hydrogen atom of the oxo acid with a hydrocarbon group, and the hydrocarbon group is, for example, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 15 carbon atoms. The phosphoric acid derivative is, for example, a phosphate such as di-η-butyl phosphate or diphenyl phosphate. Phosphonic acid derivatives such as dimethyl phosphonate, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, diphenyl phosphonate, diphenyl phosphonate, and the like. Phosphinic acid derivatives such as phosphinates such as phenylphosphinic acid. (E) The components may be used singly or in combination of two or more. The component (E) is preferably an organic carboxylic acid, particularly salicylic acid. -85 - 200914991 (E) Ingredients For the 100 parts by mass of the component (A), it is generally in the range of from 1 to 5.0 parts by mass. The photoresist composition of the present invention may be further blended with an additive which is suitable for mixing, for example, an additive resin which can improve the properties of the photoresist film, a surfactant for improving coating properties, a dissolution inhibitor, a plasticizer, and a stabilizer. , colorants, halo inhibitors, dyes, and the like. [(S) component] The photoresist composition of the first embodiment of the present invention can be produced by dissolving a material in an organic solvent (hereinafter also referred to as (S) component). The (S) component is used as long as it can dissolve the components to be used to form a uniform solution. For example, one or two or more kinds of the above-mentioned conventionally known as a chemically amplified resist solvent can be used. For example, lactones such as r-butyrolactone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-η-pentanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, a polyhydric alcohol such as ethylene glycol, propylene glycol or dipropylene glycol; an ester-bonded compound such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetic acid vinegar; a polyether or a compound having an ether bond, such as a monomethyl ether, a monoethyl ether, a monopropyl ether or a monobutyl ether; or a compound having an ether bond such as a monophenyl ether or a monophenyl ether; a derivative of a polyhydric alcohol [wherein, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred]; a cyclic ether such as dioxane; or methyl lactate, Ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid-86- 200914991 methyl ester, ethyl ethoxy propionate and other esters Category; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenyl ether, butylphenyl ether, ethylbenzene, diethylbenzene, Benzene, cumene, toluene, xylene, cumene, mesitylene and the like, aromatic organic solvents. These organic solvents may be used singly or in combination of two or more. Further, among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), and r-butyrolactone are preferably used. Further, a mixed solvent obtained by mixing PGMEA with a polar solvent is preferred, and the addition ratio (mass ratio) may be appropriately determined depending on the compatibility of PGMEA with a polar solvent, etc., preferably 1:9 to 9:1. More preferably 2: 8 to 8: 2 range. More specifically, when the polar solvent is ethyl lactate (EL), the mass of PGMEA: EL is preferably from 1:9 to 9:1, more preferably from 2:8 to 8:2. When the polar solvent is PGME, the quality of PGMEA: PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2', and most preferably 3:7 to 7:3. Further, among the components (S), for example, a mixed solvent of at least one selected from PGMEA and EL and r-butyrolactone is preferably used. At this time, in the 'mixing ratio, the former and the latter are preferably 70:30 to 95: 5 〇 and (S) components, and other mixed solvents obtained by using a mixed solvent of PGMEA and PGME and r - butyrolactone, for example. It is better. At this time, the ratio of 'mix-87-200914991' is better for the latter to be 99.9: 0.1 to 80: 20, 99.9: 0.1 to 90: 10 is better, and 99.9: 0.1 to 95: 5 is the best. . When it is within the above range, the rectangular shape of the photoresist pattern can be improved. The amount of the component (S) is not particularly limited. Generally, it can be appropriately selected in accordance with the concentration applied to the substrate, the thickness of the coating film, etc., and the solid concentration in the photoresist composition is generally 2 to 20 The mass% is preferably used in the range of 5 to 15% by mass. In the present invention, the acid generator (B1) formed by the compound represented by the above formula (bl-14) can be used. The (B 1 ) component and the aryl group-bonded hydroxyl group have a structure protected by a tertiary alkyl ester type or an acetal acid dissociable group such as an alkoxyalkyl group, and the non-exposed portion has a structure For any changes. Therefore, the compound represented by the above formula (b 1 -1 4 ) exhibits a dissolution inhibiting effect on the alkali developing solution on the (A 1 ) component in the non-exposed portion of the resist film. Further, in the exposed portion, when the acid generated is subjected to post-exposure heating (PEB), in the acid dissociable group, the hydroxyl group is dissociated from the formed oxygen atom to form a compound bonded to the aryl group. The component (A1) is presumed to exhibit a dissolution promoting effect on the alkali developer. Therefore, it is conceivable that the high contrast of the exposure portion/non-exposure portion can be improved. For the reason described above, when the photoresist composition of the present invention is a positive photoresist composition, the formation of the photoresist pattern can be improved by using the substrate component in combination with an acid generator (the aforementioned (B 1 ) component). Inter-mask reproducibility' For example, the positive-88-200914991 roundness of the through-hole at the time of forming the contact hole (C/H) pattern can be improved, and the uniformity (CDU) of the diameter (CD) can be improved. The mask error factor (MEF) has excellent C/H pattern picking and the like, and improves the lithography etching characteristics. Further, when the photoresist pattern (L/S pattern) of the line and the space is formed, the MEF is improved, and the lithography characteristics can be improved. Subsequently, the photoresist composition of the present invention is excellently used as a photoresist composition for immersion exposure in a photoresist pattern forming method including an immersion exposure step, and good lithographic etching characteristics can be obtained. In the photoresist pattern forming method including the step of forming a three-layer photoresist layer, it is also suitable as a positive-type photoresist composition for forming an upper photoresist film, and good lithographic etching characteristics can be obtained. <<Method of Forming Photoresist Pattern>> Next, a method of forming a photoresist pattern according to a second embodiment of the present invention will be described. The method for forming a photoresist pattern of the present invention includes a step of forming a photoresist film on a substrate by using the photoresist composition according to the first embodiment of the present invention, and exposing the photoresist film to a step of exposing the light. The step of developing the resist film to form a photoresist pattern. The method of forming the photoresist pattern of the present invention can be carried out, for example, in the following manner. In other words, first, the photoresist composition of the first embodiment of the present invention is applied to a support using a spin coater or the like, and then 40 to 120 at a temperature of 80 to 150 ° C. Post-apply bake (PAB)), preferably between 60 and 90 seconds, is reused after ArF quasi-89-200914991 molecular laser light is selectively exposed by the desired mask pattern. Post exposure bake (PEB) is carried out at a temperature of 80 to 150 ° C for 40 to 120 seconds, preferably 60 to 90 seconds. Then, it is subjected to development treatment using an alkali developer, for example, 0.1 to 10% by mass aqueous solution of tetramethylammonium hydroxide, preferably washed with pure water, and then dried. Further, if necessary, baking treatment (post-baking) may be performed after the above development treatment. Thus, the photoresist pattern of the faithful reaction mask pattern is not particularly limited, and a conventionally known article such as a substrate for an electronic component or a specific wiring pattern can be formed thereon. Items, etc. More specifically, for example, a metal wafer such as a sand wafer, copper, chromium, iron, or the like, or a glass substrate. For wiring pattern materials, for example, copper, inscription, mirror, gold, etc. can be used.

Further, for the support, for example, an inorganic or/or organic film may be provided on the substrate. An inorganic film such as an inorganic antireflection film (inorganic B ARC ) or the like. Organic film, such as organic anti-reflective film (organic BAR C). The wavelength used for exposure is not particularly limited, and an ArF excimer laser, a KrF excimer laser, an f2 excimer laser, an EUV (very ultraviolet ray), a VUV (vacuum ultraviolet ray), an EB (electron line) can be used. , X-ray, soft X-ray and other radiation. The above photoresist composition is effective for KrF excimer laser, ArF excimer laser, EB or EUV, especially for ArF quasi-molecular laser. Moreover, it is also effective for immersion exposure. [Embodiment] The present invention will be more specifically described by way of examples, but the present invention is not limited by the following examples. (Synthesis Example 1) &lt;Synthesis of Compound (1)&gt; [Chemical 5 1]

OH

A small amount of phosphorus oxide (8.53g) and 2,6-dimethylphenol (8.81§) and diphenylarsenium (12.2g) were added slowly to a small amount of methanesulfonic acid (60.75 g) below 2 (TC). After the temperature is controlled to 30 ° C for 30 minutes, the temperature is raised to 40 t and then matured for 2 hours. Thereafter, the reaction is dropped into pure water cooled to 15 ° C or below (1 0 9 · 3). 5 g ). After the completion of the dropwise addition, dichloromethane (5 4.6 8 g) was added, and after stirring, the dichloromethane layer was recovered. 20 to 25 t of hexane (386.86 g) was added to the other vessel, and dichloromethane was added. After the completion of the dropwise addition, the mixture was aged at 20 to 25 t for 30 minutes, and then filtered to give the objective compound (yield 7 0 · 9 %). The obtained compound was subjected to 1 H-NMR analysis. 1 Η-N RM ( DMS Ο - d 6,6 0 0 Μ Η z ) : δ ( ppm) =7.61- -91 - 200914991

7_72 ( m, 10H, phenyl ) , 7.14 ( S - 2H, Hc ) , 3.12 ( S , 3H, Hb ) , 2.22 ( s, 6H, Ha ). From the above results, it was confirmed that the obtained compound had the structure shown below.

(Synthesis Example 2) &lt;Synthesis of Compound (2)&gt;

OH

(2) 5.00 g of the compound (1) was dissolved in a mixed solution of 25.0 0 g of water and 24.03 g of methylene chloride. Thereafter, a small amount of lithium 2-naphthylmethoxytetrafluoroethanesulfonate (4.2 8 g) was gradually added thereto, and the mixture was stirred at 25 ° C for 1 hour. After completion of the reaction, the dichloromethane solution was washed with water and concentrated to dryness. -92- 200914991 The obtained powder was washed with a dispersion in a home, and then dried under reduced pressure to obtain 7.23 g of a compound (yield: 90.2%). The obtained compound was subjected to 1 H - N M R, 19 F _ N M R analysis. 1H-NRM ( DMS 0-d6, 600MHz ) : ¢5 (ppm) =7.97 ( s,1H,Hc ) , 7.94 -7.91 ( m,3H,pheny 1 + naphthy 1 ), 7.83-7.81 ( m,2H, Phenyl + naphthy 1 ) , 7.76-7.75 ( m, 8H , phenyl + naphthy 1 ) , 7.5 5-7.52 ( m , 3 H , pheny 1 + naphthy 1 ) , 7.496 ( s, 2H, Hd ) , 5.21 ( s, 2H , Hb ) 2.24 ( s, 6H, Ha ). 19F-NMR (Acetone-d6, 3 76 MHz): &lt;5 (ppm) = -82.8, -1 1 5 . From the above results, it was confirmed that the obtained compound had the structure shown below.

(Example 1) <Synthesis of Compound (b 1 -1 4 -1 0 1 )> -93- 200914991

The compound (1) (1 2 · 1 g) was dissolved in dichloromethane (6 0.4 g), and then the mixture was stirred at room temperature for 1 hour. After the liquid portion is washed, concentrated and dried, the compound (1), which is substituted with the anion butanesulfonic acid anion of the above compound (1), is dissolved in 80.9 g of dehydrated tetrahydrofuran. After sodium hydride (〇. 44 g) was added thereto, a solution of 2-metal (2-2 g) in tetrahydrofuran (4.4 g) was added dropwise. The mixture was added dropwise to the mixture at room temperature, and after stirring for 1 hour, the reaction was dropped into dichloromethane (90 g) for extraction. Thereafter, the dichloro acid water was washed and washed with water. This dichloromethane was dissolved in 150 g of the title compound to obtain 6.9 g of white powder of the objective compound. The obtained compound was subjected to 1H-NMR, 19F-NMRj*H-NRM (DMSO-d6 '400 MHz): δ 丨 7.88 (m, 1 OH, Ha-He), 7 _ 6 0 (s, 2 Η, Hf 2H, Hg ) , 3.88 ( s, 1H, Hh ) , 2.33 ( s 1.46- 1.99 ( m, 14H, Adamantane ). Alkane (5 4.6 g ) and potassium acid (11.2 g) from the organic layer water ions through the nonafluoro-n - the compound (up to 10 ° C or less. After the bundle of cyclohexane chloromethyl ether, the temperature is raised until the solution is diluted with a methane layer into a house with a dilute salt (sub-analysis. [ppm] = 7.76-), 5.24 ( s , , 6H, Η 1 ), -94 - 200914991 19F-NRM (DMSO-d6, 3 76MHz) : δ (ppm) = -80.4, -114.6, -121.1, -125.3° Based on the above results, confirm the income The compound has the structure shown below

(Example 2) &lt;Synthesis of Compound (bl-14-201)> [Chem. 5 7]

5.00 g of the compound (2) was added to a solution of 75 ml of tetrahydrofuran, and water-cooled. -95-200914991 After adding 0.34 g of sodium hydride thereto, a solution of 2-adamantanechloromethyl ether (1.713 g) in tetrahydrofuran (3.42 ml) was added dropwise. After the completion of the dropwise addition, the mixture was warmed to room temperature, and after stirring for 1 hour, the reaction was dropped into water. The solution was extracted with dichloromethane (6 0.4 g). Thereafter, the methylene chloride layer was washed with dilute hydrochloric acid water and washed with water. After the dichloromethane solution was concentrated and dried, the obtained powder was dispersed in hexane. Thereafter, it was dried under reduced pressure to give the title compound (4.2 g) (yield 68. 1%). The obtained compound was subjected to 1H-NMR and 19F-NMR analysis. *H-NRM (DMSO-d6 '600ΜΗζ) : δ (ppm) = 7.89 (s, 1H , He ) , 7.8 7-7.5 9 ( m, 13H , phenyl + naphthyl ), 7.561 ( s , 2H , He ) , 7.54-7.5 2 ( m , 3H , phenyl + naphthyl ) , 5.23-5.21 ( d,4H,Hd ) , 3.87 ( s ' 1H,Hf) , 2_33 ( s,6H,Ha ) ,1.9 9 - 1 .4 5 (m, 14 H,

Adamantane). 19F-NMR-(Acetone-d6, 3 76MHz): δ (ppm) = -82.9, -1 1 5.9. From the above results, it was confirmed that the compound had the structure shown below. -96- 200914991 [Chem. 5 8]

(Example 3) &lt;Synthesis of Compound (bl-14-301)&gt; [Chem. 5 9]

In the second embodiment, the same reaction was carried out except that 2-adamantane chloromethyl ether was changed to the molar amount of 2-methyl-2-adamantane bromoacetate. The obtained compound was subjected to 1H-NMR and I9F-NMR analysis. 1 Η - NRM ( CDC 13 , 4 0 0 Μ Η ζ ) : δ ( ppm ) = 7.84 ( s, 1 Η, Hf ) , 7.71 - 7.77 ( m &gt; 3H 1 Phenyl + Naphthyl ), 7.5 7-7.6 7 ( m, 1 0 H, Phenyl + Naphthyl ) , 7.39-7.51 ( m -97- 200914991 , 3H, Phenyl + Naphthyl ) , 7.36 ( s, 2H, Hd ) , 5.19 ( s , 2H, Hc) , 4.38 ( s, 2H, Hb ) , 2.32 ( s, 6H, Ha ), 1.69- 1. 9 7 ( m, 11H, Adamantan ) , 1.66 ( s, 3H, He ) , 1. 5 5 - 1 _ 5 8 ( d , 3 H, Adamantan ). 19F-NMR (CDC13, 400MHz): 5 (p p m) : - 7 6 _ 8 7 - -109.14. From the above results, it was confirmed that the compound had the structure shown below /

(Examples 4 to 6 and Comparative Example 1) &lt;Production of Positive Photoresist Composition&gt; Each component shown in Table 1 was mixed and dissolved to prepare a positive resist composition. -98- 200914991 [Table 1] (8) Ingredient (Β) Ingredients (D) (5) Ingredient Example 4 (ΑΗ [100] (Β)-1 [6.77] (D)-1 [0.10] (3)-1 [2200] Example 5 (Α)-1 ΠΟΟ] (Β)-2 [7· 10] (9)-1 [0.10] (S)-1 [2200] Example 6 (Α)-1 ΠΟΟ] (Β)-3 [ 6.90] (D)-1 [0.10] ¢)-1 [2200] Comparative Example 1 (Α)-1 ΠΟΟ] (Β)-4 [4.94] 0))-1 to. 1〇] (S)-1 [2200] Each of the abbreviations in Table 1 has the following meanings. Further, the number in the [] in Table 1 is the amount of addition (parts by mass) ° (A) -1: the polymer represented by the following chemical formula (A) -1 (B) -1: the aforementioned chemical formula (bl -14-101) The acid generator (compound of Example 1) shown. (B) -2 : an acid generator (compound of Example 2) represented by the aforementioned chemical formula (bl-l4-2〇l). (B) -3: an acid generator (compound of Example 3) represented by the aforementioned chemical formula (bl-14-301). (B) -4: Triphenylsulfonium nonafluoro-n-butanesulfonate. (D ) -1 : Tri-n-pentylamine. (S ) -1 : PGMEA/PGME = 6/4 (mass ratio) of mixed solvent 〇 Also, the addition amount of (B)-l~(Β)-4 is equal to the molar amount. -99- 200914991 [Chem. 6 1]

OH (A) -1 &lt;Evaluation of lithographic etching characteristics&gt; The resulting positive photoresist composition solution was used to form photolithographic etching characteristics. [Analysis and Sensitivity] The organic anti-reflection film set was applied to 8 on a hot platen at 205 ° C for 60 seconds using a rotary applicator (product name, manufactured by Privah Scientific Co., Ltd.). As a result of baking, an organic antireflection film having a film thickness of 89 nm was formed. On the reflective film, the positive-type photoresist composition dissolver obtained above is separately coated, and pre-baked (PAB) is performed on a hot plate at 1 〇〇t. Resistance film. Next, on the resist film, a coating liquid (TSRC-002) (trade name, Tokyo) was used, and after heating at 90 ° C for 60 seconds, a film J| was formed. 100- resistance pattern, evaluate the T material "ARC2 9A inch 矽 wafer, and dry it. Then use the spin coating for 60 seconds, and the film thickness of 1 20 nm will protect the film shape. Chemical Industry Co., Ltd.: Top coating of 200914991 coating on top of 2 nm. Secondly, using A r F immersion exposure apparatus NSR _ S 6 0 9 B (manufactured by Ricoh Co., Ltd.; ΝΑ (number of openings) = 1.07, 2/3 wheel illumination), ArF excimer laser (193nm) with a through-hole pattern mask arranged at equal intervals (pitch 1 3 1 nm) through a via having a via diameter (CD) of 75 nm (bias Onm) 'Selective irradiation of the above-mentioned photoresist film to which the top coating layer is formed. The top coating layer is removed by a protective film removal liquid (TS-Rememover-S) (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) Thereafter, the post-exposure heating (PEB) treatment was carried out at 95 ° C for 60 seconds, and then at 23. (under: 2.38 mass% tetramethylammonium hydroxide (TMAH) The aqueous solution "NMD-W" (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was developed for 30 seconds, and then washed with pure water for 30 seconds, and subjected to vibration drying. As a result, it was found that the photoresist was On the film, a contact hole pattern (C/H pattern) obtained by a via hole having a via diameter (CD) of 70 nm is formed at an equidistant distance (pitch of 13 nm). Further, the optimum exposure amount at this time is obtained. (sensitivity: Eop, mJ/cm2). The result '61 mJ/cm2 in Example 4, 85 mJ/cm2 in Example 5', 57 mJ/cm2 in Example 6, and 34 mJ/cm2 in Comparative Example 1 [Graph shape Using a scanning electron microscope (trade name: S_922〇, manufactured by Hitachi, Ltd.), the results of the above-mentioned through-holes of 70 nm and the pitch 丨3 i nm of 200914991 C/Η pattern results were observed. The peeling property of the Η pattern is better than that of Comparative Example 1. In the C/H pattern of Comparative Example 1, one part of the pattern cannot be peeled off. [Evaluation of Mask Error Factor (MEF)] In the above E0P, a mask pattern having a diameter of 70 nm and a pitch of 131 nm as a target is used, and a aperture of 75 nm and a pitch of 13 1 nm are used as targets. Mask pattern formed C / Η pattern, and calculated according to the following equation is obtained MEF Zhi.

MEF= | CD75-CD70 I / I MD75-MD70 I In the above formula, CD75 and CD7Q are the actual apertures (nm) of the C/Η pattern formed by using mask patterns of 75 nm and 70 nm as targets, respectively. Further, MD75 and MD7G respectively have the mask pattern as the target aperture (nm), MD75=75, and MD70=70. MEF is the same exposure amount, when the mask size is changed in the fixed pitch state (the diameter of the through hole in the C/Η pattern, and the line width in the line and space pattern), the different sizes are displayed. How the mask pattern can faithfully reproduce the parameters, the closer the MEF number is to 1, the better the mask reproducibility. As a result of the evaluation, it was confirmed that Examples 4 to 6 showed better mask reproducibility than Comparative Example 1'. [CD uniformity (CDU) evaluation] In the C/Η pattern obtained by the above EOP, CD's of 25 through holes in each C/Η pattern-102-200914991 were measured and calculated from the results. The standard (σ) is 3 times 値 (3σ). The 3σ obtained in this way, when the number is 値, means that the CD uniformity ( ) formed in each of the through holes of the photoresist film is high. As a result of the evaluation, Example 4 was 1 3 . 6 5 'Example 1 4.5 1 , Example 6 was 1 1 · 9 9, and Comparative Example 1 was 1 6.6 0. [Positive roundness evaluation] From the top of the C/H pattern obtained by the above EOP, the long SEM (product name: S-9220, manufactured by Hitachi, Ltd.) was used to measure 25 through holes in the C/H pattern. The standard deviation (σ) times 値(3σ) calculated from the result is obtained from the distance from the center of the through hole to the direction of the 24 directional edge. The 3σ obtained in this way, the smaller the number, the higher the roundness of the through hole. As a result of the evaluation, it was found that Example 4 was 5.5, Example 5 was 4, Example 6 was 4·1, and Comparative Example 1 was 5.2. Example 4 and Comparative Example The roundness of ruthenium and the like, and Examples 5 to 6 were more excellent in roundness as compared with Comparative Example 1. From the above results, it is known that the photo-formed product containing the acid generator of the present invention has a good pattern shape and has excellent MEF and CDU roundness, so that it is compared with a photoresist composition containing a conventional acid generator. Confirm that it can obtain good lithography characteristics. (Example 7) &lt;Compound (bl-14-501) The smaller the deviation, the smaller the CDU 5 is, and the other is 3, that is, Table 7 &gt; 1 is the resistance group, timing, (bl-14-503) -103- 200914991 ) Synthesis [Chemistry 6 2]

Compound (1) (4 g) was dissolved in dichloromethane (7 9 _8 g). After confirming dissolution, potassium carbonate (6·8 7 g) was added to add 2-methyl-2-adamantane (3.4 2 g). After reacting for 24 hours under reflux, it was filtered, washed with water and crystallized from hexane. The obtained powder was dried under reduced pressure to give the title compound 3.9 8 g (yield: 6 6 %). The compound was analyzed by 1 H-NMR. The results are as follows. ^-NRM ( CDC13 ' 600MHz ) : δ (ppm) =7.83-7.86 (m,4H,phenyl ) , 7.69-7.78 ( m &gt; 6H,phenyl ) ' 7.51 (s,2H,Hd ) ,4.46 ( s, 2H, He) , 2.39 ( s, 6H, Ha ), 2 _ 3 3 ( s, 2H, Adamantane ) , 2_17 ( s, 2H,

Adamantane ) , 1.7 1 - 1.976 ( m,1 1H ' Adamantane ) ' 1.68 ( s,3H,Hb ) ,1.57-1.61 ( m &gt; 2H &gt; Adamantane) o From the above results, it is confirmed that the obtained compound is The compound (bl_14-501) having the structure shown in the following -104-200914991 is contained. Further, in the obtained compound, the NMR data of the cation portion contains the same compound (bl-1 4- 5 02 ) and (b Bu 1 4-5 03 ) as the above, and is analyzed by ion permeation chromatography. Confirmed by the measurement results. The ratio of the above compound, the compound (b 1 - 1 4-501) was 21.4 mol%, the compound (bl-14-502) was ll_4 mol%, and (b 1 - 1 4- 5 03 ) was 67.2 mol%.

(Example 8) &lt;Synthesis of Compound (bl-14-401)>

[Chem. 6 4] Compound (b Bu 1 4 - 5 0 1 ) 2 1 · 4 m 〇 1%, compound (b 1 -1 4 - -105- 200914991 502 ) 1 1.4 mol%, ( b 1 - 1 4 - 5 0 3 ) 6 7.2 m ο 1 % of the mixture 2 5 . 5 g Dissolved in 200 g of pure water, to which dichloromethane (127.4 g) and potassium nonafluoro-η-butane sulfonate (16.0) were added. g), stirred at room temperature for 14 hours. Thereafter, the methylene chloride layer was separated, and then washed with dilute hydrochloric acid, ammonia washing, water washing, etc., and the methylene chloride layer was concentrated and dried to give a white solid object (3 2 · 9 g ). The obtained compound was analyzed by 1H-NMR and 19F-NMR. 'H-NRM ( DMSO-d6 ' 400MHz) : &lt;5 ( ppm ) =7.75- 7.86 ( m,10H,ArH) , 7.61 ( s,2 H,A r H ) ,4.62 ( s ' 2H &gt; CH2 ), 2.31 (s, 6H, CH3), 1.49-1.97 (m, 17H,

Adamantane). 1 9 F-N RM ( D M S O - d 6 , 3 7 6 MHz ) : δ (ppm) = -77.8 , -112.2 &gt; -118.7 &gt; -123.0 ° From the above results, it was confirmed that the compound had the structure shown above. (Example 9) <Synthesis of Compound (bl-1 4-402)>

【化6 5】

Compound (b 1 -1 4 - 5 0 1 ) 2 1 . 4 m ο 1 %, compound (b 1-14- -106- 200914991 5 0 2 ) 1 1 .4 m ο 1 % ' (bl-14 -503) 67.2 mol% of a mixture of 8.93 g was dissolved in 70.4 g of pure water, and dichloromethane (44.7 g) and potassium trifluoromethanesulfonate (3.12 g) were added thereto, and stirred at room temperature for 1 4 hour. Thereafter, the methylene chloride layer was separated, and then subjected to dilute hydrochloric acid washing, ammonia washing, water washing, etc., and the methylene chloride layer was concentrated and dried to give a white solid object (8.70 g). The obtained compound was analyzed by 1H-NMR and 19F-NMR. 1H-NRM (DMSO-d6, 4 00MHz): 5 (ppm) = 7.74 - 7· 86 ( m,1 OH ' ArH ) , 7.60 ( s, 2H, ArH ) , 4.62 ( s, 2H'CH2) , 2.31 (s,6H,CH3), 1.49-1.97 (m,17H,

Adamantane) 〇 19F-NMR (DMSO-d6, 376 MHz): &lt;5 (ppm) = -75.2 o From the above results, it was confirmed that the compound had the structure shown above. (Examples 10 to 17 and Comparative Example 2) &lt;Production of Positive Photoresist Composition&gt; Each component was mixed and dissolved as shown in Table 2 to prepare a positive resist composition. -107- 200914991 [Table 2] (Part A) (Part B) (D) (5) Ingredient Example 10 (A)-2 (B)-5 (D)-1 (S)-1 [100] [11.5 [1.2] [2200] Example 11 (A)-3 (8)-5 (D)-1 (5)-1 [100] [11.5] [1-2] [2200] Example 12 (A)-2 (A) )-4 (B)-5 (D)-1 (S)-1 . [80] [20] [11.5] [1.2] [2200] Example 13 (A)-2 (A)-4 (B) -5 (D)-1 (S)-1 [60] [40] [11.5] [1.2] [2200] Example 14 (A)-2 (B)-1 (B)-6 (D)-1 (S)-1 [100] [9.6] [1.0] [1.2] [2200] Example 15 (A)-2 (B)-1 (B)-6 (D)-1 (5)-1 [100] [ 5. 6] [3. 0] [1.2] [2200] Example 16 (A)-2 (B)-1 (B)-7 (D)-1 (5)-1 [100] [9.2] [1.9] [1.2] [2200] Example 17 (8)-2 (B)-1 (B)-7 (D)-1 (5)-1 [100] [6.9] [3.8] [1.2] [2200] Comparative Example 2 (A) )-2 (B)-8 (D)-1 (S)-1 [100] [8.0] [1.2] [2200] Each of the abbreviations in Table 2 has the following meaning. Also, in [] in Table 2 The number of enthalpy is the amount of addition (parts by mass). (A) -2. The polymer of the following chemical formula (A) -2 (Mw = 7000, Mw / Mn = 1.8). (A) -3 : Polymer of formula (A)-2 (Mw = 1 0000 ' Mw/ Mn = 2.0 ) (A ) -4 : a polymer represented by the following chemical formula (A ) -4 (Mw = 5 000 ' Mw / Mn = 1.5). (B ) -5 : The aforementioned chemical formula (bl-14- 401) The acid generator (compound of Example 8) is shown. -108- 200914991: Triphenylsulfonium trifluoromethanesulfonate. '•Di(1-naphthyl)phenylphosphonium hexafluoro-η-butyl Alkane sulfonate. (Β) 【化6 6】

<Evaluation of lithography axising characteristics> 4. Methylphenyl diphenyl quinone nonafluoro-η-butane sulfonate.

The resulting resist pattern was formed using the resulting positive resist composition solution, and the following lithographic etching characteristics were evaluated. [Analytical property and sensitivity] The organic anti-reflection film composition "ARC29" (trade name "Puliva Scientific Co., Ltd.") was applied onto a 8 inch silicon wafer by a spin coater on a hot plate. The baking was performed at 2 0 5 t: for 60 seconds, and drying was carried out to form an organic anti-reflection film having a film thickness of 75 nm. Subsequently, the positive photoresist composition solution obtained above was coated on the anti-reflection film using a spin coater, and dried on a hot plate at 110 ° C for 60 seconds. The pre-baked (PAB) treatment is dried to form a photoresist film having a film thickness of 120 ηηι. Next, an ArF immersion exposure apparatus NSR-S 609B (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 1.07, illumination condition = Xp〇le·(-109-200914991 0.78/0.97), polarizing condition = w/P), ArF excimer laser (

1 93 nm) Selective illumination via a mask pattern (6% half-tone). Subsequently, post-exposure heating (PEB) treatment was carried out under conditions of 1 1 and 60 seconds, and then 2 · 38 % by mass of aqueous solution of tetramethylammonium hydroxide (TMAH) was used at 2 3 〇C (NMD- 3) (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was subjected to development for 40 seconds, and was washed with pure water for 40 hours thereafter, and subjected to vibration drying. As a result, it was found that the wiring and the space resist pattern (L/S pattern) having a line width of 65 nm and a pitch of 130 nm were formed in any of the examples obtained by using any of the positive resist compositions. Further, the optimum exposure amount at this time (sensitivity: Eop, mJ/cm2) was obtained, and the results are shown in Table 3. [Evaluation of Mask Error Factor (MEF)] In the above Ε ο p, the mask pattern of the line width IE is 6 1 nm, 6 3 nm ' 65 nm, 67 nm, 69 nm, respectively. An L/S pattern with a pitch of 130 nm is formed. At this time, the inclination of the straight line when the target size (nm) is plotted as the horizontal axis and the line width (nm) of each of the mask patterns formed on the photoresist film is plotted as the vertical axis is calculated as the MEF. The closer the MEF (the inclination of the line) to the number 1, the better the reproducibility of the mask. The results obtained are shown in Table 3. -110- 200914991 [Table 3] Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Comparative Example 2 E叩(mJ/cm2) 27.0 29.9 28.8 31.6 29.0 26.5 32.5 38.0 23.5 MEF 3.29 3.3 3.49 3.43 3.76 3.69 3.22 3.28 3.92 It is clear from the above results that it was confirmed that the photoresist composition of Example 1 to 17 containing the acid generator of the present invention was used as compared with the photoresist of Comparative Example 2. The composition shows better mask reproducibility. 111 -

Claims (1)

200914991 X. Patent Application No. 1 · A photoresist composition which is a substrate component (A) containing a change in solubility of an alkali developer via an action of an acid and an acid generator component which generates an acid by exposure ( The photoresist composition of B), wherein the acid generator component (B) is an acid generator (B 1 ) formed by a compound represented by the following formula (b 1 -1 4 ). 1] R7*·r8-s+ χ-上上9&quot; · · · (b 1 - 1 4) [wherein, R7''~R9'' each independently represent an aryl group or an alkyl group; any of R7"~R9" Two may be bonded to each other to form a ring together with a sulfur atom in the formula; at least one of R7" to R9' is a part or all of a hydrogen atom by an alkoxyalkyloxy group or an alkoxycarbonylalkyloxy group. The substituted aryl group substituted by the group; X. is an anion]. The photoresist composition according to claim 1, wherein the alkoxyalkyloxy group is represented by the following formula (bl4-l) [Chemical 2] R47 R49 [In the formula, R4 7 and R48 are each independently a hydrogen atom or a linear or branched alkyl group. R 4 9 is an alkyl group, and R 4 8 and R 4 9 may be bonded to each other to form a ring structure, wherein ' At least one of R47 and R48 is a hydrogen atom]; -112- 200914991 The alkoxycarbonylalkyloxy group is represented by the following formula (bl4-2) [Chemical 3] (b 1 4-2) [wherein R5() is a linear or branched extending matrix, and R51 is an acid dissociable group]. The photoresist composition according to the first aspect of the invention, wherein the substrate component (A) is a substrate component which increases the solubility to the alkali developer via the action of an acid. The photo-resist composition of claim 3, wherein the substrate component (A) is a resin component (A1) having a structural unit derived from an acrylate having an acid-dissociable dissolution inhibiting group (a) 1 ). 5. The photoresist composition of claim 4, wherein the substrate component (A) has a structural unit (a2) derived from an acrylate containing a lactone-containing cyclic group. 6. The photoresist composition according to claim 4, wherein the substrate component (A) has a structural unit derived from an acrylate having a polar group-containing aliphatic hydrocarbon group (a3). The photoresist composition of claim 5, wherein the aforementioned substrate component (A) has a structural unit derived from a acrylate containing a polar group-containing aliphatic hydrocarbon group (a3) ° 8 as claimed in the patent application. The photoresist composition of the first item contains the organic compound (D) containing nitrogen-113-200914991. A method for forming a photoresist pattern, comprising the step of forming a photoresist film on a support using the photoresist composition according to any one of claims 1 to 8, and exposing the photoresist film And a step of alkali developing the aforementioned photoresist film to form a photoresist pattern. 10. A compound of the following formula (bl-14), wherein R7&quot;R9&quot; r8-s+ χ- (b 1 - 1 4) [wherein R7''~R9'' Independently represents an aryl group or an alkyl group; any two of R7''~R9'' may be bonded to each other to form a ring together with a sulfur atom in the formula; at least one of R7''~R9' is one of hydrogen atoms a substituted aryl group partially or wholly substituted with an alkoxyalkyloxy group or an alkoxycarbonylalkyloxy group; X' is an anion]. A compound according to the first aspect of the invention, wherein the alkoxyalkyloxy group is represented by the following formula (bl4-l). Wherein R47 and R48 are each independently a hydrogen atom or a linear or branched alkyl group, R49 is an alkyl group, and R48 and R49 may be bonded to each other to form a ring structure 200914991, wherein R47 and At least 1 f of R48 [the aforementioned alkoxycarbonylalkyloxy group is as follows] [wherein, R5() is a linear or branched exudate]. An acid generator characterized by being formed of a compound of item 11.丨 is a hydrogen atom]; formula (bl4-2) shows a 2): group, R51 is acid dissociation, please patent range 10 or -115- 200914991 VII. Designated representative map: (1) For: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: [Chemical 1] (b 1 — 1 4) -5-