TW200844101A - Compound, acid generator, resist composition and resist pattern formation method - Google Patents

Abstract

A compound represented by the following general formula (b1-5): where R41, R42 and R43 represent an alkyl group, an acetyl group, an alcoxyl group, a carboxy group or a hydroxyalkyl group; and n0 represents an integer of 1 to 3; n1 represents an integer of 0 to 3; and n2 and n3 represent an integer of 0 to 3; and X- represents an anion.

Description

200844101 IX. Description of the Invention The present invention relates to a compound suitable as an acid generator for a photoresist composition, an acid generator formed of the compound, and a photoresist composition containing the acid generator. And a method of forming a photoresist pattern using the photoresist composition. This case is based on the priority of 2006-3 1 1 708, which was filed on November 17, 2006 in the Japan Patent Office. The contents are used in this specification. [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 photomask of a specific pattern is formed by radiation such as light or electron lines. The selective exposure is carried out by applying a development process 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, the pattern of the pattern has been rapidly refined with the progress of the lithography technique. 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, EUVs (polar 200844101 ultraviolet rays) or X-rays having shorter wavelengths for the aforementioned quasi-molecular lasers have also been studied. 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 to contain a base resin which changes the alkali solubility based on the action of an acid, and an enhanced chemical type resist which generates an acid generator by exposure. For example, a positive type enhanced chemical type photoresist, which 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. Up to now, the base resin for enhancing chemical resist is a polyhydroxystyrene (PHS) which is highly transparent to KrF excimer laser (24 8 nm) or a resin which is protected by an acid-dissociating 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 248 nm, for example, light of 193 nm is still insufficient. Therefore, the use of a PHS-based resin as a base resin component for enhanced chemical resistance, for example, a process using a 93 nm light, still has disadvantages such as low resolution. 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, the main chain is generally used to have a (meth) acrylate. Derived resin (acrylic resin). In the case of a positive type, the above-mentioned resin is mainly a constituent unit derived from a (meth) acrylate containing a third-stage alkyl ester type acid dissociable dissolution inhibiting group containing an aliphatic polycyclic group, for example, a main use contains 2 a resin having a constituent unit derived from an alkyl-2-adamantyl (meth)acrylic acid (meth)acrylic acid 200844101 or the like (for example, Patent Document 1) ° Further, "(acrylic acid ester) means α-position An acrylate having a hydrogen atom bonded to it, and one or both of the methyl methacrylate bonded to the α-position. "(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 types of substances have been proposed for enhancing the acid generator used in chemical resists, such as a key salt acid generator such as an iodine salt or a phosphonium salt, 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 dinaphthyl monophenyl mirror skeleton or the like has been used as the acid generator. (Patent Document 2). [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2005- 1 00203 (Patent Document 2) In recent years, with the miniaturization of the resist pattern, there is a higher resolution. Further expectations, and in turn, seek to improve the various lithographic etching characteristics. One of the aforementioned characteristics is, for example, Line Width Roughness (hereinafter, also referred to as "LWR"). When LWR is used to form a photoresist pattern using a photoresist composition, the line width of the line pattern is uneven -8-200844101. As the pattern is refined, the improvement is more important. Further, the cation of the key salt-based acid generator generally uses a highly hydrophobic cation such as a triphenylsulfonium or a dinaphthyl monophenyl mirror, but has a cation-based key acid generator for the dissolution of the photoresist. The organic solvent (photoresist solvent) used in the various components has a problem of low solubility. The low solubility of the above-mentioned photoresist solvent causes a decrease in the storage stability of the photoresist, which may cause deterioration of the shape of the photoresist pattern. The present invention has been made in view of the above circumstances, that is, to propose a novel compound suitable as an acid generator for a photoresist composition, an acid generator formed of the compound, a photoresist composition containing the acid generator, and A method of forming a photoresist pattern of the photoresist composition is used. The present inventors have proposed the following means in order to solve the above problems. That is, the first aspect of the present invention is a compound represented by the following formula (bl-5). 【化1】

• · · · (b 1 - 5) 200844101 [wherein R41, R42 and R43 are each independently alkyl, ethoxy, alkoxy, carboxy or hydroxyalkyl; n〇 is an integer from 1 to 3,... An integer of 0 to 3, n2 and n3 are each independently an integer of 〇~3, and X- is an anion. Further, the second aspect of the present invention is an acid generator formed of the compound represented by the above formula (bl-5). Further, a third aspect of the present invention is a photoresist composition which is a substrate component (A) which contains a change in alkali solubility based on an acid action, and an acid which generates an acid via exposure. The photoresist composition of the component (B) is characterized in that the acid generator component (B) is an acid generator (B1) containing a compound represented by the above formula (bl-5). Further, a fourth aspect of the present invention is a method for forming a photoresist pattern which comprises a photoresist composition using the third aspect of the present invention described above on a substrate. a step of forming a photoresist film, a step of exposing the photoresist film, and a step of developing the photoresist film to form a photoresist pattern. Further, the "constituting unit" in the specification and the scope of the patent application means the monomer unit (monomer unit) constituting the resin component (polymer). "Exposure" is a general tribute to radiation exposure. The "alkyl group" is a linear monovalent, branched chain or cyclic monovalent saturated hydrocarbon group unless otherwise specified. The "lower alkyl group" means an alkyl group having 1 to 5 carbon atoms. The present invention provides a novel compound of -10 200844101 suitable as an acid generator for a photoresist composition, an acid generator formed by the compound, and a photoresist composition containing the acid generator, and the composition using the photoresist The formation method of the photoresist pattern of the object. <<Compound>> The compound of the first embodiment (a s p e c t ) of the present invention is as shown in the above formula (bl-5). In the above formula (bl-5), R41, R42 and R43 are each independently an alkyl group, an ethyl group, an alkoxy group, a carboxyl group or a hydroxyalkyl group. In R41, R42 and R43, the alkyl group is preferably a lower alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, and a methyl group, an ethyl group, a propyl group or a different group. More preferably, propyl, η-butyl, tert-butyl, tert-pentyl or isopentyl. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a linear or branched alkoxy group, and most preferably a methoxy group or an ethoxy group. The hydroxyalkyl group is preferably a group obtained by substituting one or a plurality of hydrogen atoms of the above alkyl group with a hydroxyl group, for example, a methylol group, a hydroxyethyl group, a hydroxypropyl group or the like. N 〇 is an integer of 1 to 3, preferably 1 or 2, more preferably 1. ~ is an integer of 0 to 3, preferably 1 or 2, more preferably 2. N2 and n3 are each independently an integer of 〇~3, preferably each independently 〇 or 1, and more preferably any of them is 0. In the above formula (bl-5), X - is an anion. The anion portion of X - is not particularly limited, and those known as an anion portion of the gun salt acid generator can be suitably used. For example, the formula "R14S03_ (R14 is a straight -11 - 200844101 chain, branched chain or cyclic alkyl group or halogenated alkyl group) can be used. In the above formula "R14S〇3-", R14 is a linear or cyclic alkyl group or a halogenated alkyl group. The linear or branched alkyl group of R14 is preferably a carbon number of 1 to: ', preferably 1 to 8 carbon atoms, and the carbon number is 1 to 4, preferably the cyclic alkyl group of the above R14, in carbon number. 4 to 15 are better for 4 to 1 为, and the best for carbon 6 to 10. The above R14 is preferably a halogenated alkyl group. That is, the above formula ('X- is preferably a halogenated alkylsulfonic acid ion. The halogenated alkyl group is a part or all of the alkyl atom substituted by a halogen atom. The base system is the aforementioned R41, R42 and R43" Alkyl group substituted by the same internal atom. A halogen atom which may be substituted, such as a fluorine atom, a bromine atom, an iodine atom, etc. In the halogenated alkyl group, 50 to 100% of the hydrogen atom is replaced by a halogen atom. Preferably, the whole is more preferred. Among them, the halogenated alkyl group is preferably a fluorinated alkyl group. The fluorinated alkane is preferably 1 to 10, and the carbon number is preferably 1 to 8 and the carbon number is the most 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 before fluorination) is preferably 10 to 100%, more preferably 50. ～100%, the atom is completely replaced by a fluorine atom, and the strength of the acid is improved. In the above formula (bl-5), X - can be expressed by the following formula: For better, the hydrogen in the bl-5) carbon group, the halogenated alkane is replaced by a halogen or a chlorine atom, and the number of carbon atoms is ~. Among the alkyl groups, the following phase is particularly preferred as hydrogen (b-3) -12-200844101 Anion, anion represented by the following formula (b-4)

[wherein, X'' is an alkylene group in which at least one hydrogen atom is replaced by a fluorine atom; and Y'' and Z'' are each independently an alkyl group having 1 to 10 carbon atoms substituted with at least one hydrogen atom] . In the formula (b-3), X'' is a linear or branched alkyl group having at least one hydrogen atom, and the carbon number of the alkyl group is 6, more preferably 3 to 5 carbon atoms. Good for carbon number 3. In the formula (b-4), Y'' and Z'' are each independently a linear or branched alkyl group substituted with at least a fluorine atom, and the alkane is preferably from 1 to 10, more preferably from 1 to 10. 7. It is preferable that the carbon number of the alkyl group of the carbon number X'' or the carbon number of the alkyl group of Y'', Z'' is excellent in solubility based on the photoresist solvent. Further, in the alkyl group of X''-alkyl or Υ'', Ζ'', the more the number of hydrogen atoms is, the stronger the strength of the acid is, and the higher the energy or electron line is. The transparency can be improved: the carbon number of 2 to 6 is substituted by a fluorine atom of a fluorine atom, preferably 2 to 1 of a hydrogen atom group, and the number of carbon atoms is 1 to 3. It is preferable to use the smaller fluorine atom instead of 200 nm for the above-mentioned range -13-200844101. The fluorination ratio in the alkylene group or the alkyl group is preferably from 70 to 100%, more preferably from 90 to 100%, most preferably a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms. . The compound of the first aspect of the present invention is preferably, for example, the following. [化3]

Among them, a compound represented by the aforementioned chemical formula (b 1 - 5 1 ) is preferred. -14- 200844101 &lt;Production Method of Compound&gt; The compound (bl-5) of the first embodiment of the present invention can be added, for example, to a methanesulfonic acid solution of phosphorus pentoxide. After cooling to room temperature, the compound of the formula (bl-5-20) is gradually added to the compound represented by the following formula (b 1 - 5 - 2 1 ), and is subjected to 2~ at room temperature. 40 hours, more preferably 5 to 2 hours of reaction. The reaction product is washed with a mixed solution of water and an organic solvent (for example, dichloromethane, chlorobenzene, iodobenzene, etc.), and the aqueous phase is taken out, and then, for example, the following formula (b 1 - 5 - 2) is added thereto. 2) The alkali salt is obtained by performing a reaction at room temperature for 5 to 8 hours, more preferably 1 hour to 4 hours. 【化4】

Wherein R41 is the same as R41 in the above formula (bl-5); n〇 is η in the above formula (bl-5). , ~ for the same content] -15- 200844101

Wherein R42 and R43 are the same as those of R42 and R43 in the above formula (b1-5); n2 and n3 are the same as those of n2 and n3 in the above formula (bl-5). K+X ...... ( bl-5-22) [X - is the same as X - in the above formula (bl-5)]. <<Acid generator>> The acid generator of the second aspect of the present invention (hereinafter also referred to as an acid generator (B 1 )) is represented by the above formula (b 1 - 5 ) The compound is formed. Wherein R41, R42 and R43; n?, m, n2 and n3; and X- are the same as those recited in the above-mentioned first embodiment of the present invention. <<Photoresist composition>> The photoresist composition of the third aspect of the present invention, -16- 200844101

A substrate component (A) (hereinafter referred to as (A) component) which changes the solubility of an alkali based on an acid action, and an acid generator component (B) which generates an acid by exposure (hereinafter, also referred to as ( B) a component), and the component (B) is an acid generator (B1) containing a compound represented by the above formula (b 1 - 5). In the resist composition of the present invention, the component (A) may be a polymer material which changes the solubility of the alkali by the action of an acid, or a low molecular material which changes the solubility of the alkali by the action of an acid. Further, the photoresist composition of the present invention may be a negative photoresist composition or a positive photoresist composition. In the case where 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-type photoresist composition is added with a crosslinking agent (C). In the negative resist composition, when an acid is generated in the component (B) by exposure when the photoresist pattern is formed, the exposed portion causes a cross between the alkali-soluble resin and the crosslinking agent via the action of the acid. And a change to an alkali-insoluble saponin-soluble resin to use a resin having at least one unit selected from a lower alkyl ester of α-(hydroxyalkyl)acrylic acid or α-(hydroxyalkyl)acrylic acid It is preferred to form a good photoresist pattern with lower swelling. Further, ^-(hydroxyalkyl)acrylic acid means that the acrylic acid of the carbon atom bonded to the hydrogen atom at the α-position of the carboxyl group is bonded to the carbon atom of the α-position to a hydroxyalkyl group (preferably having a carbon number of 1 to 5). One or both of the hydroxyalkyl) a-hydroxyalkylacrylic acids. -17- 200844101 The crosslinking agent (c), for example, is usually an amine-based crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group, which can form a good photoresist pattern with lower swelling. It is better. The amount of the crosslinking agent (C) to be added is preferably from 1 to 50 parts by mass based on 100 parts by mass of the alkali-soluble resin. In the case where the photoresist composition of the present invention is a positive photoresist composition, the component (A) is an alkali-insoluble component having an acid-dissociable dissolution inhibiting group. When the photoresist pattern is formed, an acid is generated by the (B) component by exposure, and the acid dissociable dissolution inhibiting group is dissociated by the action of the acid to change the (A) component to alkali solubility. 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 simultaneously exposed. It is still in an alkali-insoluble, unaltered state, and can be subjected to alkali development. In the resist composition of the present invention, the component (A) is preferably a resin component (A1) (hereinafter, also referred to as (Α; i) component) which increases alkali solubility based on the action of an acid. That is, the photoresist composition of the present invention is preferably a positive photoresist composition. Further, the photoresist composition of the present invention is preferably used as a photoresist composition for immersion exposure in a method for forming a photoresist pattern containing an immersion exposure step, and further comprises a photoresist layer formed of three layers. In the method for forming a photoresist pattern of the step, it can be suitably used as a positive photoresist composition for forming an upper photoresist film. Next, in the formation method of the photoresist pattern including the immersion exposure step and/or the step of forming the three-layer photoresist layer, the (A 1 ) component which is more suitable as the positive photoresist composition will be for example. &lt; (A1) component&gt; -18- 200844101 The (A 1 ) component preferably used in the positive resist composition is a constituent unit derived from an acrylate having an acid dissociable dissolution inhibiting group (a 1 ) is better. Further, the component (A1) is preferably a constituent unit (a2) derived from an acrylate having a cyclic group containing a lactone. Further, the component (A 1 ) is preferably a constituent unit (a3) derived from an acrylate further having an aliphatic hydrocarbon group having a polar group. In the specification and the scope of the patent application, "the constituent unit derived from the acrylate" means a constituent unit composed of the cleavage 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 halogen atom, a lower alkyl group, a halogenated lower alkyl group or the like. A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like is preferable, particularly preferably a fluorine atom. Further, the α-position (carbon atom of the α-position) of the constituent unit derived from the acrylate is 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 chain lower alkyl group such as a benzyl group or a neopentyl group. The halogenated lower alkyl group having an α-position substituent is specifically, for example, one obtained by substituting at least one hydrogen atom of the above-mentioned lower alkyl group with a halogen atom. In the present invention, the α-position of the acrylate is bonded by a hydrogen atom, a halogen-19-200844101 atom, a lower alkyl group or a halogenated lower alkyl group, and a hydrogen atom, a fluorine atom, a lower alkyl group or a fluorine atom. The lower alkyl group is more preferable, and it is industrially easy to obtain, and the hydrogen atom or the methyl group is most preferable. • Constituent unit (al) The constituent unit (a 1 ) is a constituent unit derived from an acrylate containing an acid dissociable dissolution inhibiting group. The acid dissociable dissolution inhibiting group in the constituent unit (a 1 ) is such that, as long as the (A 1 ) component has an alkali-insoluble alkali dissolution inhibiting property before dissociation, the entire component (A1) is changed to a base after dissociation. The soluble group may be used, and it is possible to use an acid dissociable dissolution inhibiting group which has been proposed as a base resin for enhancing a chemical type 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. Wherein, a "trialkyl ester" such as a hydrogen atom of a carboxyl group is substituted with a chain or a cyclic alkyl group to form an ester 'the oxygen atom at the terminal of the carbonyloxy group (-C(0)-0-) 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 cut off by the action of an acid. Further, the aforementioned 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 tertiary alkyl ester type acid dissociable dissolution inhibition -20- 200844101 tertiary alkyl ester type acid dissociation a dissolution inhibiting group, for example, an aliphatic branched chain acid dissociable dissolution inhibiting group, an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, etc., wherein the scope of the present application and the "aliphatic" referred to in the specification are It refers to the relative complication with respect to aromatics, that is, it is defined as a group or a compound having no aromaticity. The "aliphatic branched chain" means a branched chain structure having no aromaticity. The structure of the "aliphatic branched chain acid dissociable dissolution inhibiting group" is not limited to a group (hydrocarbon group) formed of carbon and hydrogen, 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 chain acid dissociable dissolution inhibiting group is preferably a C 4 to 8 tertiary alkyl group, specifically, for example, tert-butyl, tert-pentyl, tert-heptyl, etc. "aliphatic ring" "Formula" means a monocyclic or polycyclic group having no aromaticity. The "aliphatic cyclic group" in the constituent 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 alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, an oxygen atom (20), or the like. The "aliphatic cyclic group" removes the basic ring structure of the substituent, and does not limit the group (hydrocarbon group) composed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, -21 - 200844101, "hydrocarbon group" can be saturated or unsaturated, and it is generally preferred to saturate. The "aliphatic cyclic group" is preferably a polycyclic group. Specific examples of the aliphatic cyclic group include, for example, a group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane. The lower alkyl group may be substituted by a fluorine atom or a fluorinated alkyl group, and specifically, for example, a monocyclic alkane such as cyclopentane or cyclohexane or adamantane, norbornane or isoborn A group obtained by removing at least one or more hydrogen atoms from a polycyclic alkane such as an alkane, a tricyclodecane or a tetracyclododecane. Further, the acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, for example, a group having a tertiary carbon atom in a ring skeleton of a cyclic alkyl group, etc., specifically s ', for example, 2-methyl-2-golden Base, or 2-ethyl-2-golden hospital base, etc. Or, for example, an aliphatic ring group such as an adamantyl group, which is bonded to a group of an oxygen atom of a carbonyloxy group (-C-(〇)-0-), in the structural unit represented by the following formula, a group having a branched chain alkyl group having a tertiary carbon atom bonded thereto, etc. -22- 200844101 [Chem. 6]

• (a 1)) wherein R is the same as the hydrogen atom or substituent bonded to the carbon atom of the above acrylate; R15 and R16 are alkyl groups (may be linear, 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 such as a carboxyl group or a hydroxyl group, which is preferably a carbon number of 1 to 5). 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 ). •23- 200844101 【化7】

• (P 1) [wherein, Ri', r2, each independently a hydrogen atom or a lower alkyl group 'η is an integer from 0 to 3, and hydrazine is a lower alkyl group or an aliphatic cyclic group. η is preferably an integer of 0 to 2, more preferably 〇 or 1 and most preferably 0. R1' and R2' are each independently a hydrogen atom or a lower alkyl group. The lower alkyl group of r1', r2' is, for example, the same as the lower alkyl group of the above R', specifically, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert a lower linear or branched alkyl group such as a butyl group, a pentyl group, an isopentyl group or a neopentyl group. The lower alkyl group of R1, and r2' is preferably a methyl group or an ethyl group, and the methyl group is most preferred. 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 (p 1) is preferably a group represented by the following formula (p 1 -1). 【化8】 • · · (p 1 — 1)

—C-O-fcHa^Y -24- 200844101 [In the formula, R1', η, and Y are the same as those described 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 and used, for example, from the conventionally proposed one-ring or polycyclic aliphatic cyclic group among ArF photoresists, 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).化 - -c - Ο - R19 R18 · · (P2) [wherein, R17 and R18 are each independently a linear or branched alkyl or hydrogen atom, and R19 is linear. a branched or cyclic alkyl group, or R17 and R19 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 carbon number of the alkyl group is preferably from 1 to 15, which may be linear or branched, and preferably ethyl or methyl, and methyl is preferred. Any of R17 and R18 is a hydrogen atom, and the other is preferably a methyl group. -25- 200844101 When R19 is a linear, branched or cyclic alkyl group, the carbon number is preferably from 1 to 15'. It may be linear, branched or cyclic. When R19 is a linear or branched chain, the carbon number is preferably from 1 to 5, and the ethyl group and the methyl group are more preferably 'ethyl group. 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 1 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 alkane such as cyclopentane or cyclohexane or one or more polycyclic alkane such as adamantane, norbornane, isopentane, tricyclodecane or tetracyclododecane is removed. The base of a hydrogen atom, etc. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferred. Further, in the above formula, R17 and R19 are each independently a linear or branched alkyl group (preferably a C 1 to 5 alkyl group), and the end 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 constituent unit (al) is one or more selected from the group consisting of the following formula (al-0-1) and the constituent unit represented by the following formula (al-0-2). good. -26- 200844101 【化1 〇】

• « · (a 1 - Ο - 1) (wherein R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; and X 1 is an acid dissociable dissolution inhibiting group). [1 1]

(wherein 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 (a 1 - 0 -1 ), the halogen atom, the lower alkyl group or the halogenated lower alkyl group of R is a halogen atom which is bonded to the α-position of the acrylate, a low-grade courtyard group, and a halogenated lower-grade hospital base. The same meaning. -27- 200844101 χ1 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 acid dissociating dissolution inhibiting group. A tertiary alkyl ester type acid dissociable dissolution inhibiting group is preferred.

In the formula (al-0-2), R has the same meaning as R in the above formula (al-0-1). X2 is the same as X1 in the formula (al-0-l). Y2 is preferably an alkylene group having 1 to 4 carbon atoms or a divalent aliphatic cyclic group. In the case of the aliphatic cyclic group, the same as the above-mentioned "aliphatic cyclic group" can be used, for example, in addition to the group in which two or more hydrogen atoms are removed. In the constituent unit (al), more specifically, for example, a constituent unit represented by the following general formulae (a 1 -1 ) to (a 1 - 4 ). -28- 200844101 【化1 2】

[In the above formula, X' is a tertiary alkyl ester type acid dissociable dissolution inhibiting group; Y is a lower alkyl group having 1 to 5 carbon atoms, or an aliphatic cyclic group; η is an integer of 0 to 3; m is 0 or 1; R is the same meaning of R in the above formula (al-0-l); R1, R2' are each independently a hydrogen atom or a lower-order courtyard having a carbon number of 1 to 5. It is preferable that at least one of R1 and R2' is a hydrogen atom, and more preferably a hydrogen atom. η is preferably 〇 or 1. X is the same as the cyclic tertiary alkyl ester type acid dissociable dissolution inhibiting group exemplified in the above X1. -29 - 200844101 The aliphatic ring group of γ is, for example, the same as that exemplified in the description of the above "aliphatic ring group". The following are specific examples of the constituent units represented by the above formulas (al-l) to (al-4), -30-200844101 [Chemical Formula 1] H3 x ch3 ch3 0 V &lt;?H3. =^ Q==l ρ2Μ2(^3一. Force

0·

(a1 -1 -1) (a1-1-2) (a1+3)

(a1 -1-11) (a1-1-12) (a1-1-13) CH3--fcH2—04- 0=( &lt;?h3 O-

(a1-1-14) (al-1-15)

CH〇 f c2h5

(a1-1-16) -31 - 200844101 [Chemical 1 4] ch3 -ch2~ch^- 〇==( CH: 0,

Ch3

(a1+19)

(a1-1-20) ch3 ch3 *ch2~c^- —^ch2—CH^· -^CH2 0=^ ch3 0=^ ch3 〇==\)( -CH2—CH^»4

〇=\ c2h5〇,

(a1-1-24) (a1-1-21) (al-1-22) (al-1 -23) CH3 Brewing —fCH2~CH^—, 2-. D -{CH2 - H0==^ Ch3/CH3 〇=\CHj^H3 〇=\〇CH3 ‘ o ,CH2—c •ch2 (a1-1

Ch3 CH:

CH3 (a1H-26) (a1+27) 〇.

(at-1-28) -CH2-C^r 0=1^ £ 〇,

Ch3 -^ch2-〒 j 〇=\ ch3 ch3 (al-1-29) —^CH2—CH^ -^CH2—cj- 〇==\ ?2H5 〇=\ c2h5°6 °δ °6 (a1 - 1-30> ("1-1-31" (at-1-32) 32- 200844101 [Chemical 1 5]

Ca1-1-37) (a1 -1 - 38) (al -1-39) (a1 -1-40) ch3 -^ch2-ch)-0=4 9 〇&gt; (al-1-41) [ 1 6] 0= 0 ?h3 :CH2—*^ch2_ 〒+ -^&gt;CH2 A CHy 0==\ 〇=\ o==4 0 Ο n H3G a ch3 (at-1-42) CHa H3C 〆ch3 (al+43) CH3 h3C a 0 &quot;CH3 h3C&quot; C2H5 (al-Bu 44) O', Ch3 C2H5 (a1+45)

33- 200844101 【化1 7】

-34- 200844101 【化1 8】

(•1+30) Cal-2-31) -35- 200844101 【化1 9】

-36- 200844101 【化2 0】

Cat-3-1)

(al-3-2)

(al -3 - 9)

O

O 纪七Η3〇ίθ 200844101 【化2 1】 CH3 ch3 inch CH2-〒+ 十 CH2-〒十-^CH2-CHj- 0=4 0=\ 〇=\ O O 0

O C2H5^T^ 1 h3c-(a1-3-13) (a1-3-14) (a1-3-15)

T 〇 / \

(a1-3-22) (a1-3-23) -|ch2-ch| 0=(

(a1-3-24) -38- 200844101 [Chemical 2 2] ^ςΗ2^Η)- ^CHa-C-)- -f-CH2^CH)- ^CH2-C-)-〇 〇 p V 〇

o r° Q °v

o 〇 o &gt;

0 o

o 〇&gt; o 0&gt; (a1-4-1) (a1-4-2) (al+3) (a1.4e4) io (a 1-4-5) Ten CH, H2-〒吟10 CH Wide Έ-j—^ch2—ch)— ch3〇4〇〇=\&gt; 0Λ ten% ten ch2-?h 卜rA Μ ”° 0 gas 4 〇so r

Q

0 to O'

(a1-4-6)

〇( oO; (a 1-4-7) (a1+8) (a1-4-9) (a1-4-10) H2-C-) ^CH2--CH^ --^CH2—C-^ - ^CHa—C-)~i 〇P 〇P %

° &gt;=〇 &gt;0Q a

(a1-4-11) (al-4-12)

0

Q (a1-4-13) (al-4-14) ^ (a1-4-15) -39- 200844101 [Chem. 2 3]

-fcH2-CHy -(CH2-C^ *fCH2--CHj- -^CH2-C-^-〇 〇 〇 P P P &gt;4

〇 &gt;=〇 O 〇 〇&gt;〇&gt;

o y=z〇 } °&gt;〇, o

Ch)- 0

o O (al-4-16) CH3 to ^ (a1-4-17) (a1-4-18) (a1-4-19)

Q % (a1-4-20)

Ο

ο &gt;=0ο ο (al+21) (ai^22) (a1-4-23) (a1-4-24)(4)+25) ο Ο) ο

^CH24^ ^CH24^ ^CH2〇^

O )=〇 &gt;〇 )=0 d 〇 〇 〇

0 o o: 〇No °b V (a1-4-26) (a1-4-27) (a1-4-28) (al -4_29) Ca1^4-30)

P -40- 200844101 The constituent unit (a 1 ) may be used singly or in combination of two or more. Among them, the constituent unit represented by the formula (al-Ι) is preferred. Specifically, at least one selected from the constituent units represented by the formula (al-1-l) to (al-1-6) or the formula (al-1-35) to (a 1 -1 - 4 1 ) One is the best. Further, the constituent unit (a 1 ) is, in particular, a unit represented by the following general formula (al-1-O1) including constituent units of the formulae (a 1 -1 -1 ) to (al-1-4), or The following formula (al-1-02) containing a constituent unit of the formula (al-1-35) to (al-1-41) is preferred. [Chem. 2 4]

[In the formula, R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R11 is a lower alkyl group]. -41 - 200844101

Wherein R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R12 is a lower-grade courtyard group 'h is an integer of 1 to 3).

In the formula (al-1-Ol), R has the same content as R of the above formula (al-0-l). 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-1-02), 'R has an inner valley which is opposite to R of the above formula (al-0-l). The lower-grade courtyard of R is the same as the lower-grade courtyard shown by R, and it is preferably methyl or ethyl, and ethyl is preferred. h is preferably 1 or 2, and 2 is the best. In (A), the ratio of the constituent unit (a 1 ) is preferably from 10 to 80 mol%, more preferably from 2〇 to 70 °旲%, based on the total constituent unit constituting the component (a). It is best to use 2 5 to 50 mole %. When the lower limit is 値 or more, the pattern can be easily formed when it is a positive resist composition, and when it is below the upper limit 値, it can be balanced with other constituent units. -42- 200844101 constituting unit (a2) In the present invention, the component (A1) is a constituent unit derived from an acrylate having a cyclic group containing a lactone in addition to the above-mentioned constituent unit (a1) (a2) ) is better. Here, the cyclic group containing a lactone is a cyclic group containing one ring (lactone ring) of the -〇-C(0)- 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 constituent unit (a2) can effectively improve the adhesion of the photoresist film to the substrate in the case where the (A 1 ) component is used to form the photoresist film, and can effectively improve and contain water. The affinity of the developer. Here, the constituent unit (a2) may be 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 example of the constituent unit (a2), more specifically, for example, the constituent units shown in the following general formulas (a2-l) to (a2-5). -43- 200844101 【化2 6】

Wherein R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R' is each independently a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms, and m is 0 or 1 An integer, A is an alkyl or oxygen atom having a carbon number of 1 to 5. In the formulae (a2-l) to (a2-5), R has the same content as R in the above formula (al-0-l). The lower alkyl group of R' has the same content as the lower alkyl group of R in the above formula (al-0-1). The alkyl group having a carbon number of 1 to 5, specifically, for example, a methyl group, an ethyl group, an η-propyl group, an iso-propyl group or the like. Among the formulae (a2-l) to (a2-5), R' is preferably a hydrogen atom in terms of industrial availability. The following are examples of specific constituent units of the above general formulae (a2-l) to (a2-5). -44- 200844101 [Chem. 2 7] A is &lt;age 1&gt; (10)·1·2) {a2 is called ^ Wf and /3 0==^

(a2-1-4) -^ch2-c^ 〇s=\ 0==^Jf-square (a2-1^) (a2«14) -45- 200844101 [Chem. 2 8] -(CH2-Cf- 0==4^ -(CH2-CHf _{CH2-Cf 〇a^ ^ ° ch3 ch3 +ch2—c)· 〇= {a2-2-1} 〇ch3 (a2-2-2) CH3

(a2-2-3) ch3

(a2-2-4) CH3

O -(CH2-C+ -(CH2-C·}- &quot;(〇H2—CH)- +CH2—9 孓 0==1^ CH3 0=4^ 〇=\

(a2*2-6)

(d2-2-€)

CH3- (a2-2-7) (32-2-8) icH2-cf-

(a2-2-9) 〇 (a2-2-10) -46 - 200844101

-47- 200844101 【化3 0】

-48- 200844101 【化3 1】

Wherein, at least one selected from the constituent units represented by the formulas (a2-1) to (a2-3) is preferably used, and at least one selected from the formulas (a2-1) to (a2-3) One is better. Specifically, use the formula (&amp;2-1-1) &gt; (a2-l-2) ^ (a2-2-l) ' (a2-2-2) ' (a2-3-l) It is preferable that one or more selected from (a2-3-2) a2-3-9) and (a2-3_10). In the component (A2), the component (a2) may be used alone or in combination of two or more. -49 - 200844101 (A 1 ) The proportion of the constituent units (a2) in the composition is preferably 5 to 60 mol%, and 10 to 50 mol%, based on the total of the constituent units constituting the component (A1). Preferably, it is preferably 20 to 50 mol%. When the lower limit is 値 or more, the effect can be sufficiently obtained when the constituent unit (a2) is contained, and when it is equal to or less than the upper limit ,, the balance with other constituent units can be obtained. • constituent unit (a3) In the present invention, the component (A1) contains, in addition to the above-mentioned constituent unit (al), or the constituent units (al) and (a2), and further contains (a3) an aliphatic group having a polar group. The constituent unit derived from the hydrocarbyl acrylate is preferred. When the constituent unit (a3) is contained, the hydrophilicity of the component (A1) 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 is, for example, a linear or branched chain 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 may be, for example, a resin for use in an ArF excimer laser resist composition, and is appropriately selected from the contents of most proposals. Further, it is more preferably a constituent unit derived from an acrylate having a hydroxyl group, a cyano group, a carboxyl group, or an aliphatic polycyclic group having a hydroxyalkyl group in which a part of hydrogen atoms in the alkyl group is substituted by a fluorine atom. The polycyclic group is, for example, a group obtained by removing one or more hydrogen atoms -50-200844101 from a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, for example, a group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, iso-serane, tricyclodecane or tetracyclododecane is used. 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 constituent 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 constituent unit derived from the hydroxyethyl acrylate is When the hydrocarbon group is a polycyclic group, for example, a structural unit represented by the following formula (a3-1), a structural unit represented by (a3-2), a structural unit represented by (a3-3), or the like is preferable. [化3 2]

(a3-3) [wherein, R is the same meaning as R in the above formula (a1·0-1),] is an integer of 1 to 3, k is an integer of 1 to 3, and t' is 1 to An integer of 3, 1 is an integer from 1 to 5, and s is an integer from 1 to 3. In the formula (a3-l), j is preferably 1 or 2, and more preferably 1 is further preferred. j 200844101 In the case of 2, it is more preferable that the hydroxyl group is bonded to the 3 and 5 positions of the adamantyl group. In the case where j is 1, it is particularly preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group. Further, it is preferable that j is 1 and it is particularly preferable that the hydroxyl group is bonded to the adamantyl group. 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 1 and 1 is preferable, and s is preferable. Preferably, the compound of the above-mentioned carboxyl group of the acrylic acid is bonded to a compound of 2-norbornyl group or 3-norbornyl group. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the norbornyl group. In the component (A1), the constituent unit (a3) may be used singly or in combination of two or more. The ratio of the constituent unit (a3) in the component (A1) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on the total constituent unit of the component (A1). Up to 2 5 mol% is the best. When the lower limit is 値 or more, the effect of containing the constituent unit (a3) can be sufficiently obtained, and when it is less than or equal to the upper limit, the balance with other constituent units can be obtained. The constituent unit (a4) (A1) may further contain other constituent units (a4) other than the above constituent units (al) to (a3) insofar as the effects of the present invention are not impaired. -52- 200844101 The constituent unit (a4) is not particularly limited as long as it is a constituent unit not classified into the above-mentioned constituent sheets to (a3). A conventionally known multi-layer used for a photoresist composition such as an ArF excimer laser or a KrF excimer laser (preferably for sub-laser). The constituent unit (a4), for example, a constituent unit derived from an acrylate having a non-acid dissociable aliphatic group is preferable. For example, the resin composition of the photoresist composition such as the ArF excimer laser or the ArF excimer laser for KrF excimer laser can be used in the same manner as the above-mentioned constituent unit (a1). To the majority of the known constituent units. In particular, when at least one selected from the group consisting of a tricyclodecylalkyl group, an adamantyl group, a tetracyclododecyl group, and a norbornyl group is used, it is preferably obtained. The polycyclic group may be substituted by an alkyl group having a carbon number of 1 chain or a branched chain. The constituent unit (a4), specifically, for example, a constituent unit represented by the following general formula to (a4-5). Position (a 1 ) which can form a single aliphatic polycyclic ring group using ArF quasi-fraction, showing content, (preferably using alkyl, different from industrial to 5 straight (a4-l) -53- 200844101 【化3 3】

[In the formula, R is the same as R in the above formula (al-0-1)] 〇 When the above-mentioned constituent unit (a4) is contained in the component (A1), the ratio of the constituent unit (a4) is relatively The total of the constituent units constituting the component (A 1 ) is preferably from 1 to 30 mol%, more preferably from 10 to 20 mol%. In the present invention, the component (A 1 ) is a resin component (polymer) which is increased in solubility based on the action of an acid, and is suitable as a unit of the resin component (polymer), for example, having a constituent unit (al ) and a constituent unit ( A2), and a copolymer constituting the unit (a3), the copolymer, for example, a copolymer obtained from constituent units (al), (a2), and (a3), constituting units (al), (a2), (a3) And the copolymer obtained by (a4). In the present invention, the component (A) is particularly preferably a copolymer (A 1 -1 ) containing a combination of units represented by the following formula (A 1 -1 ). -54- 200844101 【化3 4】 Ρ η

[In the formula, R is the same as described above. R2 Q is a lower alkyl group]. In the formula (A1-1), R is the same as described above. Among them, a hydrogen atom or a methyl group is preferred. R2Q is a lower alkyl group, preferably a carbon number of 1 to 5. Among them, methyl or ethyl is preferred, and methyl is preferred. In the component (A), the copolymer (A1-1) may be used singly or in combination of two or more. The content of the copolymer (A 1 -1 ) in the component (A) is preferably 70% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass. When the lower limit of the range is 値 or more, when the positive resist composition is used, the lithographic lithography characteristics can be further improved. The component (A 1 ) can be obtained, for example, by polymerization of a monomer derived from each constituent unit, for example, by radical polymerization such as azobisisobutyronitrile (AIBN) by a known radical polymerization. Further, the component (A1) may be a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH at the time of the above polymerization, and may be introduced at the end - 55-200844101 C (CF 3) 2 _ 〇Η base. Thus, a copolymer in which a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted by a fluorine atom is obtained can be effectively reduced in defects or reduced in LER (Line Edge Roughness). The mass average molecular weight (Mw) of the component (A1) (polystyrene equivalent amount of the gel permeation chromatography method) is not particularly limited, and is generally preferably 2,000 to 50,000, and more preferably 3,000 to 30,000. 5,000 to 20,000 is the best. When it is less than the upper limit of the range, sufficient solubility is obtained for the photoresist as a photoresist, and when it is larger than the lower limit of the range, a good dry etching resistance or a resist pattern cross-sectional shape can be obtained. Further, the degree of dispersion (Mw/Mn) 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 component (A 1 ), the alkali-soluble resin component other than the copolymer (A 1 -1 ), for example, other local molecular compound 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 can be appropriately adjusted 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丨) containing a compound of the above formula (b 1 · 5 ) (hereinafter also referred to as For those who are (B1) ingredients. Where R41, R42 and R43 ·, n. , ηι, -56- 200844101 n2 and n3; The X-system is the same as those enumerated in the above-mentioned first aspect of the present invention. (B) component, because it contains this (B 1 ) component, it has good properties for general photoresist solvents such as propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and ethyl lactate (EL). It is soluble, so it is used as a photoresist composition for immersion exposure or as an upper photoresist film in a method for forming a resist pattern containing an immersion exposure step or a step of forming a three-layer photoresist layer. At the time of the photoresist composition, good lithography characteristics can be obtained. Further, the (B 1 ) component can be added in a large amount to the photoresist composition used in the formation method of the resist pattern which comprises the step of the immersion exposure or the step of forming the three-layer photoresist. It is presumed that it is a cause of high transparency (inhibition of absorption of light) in the exposure wavelength region (particularly, the wavelength region of the ArF excimer laser). (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 70% by mass or more, and particularly preferably 1% 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 (B 1 ) component, phase -57 - 200844101 is preferably 1 to 30 parts by mass, and 5 to 5 parts by mass of the above (A) component. 20 parts by mass is more preferably, and it is particularly preferably 7 to 18 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 (Β) component, the acid generator (Β2) other than the above (Β1) component (hereinafter also referred to as (Β2) component) may also be used in the above (Β 1 ) component. The (Β2) component is not particularly limited as long as it is a component other than the above (Β 1 ) component, and the component which has been proposed as an acid generator for enhancing chemical resist can be used. The acid generator, for example, an iron salt/acid generator such as an iodine salt or a phosphonium salt, an oxime sulfonate acid generator, a dialkyl or bisarylsulfonium S diazomethane, or a poly (double) Sulfhydryl)diazomethanes such as diazomethanes, gas generators, nitrobenzylsulfonate acid generators, iminosulfonates #@producers, diterpenoid acid generators, etc. Know the compound. The key salt acid generator is, for example, an acid generator and the like represented by the following formula (b-Ο). [化3 5]

-58- 200844101 [wherein R51 is a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group; and R52 is a hydrogen atom, a hydroxyl group or a halogen. An atomic, linear or branched alkyl group, a linear or branched chain halogenated alkyl group, or a linear or branched alkoxy group; R53 is an aryl group which may have a substituent; ' is an integer from 1 to 3. In the formula (b-Ο), R51 is a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group. The linear or branched chain 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. The above cyclic alkyl group is preferably a carbon number of 4 to 12, preferably a carbon number of 5 to 10, and particularly preferably a carbon number of 6 to 10. 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 to be substituted with respect to the number of all hydrogen atoms in the alkyl group) is preferably from 1 Torr to 100%, more preferably From 50 to 100%, in particular, all of the hydrogen atoms are replaced by fluorine atoms, and it is more preferable to increase the strength of the acid. R51 is preferably a linear alkyl group or a fluorinated alkyl group. R52 is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched chain, a linear or branched chain halogenated compound, or a linear chain; a chain alkoxy group. The halogen atom in R52, for example, a fluorine atom, a bromine atom, a chlorine atom, an iodine atom or the like, is preferably a fluorine atom. -59- 200844101 In R52, the alkyl group is linear or branched, and its carbon number is preferably from 1 to 5, more preferably from 1 to 4, most preferably from 1 to 3. In R52, a halogenated courtyard group is a group in which a part or all of a hydrogen atom in a hospital base is substituted by a halogen atom. The alkyl group thereof is, for example, the same as the "alkyl group" in the above R52. The halogen atom to be substituted is, for example, the same as the content described in the above "halogen atom". The halogenated alkyl group is preferably one obtained by substituting 50 to 100% of the total number of hydrogen atoms with a halogen atom, and more preferably all of them are substituted. In R52, the alkoxy group is linear or branched, and its carbon number is preferably from 1 to 5, particularly from 1 to 4, most preferably from 1 to 3. R52, wherein a hydrogen atom is preferred. R53 is a structure of a radical which may have a substituent, which is a basic ring (parent ring) from which a substituent is removed, and may be, for example, a naphthyl group, a phenyl group, a fluorenyl group or the like, and is exposed to the effect of the present invention or an ArF excimer laser or the like. From the viewpoint of light absorption and the like, a phenyl group is preferred. The substituent is, for example, a hydroxyl group or a lower alkyl group (linear or branched, preferably having a carbon number of 5 or less and more preferably a methyl group). The aryl group of R53 is more preferably one having no substituent. u' ' is an integer from 1 to 3, more preferably 2 or 3, and particularly preferably 3 is preferred. Preferred examples of the acid generator represented by the formula (b-0) are as shown below. -60· 200844101 【化3 6】 〇-〇cf^ h〇-〇~0 〇-〇h〇-hQO O^Ocf^ h〇~OO C4F«SCf3 H3C~^3^Z^ (4)〇; CHj h 〇~Q^O ch3 The acid generators of the formula (b-0) may be used alone or in combination of two or more kinds. Further, the agent other than the acid generator represented by the above formula (b - 〇) is, for example, a compound 1 represented by the following formula (b-Ι) or (b-2).

...(b-1)

C4F9S〇3 CFjSO; CF, S〇iC4F9SOI, or 2 iron salts acid ^ °B(b-2) -61 - 200844101 [where R1'' to R3&quot;, R5'' to R6'', each Independently an aryl or alkyl group; R4'' is a linear, branched or cyclic alkyl or fluorinated alkyl group; at least one of R1'' to R3'' is an aryl group, R5'' to R6 At least one of '' is an aryl group). In the formula (b-Ι), R1'' to R3'' are each independently an aryl group or an alkyl group; at least one of R1'' to R3'' is an aryl group. It is preferable that two or more of R1'' to R3'' are used as a square base, and that all of R1 to R3 are aryl groups. The aryl group of R1'' to R3'' is not particularly limited, and is, for example, an aryl group having a carbon number of 6 to 20' and a part or all of a hydrogen atom of the aryl group may be an alkyl group, an alkoxy group, A halogen atom or the like may be substituted or unsubstituted. From the viewpoint of inexpensive synthesis of an aryl group, it is preferred to use an aryl group having 6 to 10 carbon atoms. Specifically, for example, a phenyl group, a naphthyl group or the like. The alkyl group which may be substituted for the hydrogen atom of the above aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group. The alkoxy group which may be substituted for the hydrogen atom of the above aryl group is preferably a methoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group or an ethoxy group. The halogen atom which may be substituted for the hydrogen atom of the above aryl group, and the fluorine atom is preferably an alkyl group of R1'' to R3'', and is not particularly limited, and may be, for example, a linear chain having a carbon number of i to 1 Å. The number of carbon atoms is preferably from 1 to 5, from the viewpoint of having excellent resolution, such as a branched chain or a cyclic alkyl group. Specifically, for example, methyl, ethyl, η-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, cyclopentyl-62-200844101, hexyl, cyclohexyl, decyl, fluorene Base. From the viewpoint of having excellent resolution and being inexpensively synthesized, it is more preferable to use a methyl group. Among them, those in which R1'' to R3'' are each a phenyl group or a naphthyl group are preferred. R4'' is a linear, branched or cyclic alkyl group or a fluorinated alkyl group. The linear or branched 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. The cyclic alkyl group is a ring group represented by the above R1", preferably having a carbon number of 4 to 15, preferably 4 to 10 carbon atoms, and most preferably having a carbon number of 6 to 10 carbon atoms. Preferably, 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 fluorinated alkyl group is fluorinated. The ratio (ratio of fluorine atom in the alkyl group) is preferably from 10 to 100% 'more preferably from 50 to 100%, especially in the case where all of the hydrogen atoms are replaced by fluorine atoms', and the strength of the acid is stronger. More preferably, R4'' is preferably a linear or cyclic alkyl group, or a linear or cyclic fluorinated alkyl group. In the formula (b-2), R5'' to R6'' Each of them is independently an aryl group or an alkyl group; at least one of R5, to R6, is an aryl group, and all of R5'' to R6'' are preferably an aryl group. R5'' to R6'' The aryl group is, for example, the same group as the aryl group of R1'' to R3''. The alkyl group of R5, to R6, is, for example, the same group as the alkyl group of R1'' to R3''. - 200844101 It is best to use all of R5'' to R6'' as phenyl. R4'' in (b-2) is the same as R4'' in (b-Ι). Specific examples of the key salt-based acid generators represented by the formulae (b-1) and (b-2), for example, Triphenylmethane iodide trifluoromethanesulfonate or nonafluorobutane sulfonate, bis(4-tert-butylphenyl)iodide trifluoromethanesulfonate or nonafluorobutane sulfonate, Triphenyl mirror of trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tris(4-methylphenyl)phosphonium trifluoromethanesulfonate, and heptafluoropropane sulfonate Or its nonafluorobutane sulfonate, dimethyl (4-hydroxynaphthyl) fluorene trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, monophenyl dimethyl Trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenylmonomethyl hydrazine trifluoromethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane Sulfonate, (4-methylphenyl) diphenyl vegetable trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxybenzene) Diphenyl hydrazine difluoromethyl sulfonate, Fluoropropane compound acid ester or its nonafluorobutyl sulfonate, tris(4-tert-butyl)phenyl fluorene trifluoromethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate , triphenylmethanesulfonate of diphenyl(1-(4-methoxy)naphthyl)anthracene, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, bis(1-naphthyl)phenyl a trifluoromethanesulfonate, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof, etc. Further, the anion portion of the above-mentioned key salt may be a methanesulfonate, an η-propane sulfonate, or an n- An iron salt substituted with butane sulfonate or η-octane sulfonate. Further, in the above formula (b-Ι) or (b-2), the anion moiety-64 - 200844101 is represented by the following formula ( The iron salt acid generator obtained by substituting the anion moiety represented by b-3) or (b-4) may also be the same as the above formula (b-1) or (b-2). In the present specification, the oxime sulfonate-based acid generator has, for example, at least one compound represented by the following formula (B-1), which has a property of generating an acid by radiation or line irradiation. The above-mentioned oxime sulfonate-based acid generator is generally used for the _ strong chemical type positive-type photoresist composition, and the present invention can be optionally used. [化3 8]

——0——S〇2——R31 • · · (B-1) [In the formula (B-1), R31 and R32 are each independently an organic group]. The organic group of R31 and R32 is a group containing a carbon atom, but it may contain an atom other than a carbon atom (e.g., a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)). 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. Here, "having a substituent" means that a part or the whole of a chlorine atom of an alkyl group or an aryl group is substituted by a substituent. -65- 200844101 The alkyl group preferably has a carbon number of 1 to 20, preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and a carbon number of 1 to 6 and a carbon number of 1 to 6. 4 is especially good. Among them, the alkyl group is particularly preferably an alkyl group obtained by partial or complete halogenation. Further, a partially halogenated alkyl group means an alkyl group in which one part of a hydrogen atom is replaced by a halogen atom, and a completely halogenated alkyl group means an alkyl group in which a hydrogen atom is entirely substituted by a halogen atom. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. That is, the halogenated hospital base is preferably a fluoride hospital base. 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 G. The aryl group is particularly preferably an aryl group obtained by partially or completely halogenating. Further, the partially halogenated aryl group means an aryl group in which one hydrogen atom is substituted by a halogen atom, and the fully halogenated aryl group means an aryl group in which all hydrogen atoms are replaced by a halogen atom. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine 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. The organic group of R32 is a linear, branched or cyclic alkyl group, an aryl group or an amino group. The thiol group and the aryl group of R are the same as those of the alkyl group and the aryl group listed in the above R3 2 . R32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms which does not have a 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 (Β-2) or -66-200844101 (B-3). [B] 2 · · · · (B - 2) R34—C=N—Ο—S〇2—R35 R33 In the formula (B-2), R33 is a cyano group, an alkyl group having no substituent or halogenated Alkyl; R34 is an aryl group; R35 is an alkyl group having no substituent or a halogenated alkyl group [Chemical 4 0] R37- _C==N_ R36 βΟ—SOo—R38 P,·· (B-3) In (B-3), R36 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group; R37 is a 2 or 3 valent aromatic hydrocarbon group; and R38 is an alkyl group having no substituent or a halogenated 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 1 Torr, more preferably a carbon number of 1 to 8, and a carbon number of 1 to 6. optimal. R33 is preferably a halogenated alkyl group, and more preferably a fluorinated alkyl group. -67- 200844101 The fluorinated alkyl group in R33, wherein the hydrogen atom in the alkyl group is preferably fluorinated by 50% or more, more preferably 70% or more, and more preferably 90% or more of the fluorinated one. The aryl group of R34, for example, a ring of an aromatic hydrocarbon such as a phenyl group or a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group or a phenanthroline group, and one hydrogen atom is removed. And a heteroaryl group obtained by substituting a part of a carbon atom constituting the ring of the above-mentioned group with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. Among them, the base is better. The aryl group of R34 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or an alkoxy group. The alkyl group or the halogenated alkyl group in the substituent is preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 4. Further, the halogenated alkyl group is more preferably a gasification base. The alkyl group or the halogenated alkyl group having no substituent of R3 5 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, more preferably a fluorinated alkyl group, and most preferably a partially fluorinated alkyl group. The fluorinated alkyl group in R35 preferably has a hydrogen atom in the alkyl group of 50% or more, more preferably 70% or more, and when it is fluorinated by 90% or more, the acid produced can be improved. Better. The most preferred one is a perfluorinated alkyl group in which 1 〇〇 % of a hydrogen atom is replaced by fluorine. In the above formula (B-3), the group or the halogenated alkyl group having no substituent of R36 is, for example, the same as the alkyl group or the halogenated alkyl group having no substituent represented by the above R33. -68- 200844101 A 2- or trivalent aromatic hydrocarbon group of R37, for example, a group obtained by further removing 1 or 2 hydrogen atoms from the aryl group of the above R34. The alkyl group or the halogenated alkyl group having no substituent of R3 8 is, for example, the same as the alkyl group or the halogenated alkyl group having no substituent represented by the above R35, and 〇 p ' ' is preferably 2. Specific examples of the sulfonate-based acid generator, such as a-(p-toluenesulfonyloxyimido)-benzyl cyanide (cyanide), α-(ρ-chlorophenylsulfonyloxyimino) -benzyl cyanide, α-(4-nitrophenylsulfonyloxyimino)-benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimido)- Benzyl cyanide, α-(phenylsulfonyloxyimido)-4-chlorobenzyl cyanide, α-(phenylsulfonyloxyimino)-2,4-dichlorobenzyl cyanide, --(phenylsulfonyloxyimino)-2,6-dichlorobenzyl cyanide, α-(phenylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(2 -Chlorophenylsulfonyloxyimido)-4-methoxybenzyl cyanide, α-(phenylsulfonyloxyimino)-thien-2-ylacetonitrile, α-(4-dodecane Benzosulfonyloxyimido)-benzyl cyanide, α-[(indole-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(dodecylbenzenesulfonate)醯 oxyimino)-4-methoxyphenyl]acetonitrile, α-(p-toluenesulfonyloxyimino)-4-thenyl cyanide, α-(methylsulfonyloxyimino) 1-cyclopentenylacetonitrile, (methylsulfonium) Oxyimido)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimino)-1- Cyclooctyl acetonitrile, α-(trifluoromethylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-cyclohexylacetonitrile, ^ (ethylsulfonyl-69-200844101 nonoxyimino)-ethylacetonitrile, (propylsulfonyloxyimino)-propylacetonitrile, α-.(cyclohexylsulfonyloxyimino)-cyclopentyl Acetonitrile, α-(cyclohexylsulfonyloxyimido)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonate Amino)-1-cyclopentenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, a-(n-butylsulfonyloxyimino)-1 -cyclopentenylacetonitrile, α·(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, --( η-butylsulfonyloxyimido)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-phenylacetonitrile, α·(methylsulfonyloxyimine ))-methoxyphenylacetonitrile --(trifluoromethylsulfonyloxyimido)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-fluorene-methoxyphenylacetonitrile, α-(ethylsulfonate Ominoimido)-fluorenyl-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-oxime-methylphenylacetonitrile, α-(methylsulfonyloxyimino)-ruthenium -Bromophenylacetonitrile and the like. Further, the oxime sulfonate-based acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei 9-2085-54 (paragraphs [0012] to [14] (Chemical Formula 1), WO2004/074242A2) The sulfonate-based acid generator disclosed in Examples 1 to 40 of pages 65 to 85 may also be used in combination. Further, for example, a compound shown below or the like is suitable. -70- 200844101 【化4 1】 ch3 ch3o

C^N—O—S02—CF3 (CF2)e-H

0—S0 wide CF3 |cF2)6 - H ch3o-Qk-csf7

CH30—^ O—S〇2—CF3IcF Out-H—N—0—S〇2—CF3 C3F7

C*=N—0—S〇2—C4F9CaF? C*=sN—O—S〇2—C4F9 (CF2)e-H

C=N—0—S02—CF3 (CF2)6—H

U -0—S〇2—CF3

\/^y^9=gN~°~s〇2—C4F9 (CF2)e—H

-71 200844101 Among the above exemplified compounds, the following four compounds are preferred. [化4 2] c4h9_o2s—〇

〇—S02*-C4H9 H3C—C==N—OS〇2-(CH2)3CH3 H3C—C=N——OS〇2-(CH2)3CHa

C=N-〇—S〇2—C4P9 |cf2)6-h

C*=N-O-S〇2-C4F9 cf2)4-h Diazomethane acid generator, specific examples of double-base or double-base δ page-based heavy gas methane, such as bis(isoindenyl) Sulfhydryl)diazomethane, bis(ρ-toluenesulfonyl)diazomethane, bis(1,1-methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazo Methane, bis(2,4-methylphenylsulfonyl)diazomethane, and the like. Further, it is also suitable to use a diazomethane-based acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Further, poly(disulfonyl)diazomethanes, for example, 1,3 -variable (local fluorenyldiazomethylsulfonyl)propane, 1,4 disclosed in JP-A-1-22707 - bis(phenylsulfonyl-diazomethylsulfonyl)butane, ι,6-bis(phenylsulfonyldiazepinesulfonyl)hexane, I,10-bis(phenylsulfonate) Mercaptodiazepinemethanesulfonyl), 1,2_bis (transhexylsulfonic acid-72-200844101 diazomethyl mineral acid) acetamidine, 1,3 -bis (cyclohexyl fill) Heavy gas methylsulfonyl)propane, 1,6-bis(cyclohexylsulfonyldiazomethylsulfonyl)hexane, 1,10-bis(cyclohexylsulfonyldiazomethylsulfonyl) ) decane, etc. (B2) The above-mentioned acid generator may be used alone or in combination of two or more. In the photoresist composition of the present invention, the content of the component (B) is from 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, the post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer When the nitrogen-containing organic compound (D) (hereinafter also referred to as (D) component) of any component is 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. -73- 200844101 An amine (alkylamine or alkanolamine) or a cyclic amine obtained by substituting at least one hydrogen atom of ammonia NH3 with an alkyl group or a hydroxyalkyl group having a carbon number of 12 or less. Specific alkylamines and alkanolamines such as η-hexylamine, η-heptylamine, n-octylamine, η-decylamine, η-decylamine, etc.; monoethylamine; a dialkylamine such as η-propylamine, di-η-heptylamine, di-η-octylamine or dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine , tributylamine, tri-n-hexylamine, tripentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine, a secondary amine such as tris-n-taucanylamine; an alkane such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine or tri-n-octanolamine Alcoholamine. Among them, a trialkylamine having 5 to 10 carbon atoms is preferred, and a tri-n-pentylamine or a tri-n-octylamine is more preferred, and a tri-n-pentylamine is preferred. The cyclic amine is, for example, a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine). The aliphatic monocyclic amine is specifically, for example, piperidine, piperazine or the like. The aliphatic polycyclic amine is preferably a carbon number of 6 to 10, specifically, for example, 1,5-diazabicyclo[4.3.0]-5-decene, 1,8-diaza Ring [5.4.0]-7-undecene, hexamethylenetetrazole, 1,4-diazabicyclo[2.2.2]octane, and the like. They may be used alone or in combination of two or more. (D) The component (A) component is 100 parts by mass, and is generally in the range of -74 to 200844101 0.01 to 5.0 parts by mass. &lt;Arbitrary component&gt; [(E) component] Further, the photoresist composition of the present invention is used for preventing deterioration of sensitivity, or for improving the shape of the resist pattern and the stability of post exposure stability. The latent image is formed by the pattern-wise exposure of the resist layer; and the like, at least one compound selected from the group consisting of an organic carboxylic acid of any composition or an oxyacid of phosphorus or a derivative thereof may be further added ( E) (hereinafter also referred to as (E) component). 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. Pity oxyacids such as pity 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-n-butyl phosphate or diphenyl phosphate. Phosphonic acid derivatives such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and the like. -75- 200844101 Phosphonic acid (P h o s p h i n i c a c i d ) derivatives such as phosphinates such as phenylphosphinic acid. The component (E) may be used singly or in combination of two or more. The component (E) is preferably an organic carboxylic acid, particularly salicylic acid. The component (E) is generally used in an amount of from 1 to 5.0 parts by mass based on 100 parts by mass of the component (A). [(〇) component] 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, and a surfactant for improving coating properties and a dissolution inhibitor. , plasticizers, stabilizers, colorants, halo inhibitors, dyes, etc. [(S) component] The photoresist composition of the third aspect 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 can be used as long as it can dissolve the components to be used, and a suitable solution can be used. For example, one or two or more kinds of them can be appropriately selected from known solvents which are conventionally used as a reinforced chemical resist solvent. -76- 200844101 For example, lactones such as r-butyrolactone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-η-pentanone, methyl isoamyl ketone, and 2-heptanone; Polyols such as diol, diethylene glycol, propylene glycol, dipropylene glycol and derivatives thereof; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetic acid a compound having an ester bond such as an ester; a monoalkyl ether or a monophenyl group such as a monomethyl ether, a monoethyl ether, a monopropyl ether or a monobutyl ether of the above polyol or a compound having an ester bond; a derivative of a polyol such as an ether-bonded compound or the like (wherein, propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) is preferred); a ring such as dioxane Ethers; or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxypropyl Ester such as ethyl ester; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenylethyl ether, butylphenyl ether, B Benzene, diethylbenzene, pentylbenzene, isopropylbenzene, 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, it is preferred to use propylene glycol monomethyl ether acetate (PGME A), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), and r-butyrolactone. 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, it is in the range of 2:8 to 8:2. -77- 200844101 More specifically, when the polar solvent is ethyl lactate (E L ), 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 7 〇: 30 to 95: 5 〇, (S) component, using the above mixed solvent of PGMEA and PGME, and the mixture with y-butyrolactone. The solvent is preferred. 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 It is used in the range of % by mass, preferably 5 to 15% by mass. The photoresist composition of the present invention is suitably used as a photoresist composition for immersion exposure even in a method of forming a photoresist pattern containing an immersion exposure process, and good lithographic etching characteristics can be obtained. Further, in the method for forming a photoresist pattern containing a three-layer photoresist layer, the photoresist composition of the present invention is also suitably used as a positive photoresist composition for forming an upper photoresist film, and can be obtained well. The lithography etching characteristics. The above reasons are still unclear, but it is presumed that the acid generator (b 1 ) formed by the compound represented by the above formula (b 1 -5 ) used in the present invention is in the exposure wavelength band (especially the ArF excimer thunder). In the wavelength region of the shot, -78-200844101 can effectively suppress the absorption of light, and has an effect of having excellent solubility in an organic solvent (photoresist solvent) used for dissolving various components of the photoresist. Therefore, when the (B 1 ) component is added to the photoresist composition of the present invention, light absorption can be suppressed and the transparency of the photoresist composition can be improved. Further, the (B 1 ) component has a good dispersibility in the photoresist film, so that a more uniform distribution can be obtained in the photoresist film as compared with the conventional acid generator. Therefore, when an acid which causes the (B 1 ) component to be formed by exposure is used, it is presumed that a more uniform diffusion can be obtained in the photoresist film as compared with the case of using a conventional acid generator. For the above reasons, it is known that the photoresist composition of the present invention can be suitably used as a resist composition for immersion exposure even in a method for forming a photoresist pattern containing an immersion exposure process. Photolithography etching characteristics. Further, in the method for forming a photoresist pattern containing a three-layer photoresist layer, the photoresist composition of the present invention is also suitably used as a positive photoresist composition for forming an upper photoresist film, and can be obtained well. The lithography etching characteristics. Further, the photoresist composition of the present invention can be formed, for example, to have a good line width uniformity (LWR), a photoresist pattern shape (particularly a surface roughness of a photoresist pattern), and a mask error factor (mask error factor). MEF), exposure latitude (EL latitude) and other lithography characteristics of the lithography pattern, MEF is, under the same exposure, fixed spacing, change the mask size (line width and space) Width), how the size of the reticle pattern can be faithfully reproduced parameters, the closer the MEF is to its reticle weight -79- 200844101 the higher the present. The EL latitude is a parameter which varies with the amount of change in the amount of exposure, and the smaller the number, the smaller the amount of change. <<Method for Forming Photoresist Pattern>> Next, a method for forming a pattern of the fourth embodiment of the present invention will be described. The method for forming a photoresist pattern according to the present invention includes the step of forming a photoresist film on a substrate by using the photoresist composition according to the third embodiment of the present invention, and exposing the photoresist film to light. The step of developing the resist film to form a photoresist pattern. An example of a method for forming a photoresist pattern of the present invention, for example, a method for forming a photoresist pattern containing an immersion exposure (immersion η lithography) process, and a method for forming a three-layer photoresist layer The formation method of the photoresist pattern of the process. It will be explained in detail below. &lt;Formation method of photoresist pattern containing immersion exposure process&gt; First, a photoresist composition of a third embodiment of the present invention is formed on a substrate such as a germanium wafer (in this case, The photoresist composition for immersion exposure is coated with a spin coater or the like, and then subjected to post-bake (PAB) treatment to form a photoresist film. At this time, an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the photoresist composition to form a two-layer laminate. -80- 200844101 Also, a top coat film may be provided on the photoresist film. The top coat film is not particularly limited, and it can be used as usual for immersion exposure. For example, the protective film disclosed in the specification of International Publication No. 05/0 1 993 7 and International Publication No. 04/07493 7 contains -Q-NH-S02-R5 (wherein Q is a carbon number of 1 to 5) a main chain cyclic type resin in which a chain or a branched chain alkyl group, R5 is a fluorinated alkyl group, and -C0-0-R7 (wherein R7 is a fluorinated alkyl group) is dissolved in an organic solvent. A protective film or the like formed of the composition obtained by an alcohol solvent such as isobutanol. Here, the "main-chain-ring type resin" means that the constituent unit constituting the resin has a single-ring or polycyclic ring structure, and at least one, preferably two or more rings on the ring structure. The carbon atom is a constituent unit constituting the main chain (hereinafter referred to as "main chain cyclic type constituent unit"). The main chain cyclic type constituent unit is, for example, a constituent unit derived from a polycyclic olefin (polycyclic olefin). The constituent unit of the dicarboxylic acid anhydride, etc., wherein the main chain has a constituent unit derived from a polycycloolefin (polycyclic olefin, preferably norbornene, etc.) is preferably provided on the photoresist film. The top coat film is preferably one which is soluble in an alkali developer. The steps up to now can be carried out by a known method, the operation conditions and the like, in order to match the composition of the resist composition for immersion exposure used or It is preferable to appropriately set the characteristics, etc. In the formation method of the photoresist pattern containing the immersion exposure process, secondly, the photoresist film obtained by the above method is selectively immersed through the desired reticle pattern. Exposure (Liquid I Mmtion Lithography) -81 - 200844101 In this case, the photoresist can be filled with a refractive index larger than the refractive index of air between the photoresist film (or the top coating film) and the lens at the lowest position of the exposure device. Infiltration of the medium) and exposure in this state (immersion exposure) ° The wavelength used for the exposure is not particularly limited, and radiation using an ArF excimer laser, a KrF excimer laser, or an F2 laser can be used. The positive-type photoresist composition of the present invention is effective for KrF or ArF excimer lasers, particularly ArF excimer lasers. As described above, in the formation method of the present invention, when exposed, light is applied. The resist film (or top coat film) and the lowermost position of the exposure device and the lens are filled with the immersion medium, and exposure (immersion exposure) is performed in this state. At this time, the immersion medium uses a refractive index higher than air. It is preferable that the refractive index is large and is smaller than the solvent having the refractive index of the photoresist film formed by the positive-type resist composition for immersion exposure. When the refractive index of the solvent is within the above range, A solvent having a refractive index greater than that of air and smaller than the refractive index of the photoresist film, for example, water, a fluorine-based inert liquid, an oxime-based solvent, etc. Specific examples of the fluorine-based inert liquid such as c3HCl2F5, C4F9OCH3, C : 4P9 〇C2H5, CsHsF7 and other fluorine-based compounds as the main component of the liquid, and the boiling point of 70 to 18 (rc is better, 8 〇 to i6 (rc is better. Gas-based inert liquid, boiling point in In the case of the above-mentioned range, the medium used for the wetting type can be removed in a simple manner after the end of the exposure, and it is preferred that the inert gas of the inert gas is 'in particular, the hydrogen atom in the alkyl group is all fluorine-82- The perfluoroparaffin compound obtained by substituting the substituting 200844101 is preferred. The perfluorophthalic compound, specifically, for example, a perfluoroalkyl ether compound or a perfluoroalkylamine compound. Further, specifically, the perfluoroalkyl ether compound is, for example, perfluoro(2-butyl-tetrahydrofuran) (boiling point: 102 ° C), and the perfluoroalkylamine compound, for example, perfluorotributylamine (boiling point 1) 741) and so on. The photoresist composition of the present invention is not easily susceptible to the adverse effects of water, and has a refractive index greater than that of air, from the viewpoints of excellent sensitivity and shape of the resist pattern. The rate of solvent is best with water. Moreover, water is also preferable in terms of cost, safety, environmental and extensive use. Next, after the completion of the immersion exposure step, post exposure bake (PEB) is carried out, followed by development treatment using an alkali developer formed of an alkaline aqueous solution. Subsequently, it is preferred to use pure water for water washing. The water washing, for example, can be carried out by spraying or spraying the substrate on the surface of the substrate in a rotating state. The developing solution on the substrate and the positive-type photoresist composition for immersion exposure dissolved in the developing solution are washed away. Subsequently, drying is carried out, and a photoresist film (coating film of the photoresist composition for immersion exposure) is patterned in accordance with the shape of the mask pattern to obtain a photoresist pattern. &lt;Formation method of photoresist pattern containing a process for forming a three-layer photoresist layer&gt; Formation method of a photoresist pattern containing a process for forming a three-layer photoresist layer is formed on a substrate to be dried The uranium is engraved with an underlying organic film, and a material containing Si atoms is coated and heated on the underlying organic film to form an intermediate layer of -83-200844101, and the third embodiment of the present invention is used on the intermediate layer. The photoresist composition forms an upper photoresist film to form a three-layer photoresist layer, and a step of exposing the upper photoresist film to develop the upper photoresist film to form a photoresist pattern. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the following examples. (Example 1) &lt;Synthesis of Compound (b 1 - 5 1 )&gt; [Chemical 4 3]

1.99 g of phosphorus pentoxide was added to 12 m 2 of methanesulfonic acid, and 5.86 g of 2,6-dimethylphenol was added to the solution. After the solution was cooled to 20 ° C or lower in a water bath, 8.0 1 g of stilbene thiophene oxide was slowly added. Thereafter, it was taken out of the water, and the reaction was carried out at room temperature for 14 hours. After -84-200844101, a mixed solution of I80.3 g of water and 180.3 g of methylene chloride was cooled to 10 ° C or lower, and the reaction solution was gradually dropped thereto at 25 ° C or lower. The reaction solution was separated, and the aqueous phase was taken out. Further, 1 3 · 5 4 g of potassium hexafluorobutanesulfonate was added thereto, and the mixture was stirred at room temperature for 1.5 hours. Thereafter, 3 14.3 g of dichloromethane was added and stirred, and the organic phase was separated. The organic phase was washed with 11 8.2 g of pure water until neutral, and the organic phase was separated, and the organic phase was taken out. In the organic phase taken out, hexane (3 60·6 g) was added as a poor solvent to give crystals. The crystals were dried under reduced pressure at 40 ° C to give 12.0 g of the desired compound (bl-51). The compound was analyzed by 1H_NMR and 19F-NMR. iH-NMR (DMSO-d6, 600 MHz): δ (ppm) = 9.59 (br s, 1H, Hg), 8.49 (d, 2H, Ha), 8.25 (d, 2H, Hd), 7.95 (t, 2H? He), 7.74 ( t, 2H, Hb ), 7.20 ( s, 2H, He), 2.14 ( s, 6H, Hf). 19F-NMR (Acetone-d6, 3 76 MHz): δ (ppm) = 8 1.2, 114.6, 121.5, 126.0 ° From the above results, it was confirmed that the compound had the structure shown below. -85- 200844101 【化4 4】

&lt;Evaluation of Solubility&gt; The solubility of the above compound (b 1 - 5 1 ) and bis(1-sabutane sulfonate ((B) _2 ) was evaluated. The ethyl ether acetate, the propylene glycol monomethyl ether (PGME) solution, and the emulsion were adjusted in such a manner as to change the concentration. After the adjustment, the acid generator was completely dissolved, and the concentration thereof was measured. The results are shown in Table 1. The above compound (b 1 - 5 1 ) in the present invention is equivalent to bis(nonyl-naphthyl)sulfonate ((B)-2) for the general light and the solubility of EL. It is excellent. The basis of the phenyl hydrazine hexafluoride method (PGMEA) solution acid ethyl ester (EL) solution is stirred to make each of the first embodiment: PGME phenyl sulfonium hexafluorobutane - 86- 200844101 [Table 1] Example 1 (bl-51) (B)-2 Solubility to PGME (mass % 丄 10 5 solubility in EL (% by mass) 5 5 (Example 2, Comparative Example 1) &lt;Resin component (A) &gt; The polymer (A)-1 of the component (A) used in Example 2 and Comparative Example 1 is as follows. Further, the following polymer (A) The mass average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of -l are recorded therein. The mass average molecular weight (Mw) and the degree of dispersion (Mw/Mn) are determined by gel permeation chromatography (GPC). Further, the composition ratio is calculated by carbon NMR. In the chemical formula, the number attached to the lower right side of the constituent unit is the ratio (mol%) of each constituent unit in the polymer. 】

(A) — 1 -87- 200844101 (Mw : 1 0000, Mw/Mn : 2.0; using a monomer derived from each constituent unit, and synthesizing it by a known polymerization method). &lt;Preparation of positive-type photoresist composition solution&gt; Each component shown in Table 2 was mixed and dissolved to prepare a positive-type photoresist composition solution. Also, the "-" in the table means no addition. [Table 2] (A) (B) (D) (E) (s) Example 2 (A)-l [1〇〇] (B)-l [12.0] (D)-l [0.54] (E )-l [1.32] (S)-l [10] (S)-2 [2200] Comparative Example 1 (A)-l [1〇〇] (B)-2 (13.0) (D)-l [0.54 ] (E)_l [1.32] (S)-l [10] (S)-2 [2200] Each of the abbreviations in Table 2 has the following meaning. Also, the number in [] is the amount of addition (parts by mass) (B) -1: an acid generator (compound of Example 1) represented by the following chemical formula (bl-51). -88 - 200844101 [Chem. 4 6]

OH

C4F9SO3 (b 1 - 5 1) (B ) -2 : bis(1-naphthyl)phenyl mirror nonafluorobutane sulfonate. (D) ·1 : Tri-n-pentylamine. (Ε ) - 1 : Salicylic acid. (S ) -1 : r - butyrolactone. (S ) -2 : PGMEA/PGME = 6/4 (mass ratio) mixed solvent. &lt;Evaluation of lithographic etching characteristics&gt; A photoresist pattern was formed using the obtained positive-type photoresist composition solution, and the following lithography characteristics were evaluated. [Formation of the photoresist pattern] The organic anti-reflection film composition "ARC-29A" (manufactured by Privah Technology Co., Ltd.) was applied to a wafer of 8 inches on a wafer by a spin coater. The hot plate was baked at 2 0 5 ° C for 60 seconds, and dry-89-200844101 was dried to form an organic anti-reflection film having a thickness of 82 nm. Subsequently, the positive-type photoresist composition solution obtained above was separately applied to the anti-reflection film by using a spin coater, and the temperature was as shown in Table 3 on the hot platen under the conditions of 60 seconds. After prebaking (PAB) treatment, after drying, a photoresist film having a film thickness of 120 nm was formed. Next, using an ArF exposure apparatus NSR-S 3 02 (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 0.60, 2/3 wheel illumination), ArF excimer laser (1 3 3 nm) is masked by a mask pattern. Perform selective irradiation. Subsequently, the post-exposure heating (PEB) treatment was carried out under the conditions of 60 seconds at each temperature shown in Table 3, and at 23 ° C, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) was used for 30 seconds. The development was carried out under the conditions, and then washed with pure water for 30 seconds, and after vibration drying, a line and space (1:1) photoresist pattern (L/S pattern) was formed and obtained. The most appropriate exposure amount (sensitivity: Εορ ' mJ/cm 2 ) of the L/S pattern having a line width of 120 run and a pitch of 240 nm was formed. [Evaluation of MEF (mask error factor;] viask Error Factor] In the above ΕΟΡ, the L/S pattern with a line width of 130 nm and a pitch of 260 nm is used as the target mask pattern, and the line width is 12 〇 nm. The L/S pattern with the pitch of 2 60 nm is used as the reticle pattern of the target to form the L/S pattern, and the MEF 求 is obtained according to the following calculation formula. MEF- | CD13〇-CDi2〇I / I MD13〇-MDi2〇| -90- 200844101 In the above formula, CD13G and CD12〇 are formed by using a mask pattern with a line width of 130 nm and 120 nm as targets, respectively. The actual line width (nm) of the S pattern. M D 13 ο, M D 1 2 ο respectively the reticle pattern as the line width (nm) of the standard, MDi3 〇 = 130' MDi2 〇 two 120. The closer the MEF is to one, the more faithfully the reticle pattern can be reflected to form a photoresist pattern. [Exposure latitude (EL latitude) evaluation] Under the change of the exposure amount, an L/S pattern having a line width of 120 nm and a pitch of 240 nm as a target size was formed. At this time, the exposure amount of the L/S (l:1) pattern of the size (i.e., 114 to 126 nm) in the range of ±5% of the target size (12 〇 nm) was determined, and then the EL was calculated by the following calculation formula. Tolerance (unit: %). The results are shown in Table 2. EL latitude (%) = ( | E1-E2 | /Εορ) χΙΟΟ

El : Exposure amount ( mJ/cm 2 ) at the time of forming the L/S pattern of line width 126 nm ° E2 : Exposure amount ( mJ/cm 2 ) at the time of forming the L/S pattern of line width 1 14 nm 〇 where 'exposure The larger the width of the wide valley, the smaller the change in the size of the pattern caused by the change in the amount of exposure. The results are shown in Table 3. -91 - 200844101 [Table 3] Example 2 Comparative Example 1 PAB Temperature (°C) 110 1 10 PEB Temperature (t:) 110 110 Eop (mJ/cm2) 63.2 41.6 MEF 2.16 2.25 EL Tolerance (%) 7.56 6.75 As is apparent from the results of Table 3, in comparison with Comparative Example 1 of Example 2 of the present invention, it was confirmed that a more excellent photoresist pattern of MEF and EL latitude can be obtained. From the above results, it was confirmed that the photoresist composition of Example 2 of the present invention was able to obtain good lithographic characteristics. The present invention provides a novel compound suitable as an acid generator for a photoresist composition, an acid generator formed from the compound, and a photoresist composition containing the acid generator, and a photoresist having the photoresist composition. The method of forming the pattern. Therefore, the present invention is extremely useful in the industry. -92-

Claims (1)

200844101 X. Patent application scope 1 · A compound of the following formula (b丨_ 5 ) [Chemical 1] Wherein R, R42 and R43 are each independently alkyl, ethylidene, alkoxy, residue or hydroxyalkyl; n〇 is an integer of from 1 to 3, and is an integer of from 0 to 3 'η2 and Each of ns is independently an integer of 〇~3, and χ_ is an anion. 2. The compound of claim 1, wherein the aforementioned X - is a halogenated alkylsulfonic acid ion. 3. An acid generator characterized by a compound of the first item of the patent application. 4 . A photoresist composition which is a photoresist composition containing a substrate component (A) which changes alkali solubility based on an acid action and an acid generator component (B) which generates an acid by exposure, and is characterized by The acid generator component (B) is an acid generator (B 1 ) containing a compound represented by the following formula (bl-5), -93- 200844101. Wherein R41, R42 and R43 are each independently an alkyl group, an ethyl group, an alkoxy group, a carboxyl group or a hydroxyalkyl group; nG is an integer of 1 to 3, and is an integer of 0 to 3, 12 and 1! 3 are each independently an integer of 〇~3, and X is an anion. 5. The photoresist composition according to item 4 of the patent application, wherein the aforementioned X' is a halogenated alkylsulfonic acid ion. 6. The photoresist composition of claim 4, wherein the substrate component (A) is a substrate component which increases alkali solubility based on an acid action. 7. The photoresist composition according to claim 6, wherein the substrate component (A) is a resin component (A1) which is a constituent unit derived from an acrylate having an acid-dissociable dissolution inhibiting group. (ai). 8. The photoresist composition according to claim 7, wherein the substrate component (A) contains a constituent unit (a2) derived from an acrylate having a cyclic group containing a lactone. 9. The photoresist composition according to claim 7, wherein the substrate component (A) of the above -94-200844101 contains a constituent unit (a3) derived from an acrylate having a polar group-containing aliphatic hydrocarbon group. 1 〇 A photoresist composition according to item 4 of the patent application, which contains a nitrogen-containing organic compound (D). 11. A method of forming a photoresist pattern, comprising the steps of forming a photoresist film on a substrate using the photoresist composition of claim 4, and exposing the photoresist film to The step of developing the photoresist film to form a photoresist pattern. -95- 200844101 VII. Designated representative map (1) The designated representative figure of this case is: None (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 best display invention. Chemical formula of the feature: [Chemical 1]