TW200928579A - Resist composition, method of forming resist pattern, novel compound and method of producing the same, and acid generator - Google Patents

Abstract

A compound represented by formula (I); and a compound represented by formula (b1-1): [Chemical Formula 1] wherein X represents -O-, -S-, -O-R3-or-S-R4-, wherein each of R3 and R4 independently represents an alkylene group of 1 to 5 carbon atoms; R2 represents an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, a halogenated alkyl group of 1 to 6 carbon atoms, a halogen atom, a hydroxyalkyl group of 1 to 6 carbon atoms, a hydroxyl group or a cyano group; a represents an integer of 0 to 2; Q1 represents an alkyene group of 1 to 12 carbon atoms or a single bond; Y1 represents an alkylene group of 1 to 4carbon atoms or a fluorinated alkylene group; M+ represents an alkali metal ion; and A+ represents an organic cation.

Description

200928579 IX. OBJECT OF THE INVENTION [Technical Field] The present invention relates to a photoresist composition containing a novel novel, which is useful as an acid generator, a photoresist pattern, a method for forming a photoresist pattern, and a stomach and stomach. A useful compound of a compound precursor and a method for producing the same, and an acid generator formed from the compound. > This case is based on the special request φ 200 7— 23 70 54 applied for in Japan on September 12, 2007, and the Japanese wish to apply for it in Japan on October 23, 2007. 2756 5 5, January 2008 The priority is claimed on the basis of the Japanese Patent Application No. 2008-1423, the entire disclosure of which is hereby incorporated by reference. [Prior Art] In the lithography technique, for example, a photoresist film obtained by using a photoresist material is formed on a substrate, and for the above-mentioned photoresist film, radiation such as light or electron lines is formed by forming a mask of a specific pattern. The selective exposure is carried out, and the development process is carried out to form the photoresist film into a photoresist pattern having a specific shape. The portion of the exposure which is changed to have a characteristic of being dissolved in the developer is referred to as a positive type, and the portion of the photoresist which is exposed to have a property of not being dissolved in the developer is referred to as a negative type. In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, with the advancement of the lithography technique, the pattern has been rapidly refined. The method of miniaturization is generally carried out in such a manner that the exposure light source is made short-wavelength -6 - 200928579. Specifically, ultraviolet rays which are represented by g-line and i-line are conventionally used. However, KrF excimer lasers or ArF excimer lasers are now being used for mass production of semiconductor components. Further, F2 excimer lasers, electron beams, EUV (extreme 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,

V reproduces the lithographic etching characteristics such as resolution of fine-size patterns. The photoresist material which satisfies the requirements of the above-mentioned requirements generally has a chemically amplified photoresist which contains a base resin which changes the solubility of the alkali developing solution based on an acid action, and an acid generator which generates an acid by exposure. For example, a positive type chemically amplified photoresist, the base resin is a resin containing an acid-based effect to increase solubility in an alkali developer, and an acid generator is used to form an acid by exposure when a photoresist pattern is formed. The agent generates an acid, and the exposed portion is made soluble to the alkali developer. So far, the base resin of the chemically amplified photoresist is protected by a polyhydroxystyrene (〇PHS) having a high transparency to a KrF excimer laser (248 nm) or a hydroxyl group thereof which is inhibited by an acid-dissociable dissolution inhibiting group. Resin (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 chemical growth of the PHS-based resin as a base resin component is used. Type resist, for example, for the process using 193 nm light, there are still some disadvantages such as low resolution. Therefore, at present, the base resin for the photoresist used in ArF excimer laser lithography is to Since 1 93 nm has excellent transparency, a resin having a structural unit derived from (meth) acrylate (acrylic resin 200928579) is generally used in the main chain. In the case of a positive type, the above-mentioned resin is mainly used. a structural unit derived from a (meth) acrylate of an aliphatic polycyclic group-based tertiary alkyl ester type acid dissociable dissolution inhibiting group, for example, mainly containing 2-alkyl-2-adamantyl (meth)acrylic acid A tree of a structural unit derived from an ester or the like (for example, Patent Document 1). Further, "(meth)acrylic acid ester" refers to propylene having a hydrogen atom bonded to the α-position. Ester, of methyl acrylate, methyl group, or one of φ meaning both bonded to the α position. "(Meth)acrylate" means an acrylate in which a hydrogen atom is bonded to a terminal, and one or both of a methyl methacrylate bonded to the α-position. "(Meth)acrylic acid" means an acrylic acid having a hydrogen atom bonded to the α-position, and one or both of the methacrylic acid having a methyl group bonded to the α-position. Further, various acid-generating agents used in chemically amplified photoresists have been proposed, and key acid generators such as iodine salt or phosphonium salt are known. [Patent Document 1] JP-A-2003-241385 SUMMARY OF THE INVENTION - The anion portion of the above-mentioned key salt acid generator is generally a perfluoroalkylsulfonate ion. The perfluoroalkyl chain of the anion is generally preferably as long as it inhibits the diffusion of acid after exposure. However, since the perfluoroalkyl chain having a carbon number of 6 to 10 is difficult to decompose, it is safe to be treated in consideration of the accumulation of the living body, and a nonafluorobutyrene sulfonate ion or the like is often used. Therefore, there is a need for a more suitable novel compound for the acid generator for the photoresist composition. -8 - 200928579 The present invention is a useful novel compound for use as an acid generator for a photoresist composition, a useful compound as a precursor of the compound, and a method for producing the same, in view of the above circumstances, An acid generator, a photoresist composition, and a photoresist pattern forming method are intended. In order to achieve the above object, the present invention adopts the following constitution. That is, the first aspect of the present invention is a photoresist composition which is a substrate component (A) which contains a change in solubility to an alkali developer via an action of an acid, and an acid which is generated by exposure. The photoresist composition of the acid generator component (B), characterized in that the acid generator component (B) is an acid generator (B 1 ) formed by a compound represented by the following formula (bl-Ι). ,

【化1】

―, R 3 and R 4 are each independently an alkylene group having 1 to 5 carbon atoms; R 2 is an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a halogenated alkyl group having 1 to 6 carbon atoms; a halogen atom, a hydroxyalkyl group having a carbon number of 1 to 6, a hydroxyl group or a cyano group; a is an integer of 0 to 2; Q1 is an alkylene group or a single bond having a carbon number of 1 to 12; and Y1 is a carbon number of 1 to 4 Alkyl or fluorinated alkyl; A + is an organic cation]. -9- 200928579 A second aspect of the present invention is a method for forming a photoresist pattern, comprising the step of forming a photoresist film on a support using the photoresist composition of the first aspect. a step of exposing the photoresist film and a step of alkali developing the photoresist film to form a photoresist pattern. The third aspect of the present invention is a compound represented by the following formula (I) (hereinafter, also referred to as compound (I)), ❹ ❹ [Chemical 2] 0

(1) [wherein, X is -0-, an S-, a 0-R3- or -S_R4_' R3 and R4 are each independently an alkylene group having 1 to 5 carbon atoms; r2 is a carbon number of 1 to ό The alkyl group, the carbon number 丨~6 alkoxy group, the carbon number] 〜6 of the dentate group, the halogen atom, the carbon number 丨~6 hydroxyalkyl group, the hydroxyl group or the cyano group; a is an integer of 〇~2 ; Qi is an alkyl or single bond having a carbon number of 1-4 to 12; ... is an alkyl or fluorinated alkyl group having a carbon number of 1 to 4; and M + is an alkali metal ion. The fourth aspect of the present invention is a method for producing a compound characterized by 'comprising a compound represented by the following formula (I _3) (] _ 3) ' with the following formula (i-4) The method for producing a compound obtained by the step of dehydrating condensation of the compound (I-*) represented by the following formula (I) (hereinafter, also referred to as the production of the compound (I)) method). -10- 200928579 【化3】 Ο II , _ +

HO—C—Y1—SO3 M

O

(1) ❹ [wherein, x is a 〇-, a s-, _〇-R '-, R3 and R4 are independent carbon numbers 1 to 5, the number of extensions 1 to 6 alkyl, carbon number 1 Alkoxy group of 1-6, carbon number alkyl group, halogen atom, hydroxyalkyl group having 1 to 6 carbon atoms, xiang: an integer of 0 to 2; Q1 is an alkyl group having 1 to 12 carbon atoms or a carbon number of 1~ 4 alkylene or fluorinated alkyl; M + is alkali gold. The fifth aspect of the invention is a compound F represented by the following formula, also known as compound (B 1 )) -or-S - R4 group; R2 is a halogenated 1 or a cyano group of carbon 1 to 6; a single bond; Y1 is a genus ion). (b 1 - 1 ) -11 - 200928579 [Chemical 4]

[wherein, X is a 0-, an S-, a 0-R3- or -S-R4®-'R3 and R4 are each independently an alkylene group having 1 to 5 carbon atoms; R2 is a carbon number 1~ An alkyl group of 6 , an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyalkyl group having 1 to 6 carbon atoms, a hydroxyl group or a cyano group; a is an integer of 〇 2 ; Q1 is an alkylene group or a single bond having a carbon number of 1-4 to 12: Y1 is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4; and A + is an organic cation. The sixth aspect of the invention is an acid generator which is formed by the compound (B 1 ) of the third aspect described above. In the scope of the present specification and the patent application, "aliphatic" is a relative complication with respect to aromatics, and is defined as a group or a compound having no aromaticity. The "alkyl group" is a linear, branched, and cyclic monovalent saturated hydrocarbon group, unless otherwise specified. The "alkylene group" is a compound containing a linear, branched, and cyclic divalent saturated hydrocarbon group, unless otherwise specified. The "low-grade yard base" is a hospital base with a carbon number of 1 to 5. "Structural unit" means the unit of monomer (monomer unit) constituting the resin component (polymer). - 12- 200928579 "Exposure" is a tribute to the full illumination of radiation. [Effects of the Invention] The present invention provides a novel compound which is used as an acid generator for a photoresist composition, a useful compound as a precursor of the compound, a method for producing the same, an acid generator, and a photoresist composition. The method of forming the object and the photoresist pattern.最佳 [Best Mode for Carrying Out the Invention] "Compound (I)" The compound (I) of the present invention is represented by the above formula (I). In the formula (I), X is -〇-, -S-, -O-R3- or -S-R4- 〇 R3 and R4 are each independently an alkylene group having 1 to 5 carbon atoms. The alkylene group is preferably a linear chain or a branched chain, preferably having a carbon number of 1 to 3 and preferably 1 to 2 φ. X is best with _〇. *' The alkyl group in R2 is preferably a linear or branched alkyl group. Specifically, for example, methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl and the like. Among them, methyl or ethyl is preferred, and methyl is preferred. The alkoxy group in R2, for example, in the above R2, is a group derived from an alkyl group-bonded oxygen atom (_〇-) exemplified for the alkyl group. The fang atom in R2, for example, a fluorine atom, a chlorine atom, a bromine atom, an -13-200928579 iodine atom or the like, is preferably a fluorine atom. The halogenated alkyl group in R2, for example, in the above R2, a part or all of a hydrogen atom of the alkyl group exemplified as the alkyl group is substituted by the above halogen atom. The halogenated alkyl group is preferably a fluorinated alkyl group, and particularly a perfluoroalkyl group is preferably a hydroxyalkyl group in R2. For example, at least one of the hydrogen atoms of the alkyl group exemplified as the alkyl group in the above R2 is a group substituted by a hydroxyl group. φ a can be any of 0 to 2, and 0 is the best. In the case where a is 2, the plural R2 may be the same or different, and the alkyl group of Q1 may be linear or branched. The carbon number of the alkyl group is preferably from 1 to 5, more preferably from 1 to 3. The alkylene group, specifically, for example, methyl [CH2-]; -CH(CH3)-, one CH(CH2CH3)-, one C(CH3)2-, -C(CH3)(CH2CH3)- , a C(CH3)(CH2CH2CH3)-, 〇-C(CH2CH3)2-, etc. alkyl-methyl group; an extended ethyl group [-CH2CH2-]: a CH(CH3)CH2-, -CH(CH3)CH ( CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, , -CH(CH2CH3)CH2-, etc. alkyl-extended ethyl; tri-methyl (n-extended propyl)[-CH2CH2CH2- -CH(CH3)CH2CH2-'-CH2CH(CH3)CH2-etc. Alkyltri-methyl; tetramethyl-[CH-CH2CH2CH2CH2-]; -CH(CH3)CH2CH2CH2 -, -CH2CH(CH3)CH2CH2 —etc. Alkyltetramethyl; pentamethyl; a CH2CH2CH2CH2CH2-—etc. -14- 200928579 Q1 is preferably a methyl group, an ethyl group, a η-propyl group or a single bond, especially a single bond. Υ1 is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4. Υ1 is a cf2-, - cf2cf2 -, - cf2cf2cf2-, _ - CF(CF3)CF2 -, -CF(CF2CF3)-, a C(CF3)2-, -CF2CF2CF2CF2 -, a CF(CF3)CF2CF2 -,

V -CF2CF(CF3)CF2 -, - CF(CF3)CF(CF3)-, ❹-C(CF3)2CF2, -CF(CF2CF3)CF2 -, -CF(CF2CF2CF3)-, one C(CF3)(CF2CF3 ) - ; - CHF _, -CH2CF2 -, -CH2CH2CF2-, - ch2cf2cf2 -, -CH(CF3)CH2-, -CH(CF2CF3) -, -C(CH3)(CF3) - ' - CH2CH2CH2CF2-, -CH2CH2CF2CF2 -, a ch(cf3)ch2ch2-, -CH2CH(CF3)CH2-, -CH(CF3)CH(CF3)-, -C(CF3)2CH2-; -CH2 - ' - CH2CH2 - ' - ch2ch2ch2 -, one Ch(ch3)ch2-, one ch(ch2ch3)-, one c(ch3)2-, ❹-CH2CH2CH2CH2-, -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, one CH(CH3)CH( CH3)-, *-C(CH3)2CH2-, one CH(CH2CH3)CH2-, ?-CH(CH2CH2CH3)-, one C(CH3)(CH2CH3)-, and the like. Y1 is preferably a fluorinated alkyl group, and particularly preferably a fluorinated alkyl group obtained by fluorinating a carbon atom bonded to a sulfur atom adjacent thereto. The fluorinated alkyl groups, such as a CF2-, -CF2CF2-, -CF2CF2CF2-, -CF(CF3)CF2-, a CF2CF2CF2CF2-, -CF(CF3)CF2CF2, -CF2CF(CF3)CF2-, -CF (CF3)CF(CF3)-, 200928579—c(cf3)2cf2-, -CF(CF2CF3)CF2-; -CH2CF2-, -CH2CH2CF2-, -CH2CF2CF2-; - CH2CH2CH2CF2-, -ch2ch2cf2cf2-, one ch2cf2cf2cf2-, etc. . Further, -CF2-, -CF2CF2-, -CF2CF2CF2-, or -CH2CF2CF2- is preferred, and a CF2-, -CF2CF2- or -CF2CF2CF2- is more preferred, and -CF2- is preferred. ❹ M + alkali metal ions, such as sodium ions, lithium ions, potassium ions, etc., preferably sodium or lithium ions. In the present invention, the compound (I) is preferably a compound represented by the following formula (I-11). 【化5】

/--° Ο (1-11) [wherein, X, R2, a, and M + are the same as X, R2, a, and M + in the above formula (I), and b is an integer of 0 to 5, c is an integer of 1 to 3, and R3 and R4 are each independently a fluorine atom or a fluorinated alkyl group]. b is preferably 0 or 1, and 〇 is the best. c is best at 1. The fluorinated alkyl group of R3 and R4 is preferably a linear or branched alkyl group. Further, the fluorinated alkyl group is preferably a perfluoroalkyl group. The carbon number of the fluorinated alkyl group is preferably -16 to 200928579 1 to 5, and most preferably 1 is used. R and R are preferably the same as the gas atom. Compound (I) is a novel compound. The compound (I) can be used as a ruthenium precursor in the production of the compound (B1) described later. (Manufacturing Method of the Compound (I)) The method for producing the compound (I) of the present invention is not particularly limited. Preferably, for example, a compound represented by the following formula (I-3) is contained (I-3) The method of performing the step of dehydrating condensation with the compound (I-4) represented by the following formula (I-4) to obtain the compound (I) is preferred. 【化6】

R2, a, Qi, γ1, and M+ in the formulas (I-3) and (I-4) are the same as those of R_2, a, Q1, Y1, and M+ in the above formula (I). The compound (I-3) and the compound (1-4) may each be a commercially available product or a synthetic one. For example, the compound (I-3) is not particularly limited, and the compound (I-1) represented by the following formula (1 to 1) can be subjected to alkali treatment to obtain the following formula (I-1 to 200928579). — 2) The step of the compound (I-2) represented by the step (also referred to as the step (i)), and the step of preparing the compound (I-3) by heating the above compound (I-2) is also referred to as Step (ii)) is synthesized. [Chemical 7] Ο R1—O—C—Y1—S02F 0 Μ ΟC—Y1—SO; Μ+ ...d—2) [wherein R1 is an alkyl group having 1 to 5 carbon atoms; Y], M + 式 'ΝΤ in the formula (I) is the same content. In the step (i), the compound (I-1) can be carried out by a base treatment in the commercially available step (i), for example, by heating the compound in the presence of a base, and the specific example (I - 1) It is dissolved in a solvent such as water or tetrahydrofuran, and a base is added thereto, followed by heating or the like. The amount of the base to be used, for example, sodium hydroxide, potassium hydroxide or lithium hydroxide is preferably 1 mol% based on the compound (1_1), and more preferably 2 to 4 mol. The heating temperature is preferably about 20 to 120 ° C, and more preferably 50 to right. The heating time varies depending on the heating temperature, etc. 0.5 to 1 2 hours is preferred, and 1 to 5 hours is more preferred. After the aforementioned alkali treatment, neutralization can be carried out. Neutralization can be added to the reaction solution after adding hydrochloric acid, sulfuric acid, P-toluenesulfon-18- (hereinafter) to the acid (hereinafter, the above product. (I - 1), for example, will be in the solution, The reaction is carried out at a temperature of 1 to 5 / 100 ° C to the left, usually in the form of the above-mentioned acid such as alkali acid 200928579. In this case, the neutralization is preferably carried out so that the pH of the reaction liquid after the acid addition is 6 to 8. After completion of the reaction, the compound (I-2) in the reaction mixture may be isolated or purified. In the separation and purification, it may be carried out by a conventionally known method. For example, concentration, solvent extraction, distillation, and crystallization may be carried out. Any one of the methods such as recrystallization and chromatography may be used singly or in combination of two or more. 0 Step (ii), for example, the compound (1-2) may be dissolved in acetonitrile or methyl ethyl ketone. In the solvent, the acid is further added and then heated. In the step (Π), the acid is an acid having a higher acid strength than the compound (I-3). The acid, for example, p-toluenesulfonic acid, sulfuric acid The amount of citric acid used, such as hydrochloric acid, relative to the compound (丨2) 1 Moule, 0.5 to 3 Mo is better 'to 〗 ~ 2 Molar is better. 〇 Heating temperature 'is preferably around 20~150 °c, to 50~120. (: Left and right is better The heating time varies depending on the heating temperature, etc., and is usually preferably -5 Torr to 5 hours, and more preferably ～5 hours. After the reaction, the compound (1_3) in the reaction solution can be used. Isolation and purification may be carried out. Isolation and purification may be carried out by a conventionally known method, and for example, any methods such as concentration, solvent extraction, distillation, crystallization, recrystallization, and chromatography may be used, either alone or in combination. The above combination is used. The dehydration condensation reaction of the compound (I-3) with the compound (I-4), for example, 'the compound 3' and the compound (I-4) can be dissolved in the di-19-200928579 ethyl chloride, benzene, An aprotic organic solvent such as toluene, ethylbenzene, chlorobenzene, acetonitrile or N,N-methylformamide, which is applied by heating. In the above dehydration condensation reaction, the organic solvent, especially the xylene When an aromatic organic solvent such as chlorobenzene is used, the compound (I) is available. The yield, purity, etc. are preferred. The reaction temperature of the dehydration condensation reaction is from 20 ° C to 200 ° C left, preferably 5 (about TC to 150 ° C. The reaction time depends on the compound) and the compound ( I- 4) is preferably 1 to 30 hours, more preferably 3 to 30 hours, more preferably 3 to 30 hours. In the dehydration condensation reaction, the amount of the compound (1_3) is particularly limited. Usually, it is preferably about 0.2 to 3 moles per mole of the compound (I - 4 ), and about 0.5 to 2 moles is preferably about 0.75 to 1.5 moles. The dehydration condensation reaction can be carried out in the presence of an acid catalyst, for example, an organic acid such as P-toluenesulfonic acid, or the like, or an inorganic acid such as sulfuric acid, which can be used alone or in combination. Also. In the dehydration condensation reaction, the amount of the acid catalyst used may be, as long as it is equivalent to the amount of the solvent, and is usually about 0.001 to 5 moles per mole of the catalyst. The dehydration condensation reaction can be carried out using a Dean-Stark apparatus. This can shorten the reaction time. In addition, at the time of dehydration and condensation reaction, it is better to use 1,1'-carbonyl-dimethyl dimethyl to improve the practical use of toluene (1 to 3 is different, and it is not used well.) Catalyst content (I dehydration with the base diim-20- 200928579 hydrazine, N, N, dicyclohexylcarbodiimide and other dehydrating agents. In the case of using a dehydrating agent, its use relative to the compound (I - 4) 1 mol, usually about 0.2 to 5 m. It is preferably about 0.5 to 3 m. The structure of the compound obtained by the above method can be used - nuclear magnetic resonance (NMR) spectroscopy, 13C- The NMR spectrum method '19F-NMR chart ♦ spectrum method, infrared absorption (IR) pattern method, mass analysis (MS) method, φ elemental analysis method, X-ray crystal diffraction method and other general organic analysis methods are confirmed. B 1 ) The compound (B1) of the present invention is represented by the above formula (bl-1). In the formula (bl-1), X, R2, a, Q1, and Y1 are respectively the above formula (I). X, R2, a, Q1, and Y1 are the same contents. 有机 A + organic cation is not particularly limited, and may be appropriately A cation portion which is conventionally known as an iron salt acid generator is used. Specifically, the following general formula (b, 1), (b, - 2), (b1 - 5) or (b-6) The cation part indicated. [Chemical 8] R1"

[wherein 'R1'' to R3", R5" and R6" each independently represent an aryl group or a -21 - 28,928,579 alkyl group; in R1" to R3", any two of them may be bonded to each other and to the sulfur in the formula The atoms may form a ring together; at least one of R1" to R3" is an aryl group, and at least one of R' and R6'' is an aryl group.

(b-6) (b'-5) [R4Q is a hydrogen atom or an alkyl group, R41 is an alkyl group, an ethyl fluorenyl group, a fluorenyl group, or a hydroxyalkyl group, and R42 to R46 are each independently an alkyl group or an ethyl group. , oxy, carboxy, or hydroxyalkyl; ~n5 is an integer of 〇3, respectively, but ηο+ΐΜ is 5 or less, and iu is an integer of 0 to 2. In the formula (b, -1), R1'' to R3" are each independently an aryl group or an alkyl group. In R1" to R3", any two of them may be bonded to each other and form a ring together with the sulfur atom in the formula. Further, at least one of R1" to R3" is an aryl group. Among R1'' to R3'', two or more of aryl groups are preferred, and all of R1" to R3" are aryl groups. The aryl group of R1" to R3" is not particularly limited, and is, for example, an unsubstituted aryl group having 6 to 20 carbon atoms, and a part or all of a hydrogen atom of the unsubstituted aryl group may be an alkane. a substituted aryl group substituted with a group, an alkoxy group, an alkoxyalkyloxy group, an alkoxycarbonyl group 200928579 alkyloxy group, a halogen atom, a hydroxyl group, etc., -(R4.) -C(=〇)-R5' R4i is an alkyl group R5 having a carbon number of 1 to 5, which is an aryl group. The aryl group of R5' is, for example, the same as the above-mentioned aryl group of R1"~R3" 无. Unsubstituted aryl group, From the viewpoint of inexpensive synthesis, etc., it is preferred to use an aryl group having a carbon number of from 6. to 10. Specifically, for example, a phenyl group, a naphthyl group or the like. The alkyl group in the substituted aryl group is an alkyl group having 1 to 5 carbon atoms. Good, again with φ methyl, ethyl The propyl group, η-butyl group and tert-butyl group are preferred. The alkoxy group in the substituted aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and a methoxy group, an ethoxy group and a η group. Propoxy, iso-propoxy, η-butoxy, tert-butoxy are preferred. The halogen atom in the substituted aryl group is preferably a fluorine atom. The alkoxyalkyloxy group in the substituted aryl group For example, a formula: a hydrazine - C(R47)(R48) - 〇-R49 (wherein, r48 is an independently hydrogen atom or a linear or branched alkyl group, and R49 is an alkyl group) In the case of 〇R47 and R48, the carbon number of the alkyl group is preferably from 1 to 5, and it may be any of a linear chain and a branched chain, and an ethyl group or a methyl group is preferred. The base is *" optimal., R47, preferably at least one of hydrogen atoms, especially one of which is a hydrogen atom and the other is a hydrogen atom or a methyl group. The carbon number is 1 to 15, and it may be any of a straight bell shape, a branched chain, or a ring shape. The linear or branched alkyl group in R49 has a carbon number of 1 to 5 Good 'for example, methyl, ethyl, propyl, N_butyl, tert-butyl, etc. -23- 200928579 ο R49 in the cyclic alkyl group, preferably having a carbon number of 4 to 15', preferably having a carbon number of 4 to 12, and having a carbon number of 5 to 10 Specifically, it is a monocyclic alkane, a bicycloalkane or a tricyclic chain which may be substituted by an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, or may be unsubstituted. A polycyclic alkane such as an alkane or a tetracycloalkane is removed by a group of one or more hydrogen atoms, etc. Monocyclic alkanes such as cyclopentane, cyclohexane, etc. polycyclic alkanes such as adamantane, norbornane, φ isobornane, tricyclodecane, tetracyclododecane, and the like. Among them, it is preferred to remove one or more hydrogen atoms from adamantane. Substituting an alkoxycarbonylalkyloxy group in the aryl group, for example, the formula: - 〇-R5° - C(=〇) - 0-R51 (wherein R50 is a linear or branched alkyl group , R5 1 is a group represented by a tertiary alkyl group. A linear or branched alkyl group in R5 (> preferably has a carbon number of 1 to 5, for example, a methyl group, an ethyl group, a methyl group, a tetramethyl group, U-dimethylexylethyl, etc. ® A tertiary alkyl group in R51, which is 2-methyl-2-anomantyl, 2-ethyl-2-oxantyl, 1-methyl-1-cyclo Pentyl, fluorenylethyl-1, cyclopentyl, 1-methyl-1-cyclohexyl, 1-ethyl-1-cyclohexyl, '1_(1~adamantyl)-1-methyl Base, 1-(1-adamantyl)-1-methylpropyl, 1_(1_adamantyl)-1 monomethylbutyl, 1 adamantyl)-1-methylpentyl; 1 (1-cyclopentyl) 1 methylethyl, 1-(1-cyclopentyl)-l-methylpropyl, 1-(1-cyclopentyl)-1-methylbutyl, 1- ( 1 monocyclopentyl)-1-methylpentyl; 1(!-cyclohexyl)-i-methylethyl, (1-24-200928579 cyclohexyl)-1-methylpropyl, 1- ( 1 monocyclohexyl)-1 monomethylbutyl, 1-(1-cyclohexyl)-1-methylpentyl, tert-butyl, tert-pentyl, tert-hexyl, and the like. The aryl group of R1"~R3" is preferably a phenyl group or a naphthyl group, respectively. The alkyl group of R1"~R3" is not particularly limited, and is, for example, a linear chain or a branched chain having a carbon number of 1 to 10; The alkyl group or the like having a good analytical property or the like is preferably a carbon number of 1 to 5. Specifically, for example, a methyl group, an ethyl group, a η φ propyl group, an isopropyl group, or a η-butyl group. a base, an isobutyl group, an η-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a fluorenyl group, a fluorenyl group, etc., wherein, in view of excellent resolution or inexpensive synthesis, a linear alkyl group is used. For example, a methyl group, a η-butyl group, etc. may be mentioned. In R1"~R3", any two may be bonded to each other and form a ring together with a sulfur atom in the formula to form a sulfur atom. ~10 member ring is better 'again to form a 5~7 member ring for better. In the case of R1" to R3", any two of them are bonded to each other and form a ring together with the sulfur atom of the formula, and the remaining one is preferably an aryl group. The aryl group is the same as the aryl group of the above R1 "~R3". *' The specific example of the cation moiety represented by the formula (b, -l) is as 'three, phenyl mirror, (3, 5 - Dimethylphenyl)diphenylphosphonium, (4-(2-adamantyloxymethyloxy)_3,5-dimethylphenyl)diphenylphosphonium, (4-(2-adamantyloxy) Methyloxy)phenyl)diphenylphosphonium, (4-(tert-butoxycarbonylmethyloxy)phenyl)diphenylphosphonium, (4-(tert-butoxymethyloxy)) a 3,5-dimethylphenyl)diphenyl mirror, (4 (2-methyl-2-ano-adamantyloxycarbonylmethyloxy)phenyl)diphenyl-25- 200928579 4-(2-methyl-2-ano-adamantyloxycarbonylmethyloxy)- 3,5-dimethylphenyl)diphenylphosphonium, tris(4-methylphenyl)anthracene, dimethyl (4-hydroxynaphthyl)anthracene, monophenyldimethylhydrazine, diphenylmonomethylhydrazine, (4-methylphenyl)diphenylphosphonium, (4-methoxyphenyl)- • Phenyl, di(4-tert-butyl)phenyl mirror, monophenyl (1-(4-methoxy)indenyl) Mirror, __ (1_Caiji) phenyl hydrazine, 1-phenyltetrahydrothiophene, 1 (4-methylphenyl) tetrahydrothiophene gun, 1 (0 3,5-dimethyl-4) Monohydroxyphenyl)tetrahydrothiophene, 1-(4-methoxynaphthalen-1-yl)tetrahydrothiophene gun, 1-(4-ethoxynaphthalen-1-yl)tetrahydrothiophene, 1- ( 4-η-butoxynaphthalene-1-yl)tetrahydrothiophene, 1-phenyltetrahydrothiolan, 1-(4-hydroxyphenyl)tetrahydrothioate, 1 (3,5-2) Methyl 4-hydroxy-hydroxyphenyl)tetrahydrothioate, 1-(4-methylphenyl)tetrahydrothioate, etc. In the formula (b'-2), R5" and R6" are independent Aryl or alkyl. At least one of R5" and R6" represents an aryl group. It is better to use R5" and R6" for both aryl groups. The R5" and R6" aryl groups are identical to the R1"~R3" aryl groups » _ Ο - R5" and R6" The base is the same as the alkyl group of R1"~R3", wherein R5" and R6" both are preferably phenyl. The specific part of the cation part represented by the formula (b'-2) For example, a diphenyl iodine gun, a bis(4-tert-butylphenyl) iodine, etc.. In the formulae (b'_5) and (b-6), in the R4Q to R46, the alkyl group is a carbon-26- 200928579 Alkyl groups of 1 to 5 are preferred, wherein a linear or branched alkyl group is more preferred, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, or a tert-butyl group is preferred. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, wherein a linear or branched alkoxy group is more preferred, and a methoxy group and an ethoxy group are preferred. _ hydroxyalkyl group, preferably one of the above alkyl groups or a plurality of hydrogen atoms substituted by a hydroxyl group, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, etc. φ nD, preferably 0 or 1 η 1, preferably 0 to 2. η2 and η3, Preferably, each is independently 0 or 1, more preferably 〇. η4, preferably 0 to 2, more preferably 0 or 1. η5, preferably 0 or 1, more preferably 0. 116, preferably 0 or 1. In the present invention, Α+ is preferably a cation moiety represented by the formula (b'_ 1 ) or (b· - 5 ), particularly in the following formula (b1 - 1 - 1) - (b1 - 1 - 〇n), (b'-5-1)~(b, a 5-4) is a good cation part represented by the formula (b'-1 1-1)~(b, -1-8) The cation portion of the triphenyl skeleton such as the cation moiety ** is more preferably. 'In the formula (b1 - 1-8), 'R7 is an alkyl group having 1 to 5 carbon atoms. The alkyl group is linear or branched. The alkyl group is preferred, and particularly preferably a methyl group or an η-butyl group. In the formula (b'-1-9), R7 is an independent carbon number!~; For example, it is the same as the alkyl group of the above R1 "~R3 ", preferably a linear or branched alkyl group, and a linear alkyl group is more preferable, especially -27-200928579 Η-butyl is preferred. In the formula (b'-1-10-)~(b1-11-11), R8 and R9 each independently may have a substituent. a phenyl or naphthyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a hydroxyl group. The substituent which the above phenyl or naphthyl group may have is a substituent in the aryl group of the above R1 "~R3" For the same content. The substituent is particularly preferably an alkyl group. a is an integer of 1 to 3, and 1 or 2 is optimal.

-28- 200928579

[化1 0]

The method for producing the compound (B1) is not particularly limited. For example, the compound (I) can be produced by reacting with the compound (II) represented by the following formula (II). -29- 200928579 [Chemical 1 1] A+ Z~ - (II) [wherein A + is the same as a + in the above formula (bl-1)" is a low nucleophilic halogen ion, The acidity is lower than that of the compound to form an acid ion, BF4_, AsF6_, SbF6_, PF6- or cio4-]. A halogen ion of a low nucleophilic name in φ, such as a bromide ion, a chloride ion, or the like. In ζ-, acidity is lower than the compound (I) to form an acid ion, such as yttrium-toluenesulfonate ion, methanesulfonate ion, benzenesulfonate ion, trifluoromethanesulfonate ion, butyl sulfate ion, etc. . The compound (I)' and the compound (11) can be, for example, dissolved in a solvent such as water, dichloromethane, acetonitrile, methanol, chloroform or dichloromethane, followed by stirring or the like. Φ The reaction temperature is preferably from about 0 ° C to 150 ° C, preferably from about or about i 〇〇 r. The reaction time varies depending on the reactivity of the compound (I) and the compound (II), the reaction temperature, etc., and is usually preferably from 0.5 to 10 hours, more preferably from 1 to 5 hours. In the above reaction, the compound (II) is usually used in an amount of from 0.5 to 2 mol per mol of the compound (I). The structure of the compound obtained by the above method can be iH-nuclear magnetic resonance (NMR) spectrometry, 13C-NMR spectrometry, 19F-NMR spectrometry, infrared absorption (IR) spectrometry, mass spectrometry (MS) method, -30 - 200928579 Confirmation by general organic analysis methods such as elemental analysis and X-ray crystal diffraction. The compound (B1), which is a novel compound which can be used as an acid generator, can be added to the photoresist composition in the form of an acid generator. <<Acid Generator>> The acid generator of the present invention is formed of the compound (B 1 ) of the fifth aspect described above. The acid generator can be effectively used as an acid generator for a chemically amplified photoresist composition, for example, an acid generator component (B) of the photoresist composition of the present invention to be described later. <<Photoresist composition>> The photoresist composition of the present invention is a substrate component (A) (hereinafter also referred to as Q (A) component) containing a change in solubility in an alkali developer via an action of an acid. And an acid generator component (B) (hereinafter, also referred to as (B) component) which generates an acid by exposure, wherein the component (B) is a compound represented by the above formula (bl-1) The acid-generating agent (B1) formed. When the photoresist film formed by the photoresist composition is selectively exposed during the formation of the photoresist pattern, the (B) component is caused to generate an acid, and the (A) component is dissolved in the alkali developing solution via the acid. Sex changes. As a result, the solubility of the exposed portion of the photoresist film to the alkali developing solution can be changed, and the solubility of the unexposed portion to the alkali developing solution does not change -31 - 200928579, via alkali development. In the case of a positive type, it is an exposure part, and in the case of a negative type, the unexposed part is dissolved and removed, and a photoresist pattern is formed. The photoresist composition of the present invention may be a negative photoresist composition or a positive photoresist composition. &lt;(A) Component&gt; (A) The organic compound to be used as a base material for a chemically amplified photoresist can be used singly or in combination of two or more kinds. Here, the "substrate component" means an organic compound having a film forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. When the molecular weight of the organic compound is 500 or more, the film formation energy can be improved, and a photoresist pattern of a nanometer degree can be easily formed. The organic compound having a molecular weight of 500 or more can be roughly classified into a low molecular weight organic compound Φ (hereinafter, also referred to as a low molecular compound) having a molecular weight of 500 or more, and a high molecular weight resin having a molecular weight of 2,000 or more. (Polymer Materials). The aforementioned low molecular compound, *' is usually used for non-polymer. In the case of a resin (polymer, copolymer), 'medium' and "molecular weight" are mass average molecular weights in terms of polystyrene in terms of GPC (gel permeation chromatography). Hereinafter, the term "resin" alone means a resin having a molecular weight of 2,000 or more. As the component (A), it is possible to use a resin which causes an alkali solubility to be changed into a ft t resin, or a low molecular material which changes the solubility of an alkali by an action of an acid. -32- 200928579 When the photoresist composition of the present invention is a negative photoresist composition, the component (A) may be a substrate component which is soluble in an alkali developer or a crosslinking agent is added to the negative photoresist composition. . When the negative resist composition is caused to cause an acid to be generated in the component (B) by exposure, cross-linking occurs between the substrate component and the crosslinking agent by the action of the acid, and the alkali developing solution is insoluble. Therefore, in the formation of the photoresist pattern, when the photoresist film obtained by applying the negative photoresist composition on the substrate is subjected to selective exposure, the exposed portion can be converted to be insoluble to the alkali developer. The unexposed portion was formed into a photoresist pattern by alkali development without being changed to be soluble in the alkali developing solution. The component (A) of the negative resist composition is usually a resin which is soluble in an alkali developing solution (hereinafter also referred to as an alkali-soluble resin). The alkali-soluble resin, which is a resin having a unit derived from at least one selected from the group consisting of α-(hydroxyalkyl)acrylic acid or a lower alkyl ester of α-(hydroxyalkyl)acrylic acid, can form a good swelling with less swelling. The photoresist pattern is 〇, which is preferred. Further, α-(hydroxyalkyl)acrylic acid is an acrylic acid obtained by bonding a hydrogen atom bonded to a carbon atom in the alpha position of a carboxyl group, and a carbon-bonded hydroxyalkyl group (preferably a carbon number) A hydroxyalkyl group of 1 to 5 is bonded to the α-hydroxyalkylacrylic acid or both. When the crosslinking agent' is usually an amine-based crosslinking agent such as a hydroxymethyl group or an alkoxymethyl group, it is preferred to form a good photoresist pattern having less swelling. The amount of the crosslinking agent to be added is preferably 1 to 5 parts by mass based on 100 parts by mass of the alkali-soluble resin. When the photoresist composition of the present invention is a positive resist composition, (A) can be used in the range of -33 to 200928579, and a substrate component which increases the solubility to the alkali developer by the action of an acid can be used. In other words, the component (A) is poorly soluble in the alkali developer before exposure, and when the component (B) is acidified by exposure, the solubility in the alkali developer is increased by the action of the acid. When the resist pattern is formed, when the resist film obtained by applying the positive resist composition on the substrate is selectively exposed, the exposed portion is converted from soluble to soluble in the alkali developing solution, and the unexposed portion is simultaneously exposed. In the state where the alkali is poorly soluble, the photoresist pattern can be formed by alkali φ development. In the photoresist composition of the present invention, the component (A) is preferably a component of the substrate which increases the solubility in the alkali developer via the action of an acid. That is, the photoresist composition of the present invention is preferably a positive photoresist composition. The component (A) may be a resin component (A1) (hereinafter, also referred to as (A1) component) which increases solubility in an alkali developer via an action of an acid, or may be increased by an action of an acid. The low molecular compound (A2) (hereinafter also referred to as (A2) component) which is soluble in the alkali developer may be used, or a mixture thereof. *' [(A1) component], (A1) component is usually a resin component (base resin) which is used as a substrate component for chemically amplified photoresist, and may be used alone or in combination of two or more. can. In the present invention, the component (A1) is preferably a structural unit derived from an acrylate. In the specification and the scope of the patent application, "the structural unit of acrylate derived from -34-200928579" means the structural unit formed by the cracking of the ethylenic double bond of the acrylate. "Acrylate" means a compound in which the carbon atom at the alpha position is a compound having a hydrogen atom bonded to a hydrogen atom, and a compound having a carbon atom bonded to a substituent (hydrogen, an atom other than a subunit or a group) . Substituents, such as low-grade yards, halogenated lower-grade yards, etc. Further, the α-position (carbon atom of the α-position) of the structural unit derived from the acrylate means a carbon atom bonded to the carbonyl group unless otherwise specified. In the acrylate, the lower alkyl group of the substituent at the α-position, specifically, for example, methyl, ethyl, propyl, isopropyl, η-butyl 'isobutyl, tert-butyl, pentyl, isoprene A lower linear or branched alkyl group such as a benzyl group or a neopentyl group. Further, the halogenated lower alkyl group is specifically a group obtained by substituting a part or all of a hydrogen atom in the above-mentioned "lower alkyl group of the α-substituted group" with a halogen atom. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom G, an iodine atom or the like, is preferably a fluorine atom. In the present invention, the α-position of the acrylate is bonded, preferably a hydrogen atom, a low alkyl group or a halogenated lower alkyl group, and more preferably a hydrogen atom, a lower alkyl group or a fluorine or a lower alkyl group. It is preferable to use a hydrogen atom or a methyl group from the viewpoint of easy industrial availability. The component (A 1 ) is particularly preferably a structural unit (al ) derived from an acrylate having an acid-dissociable dissolution inhibiting group. Further, the component (A1) is preferably a structural unit (a2) -35-200928579 derived from an acrylate having a cyclic group containing a lactone, in addition to the structural unit (al). The component (A1) is preferably a structural unit (a3) derived from an acrylate having a polar group-containing aliphatic hydrocarbon group, in addition to the structural unit (al) or structural units (al) and (a2). • Structural unit (al) The acid dissociable dissolution inhibiting group in the structural unit (a 1 ) is an alkali-insoluble alkali-inhibiting inhibitory property of the entire (A 1 ) component before the dissociation, and after dissociation by acid It is sufficient to increase the solubility of the entire component (A1) to the alkali developer, and it is possible to use an acid dissociable dissolution inhibiting group which has been proposed as a base resin for a chemically amplified photoresist 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 the "trialkyl ester", for example, the hydrogen atom of the carboxyl group is substituted with a chain or a fluorene-substituted alkyl group to form an ester such that the carbonyloxy group (a C(o) - 〇-) is an oxygen atom at the end. A structure obtained by bonding to a tertiary carbon atom of the aforementioned chain or cyclic alkyl group. In the above tertiary alkyl ester, the bond between the oxygen atom and the tertiary carbon atom can be interrupted by the action of an acid. Further, the 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 "triester alkyl ester type acid dissociable dissolution inhibiting group". The tertiary alkyl ester type acid dissociable dissolution inhibiting group is, for example, an aliphatic branched chain-36-200928579 acid dissociable dissolution inhibiting group, an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, and the like. "Aliphatic branched" means a branched structure having no aromaticity. The structure of the "aliphatic branched acid dissociable dissolution inhibiting group" is not limited to a group (hydrocarbon group) formed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and it is generally preferred that the saturated fatty acid is preferably a fatty acid. The aliphatic branched dissociative dissolution inhibiting group is preferably a C 4 to 8 tertiary alkyl group, specifically For example, tert-butyl, tert-pentyl, tert-heptyl, and the like. The "aliphatic cyclic group" means a monocyclic or polycyclic group having no aromaticity. The "aliphatic cyclic group" in the structural unit (al) 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 alkylene group having 1 to 5 carbon atoms substituted by a fluorine atom, an oxygen atom (= fluorene) or the like. The "aliphatic cyclic group" removes the basic ring structure of the substituent, and *&quot; does not define a group (hydrocarbon group) composed of carbon and hydrogen, but a hydrocarbon group is preferred. Also, 'hydrocarbon group' can be either 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 'for example, may be substituted by a lower alkyl group, a fluorine atom or a fluorinated alkyl group' or may be substituted by a monocyclic chain, a dicycloalkane, a tricycloalkane, or a tetra A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as a cycloalkane. More specifically, for example, cyclopentane, cyclohexane, etc. -37-200928579 monocyclic alkane or a polycyclic chain such as adamantane, norbornane, isopentane, tricyclodecane or tetracyclododecane A group obtained by removing one or more hydrogen atoms from an alkane. An acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, for example, a group having a tertiary carbon atom on a ring skeleton of a cyclic alkyl group, and the like, specifically, for example, 2-methyl-2-antaphtyl group, Or 2-ethyl-2-alantayl and the like. Or, for example, in the structural unit represented by the following general formula (al"-l) to (al"-6), it has a base of an oxygen atom bonded to a carbonyloxy group (-C(O)-O-), and has a diamond An aliphatic cyclic group such as an alkyl group, a cyclohexyl group, a cyclopentyl group, a norbornyl group, a tricyclodecyl group, a tetracyclododecyl group, or the like, and a branched chain having a tertiary carbon atom bonded thereto Alkyl group and the like. [1 2]

(a 1&quot; -1) (a V* -2) (a 1&quot; -3) (a1*-4) (a 1&quot; -5) (a 1 &quot; -6) [wherein R is a hydrogen atom And a lower alkyl group or a halogenated lower alkyl group; R15 and R16 are an alkyl group (may be linear or branched, preferably having a carbon number of 1 to 5). a lower alkyl group or a halogenated lower alkyl group of the formula (al"-l) to (al"-6), for example, a lower alkyl group or a halogenated lower alkyl group which may be bonded to the α-position of the acrylate as described above. The same content. The "acetal type acid dissociable dissolution inhibiting group" is generally bonded to an oxygen atom of an ammonia atom which is substituted at the end of the soluble group, such as a carboxyl group, a carboxyl group, or the like. 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 ). [Chemical Formula 1] ❹ C—(p1) [wherein, R1', R2' each independently represent a hydrogen atom or a lower alkyl group, n is an integer of 〇 to 3, and Υ is a lower alkyl group or an aliphatic cyclic group] . In the above formula, η is preferably an integer of 0 to 2, more preferably 〇 or 1 and most preferably 〇. The lower alkyl group of 〇 R1' and R2', for example, the inner valency of the lower alkyl group of the above R 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 (ρ 1 ) is preferably a group represented by the following formula (ρ 1 - 1 ). (1) (pi-1) is an o-^ch2^-y [wherein R1, η, Y are the same as the above-mentioned contents - 39-200928579 Y lower alkyl, for example, with the above R The lower alkyl group is the same content. The aliphatic ring group of Y may be appropriately selected from among the monocyclic or polycyclic aliphatic ring groups which have been proposed many times in the conventional ArF photoresist, for example, and the above-mentioned "aliphatic ring type". The base is the same content. Further, the acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (P2).

[Chemical 1 5] R17 ——C——Ο—R19

L R18 (p2) wherein R17 and R18 each independently represent a linear or branched alkyl group or a hydrogen atom, and R19 is a linear, branched or cyclic alkyl group, or R17 and R19. Each of them independently represents a linear or branched alkyl group, and the end of Rn 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, preferably ethyl or methyl, and most preferably methyl. Any one of r18 is a hydrogen atom, and the other is preferably a methyl group. When R19 is a linear, branched or cyclic alkyl group, the number of carbon atoms is preferably from 1 to 15, and it may be any of a linear chain, a branched chain or a cyclic chain. When R19 is linear or branched, the carbon number is preferably from 1 to 5, more preferably ethyl or methyl, and most preferably ethyl. -40- 200928579 When R is a ring, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and the carbon number is preferably 5 to 10. Specifically, it may be substituted by a fluorine atom or a fluorinated alkyl group, or may be substituted by a polycyclic alkane such as a monocyclic alkane, a bicyclic chain, or a tricyclic chain, a tetracyclic alkane. More than one hydrogenogen-subunit and 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, the base obtained by removing one or more hydrogen atoms from adamantane 0 is preferred. Further, in the above formula, R17 and R18 each independently represent 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. can. At this time, 'R17 and R19' are bonded to the oxygen atom of rI9, 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', preferably a 4 to 6 member ring. Specific examples of the cyclic group include, for example, a tetrahydropyranyl group, a tetrahydrofuranyl group and the like. The 〇 structural unit (al) is formed by a structural unit represented by the following general formula (al-0-1) and a structural unit represented by the following general formula (a 1 - 0 - 2) One or more selected ones are preferred. 【化1 6】

(a1 - 0-1) wherein R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group of 200928579; and X1 is an acid dissociable dissolution inhibiting group. [化1 7]

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 (al-0-1), the lower alkyl group of R or the halogenated lower alkyl group is the same as the above-mentioned lower alkyl group halogenated lower alkyl group which may be bonded to the α position of the acrylate. X1 is not particularly limited as long as it is an acid dissociable dissolution inhibiting group, and may be, for example, a tertiary alkyl ester type acid dissociable dissolution inhibiting group or an acetal type acid dissociable dissolution inhibiting group. The ester type acid dissociable dissolution inhibiting group is preferred. In the general formula (al-0-2), R has the same content as described above. X2 is the same as X1 in the formula (al-0-l). Y2 is preferably an alkylene group having 1 to 10 carbon atoms or a divalent aliphatic cyclic group. In the case of the aliphatic cyclic group, the same as the above description of the "aliphatic cyclic group" can be used, except for the use of a group in which two or more hydrogen atoms are removed. -42- 200928579 When γ2 is an alkylene group having 1 to 10 carbon atoms, it is more preferably a carbon number of 1 to 6 and a carbon number of 1 to 4, and a carbon number of 1 to 3 is most preferable. When Υ2 is a divalent aliphatic cyclic group, 'removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane or tetracyclododecane The basis is especially good. In the structural unit (al), more specifically, the structural unit represented by the following general formulas (al-1) to (al-4).

[化1 8]

〔 [In the above formula, X' is a tertiary alkyl ester type acid dissociable dissolution inhibiting group; Y is a lower alkyl group having a carbon number of 1 to 5 or an aliphatic cyclic group; η is an integer of 0 to 3; Υ 2 It is an alkyl group or an aliphatic cyclic group; R has the same contents as described above; r1' and r2' each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms]. In the formula, X' is the same as the cyclic tertiary alkyl ester type acid dissociable dissolution inhibiting group exemplified in the above X1. -43- 200928579

Rf, R2', η, and Y are the same as η and Υ in the general formula (Ρ 1 ) described in the description of the above "acetal type inhibition group". Υ2, for example, with 1 in the above formula (al - 〇_2), the content. The following are specific examples of the above-mentioned general formulas (al-Ι) to (al-4), and the hydrazine-dissociated soluble R1', R2', and u are the same structural singles.

-44 - 200928579 【化1 9】

CH: CH2—C ’ 0=\ c2h5 (a1-1-3)

❹

(a1 -1 - 5) ^C^-c , 〇 4

(a1-1-9)

(al-1-10) (al-1—8) ch3 •CH:_C—V- ch3 ❹

CH2—CH^~ —^-CH2—C—^— 0==^ ch3 °=\ (°tX)—(al-1-12) ch3 . Gam (a1—1 -13) :CH2—CH today

CHg_C-^-°=\ C2H5. Loss (a1 - 1-15)

-45- 200928579 【化2 0】

(a1-1-17) (a1-1-18) &lt;?η3 ?η3 lch2—ch}- 〇=^ 9h3 . Plus. Add (a1-1-20) Ο -CH2—CH^h ch3 -ch2—c-V〇=^ ?2h5

•CH2—CHH ch3 0=4 ch3 0=V CzH5 °=A c2h5^ tD Cut (a1-1-21) CH3 I \ -CH2—c~ 〇4;o CH3I ch3 (al-1-25)

(a1-1~22) (a1 -1 -23> (CH2—CH^—^CH2—CH^- —\ 〇=( ch3/ch3 0==1^jh3

Ch3 Ca1—1~26) u (a1-1-27) (a1-1-24) •ch2—ch|- °=l 9H3/CH3 〇

❹ -0 CH3 H2—C-^-o CH.3 (al-1-28) ch3

(a1-1-29) -fcHa-if ten"leaf ten H2-ten + ch3 0==^ 〒2 ratio ο— ?2η5°b °b 6 (a1-1*30) (a1+31) (a1 -1-32) -46 200928579 【化2 1 •f 〒h3 ch3 CH2-〒手十CH2-〒十0=\ J~, 〇=\ ❹

(a1-1-37) CH3 ch3 Let 2-|+ °=\ ch3 ch3 -ch2—c4-〇=\ c2h5 3 °b °6 (a1-1~34) (a1-1-35) (a1- 1-36)

(a1-1-38) ch3

H3ct (aiH-39) ?H3 CH2—CH^- -^CH2—C-^-' o :CH2—CH+ 0==l ?H3°b (a1-1 - 40)

CH2—CH 0=i o CH3

'CH3 h3CT ch3 , ch3 h3c- (a1-1-42) (a1-1-43) (a1-1-44) CH3 H3C C2H5 xh3 C2H5 (a Bu 1 - 45) ❿ [Chemical 2 2]

—^CH2—ch^ —^ch2—ch)· 〇=l o 〇

(a 1-2—4)

〇4 〇,

(a 1 -2-6) 47- 200928579 [Chemical 2 3] ch3 -{ch2-f 〇=\ (a 1-2-7). (10) (ch2—ch)-〇4 〇^〆(a1-2-8) ch3 —(ch2-c-^ 〇-(a1-2-9) -(ch2^h)- (a1—2—10) —fcH2-® 〇t. -fCH2-CHW. 4 (al-2—11) ❹ ch3 —{ch2-c-)- , 〇, (al-2-13) 〇-{ch2-ch)- 〇 -^ (a1-2-16) —(ch2-c|-(al-2-19)

,〇 o -fcH2^H)» 〇一 (a1—2-14) cf3 -(cH2-c-y- 〇, ,〇

CH2-Cj—fly, (a1 -2 -15) ?F3 -(CH2-C·)-

p (a1-2-17) -(ch2^-)- 〇' — (a1-2-18) 〇= b- (a1 - 2-20) 200928579 [Chem. 2 4] ch3 十—f- 0, ο (al-2-21) ——CH) 〇4 — ch3 〇, (a1 - 2-22) ;Ό CH2-c4- 〇^. (al-2-23) -(•CH2-CH)°4 0 - ❹ (a1-2~24) ch3〇, (a1-2-25) X) -fCH2—CH) '4) 〇—^· (a1-2-26) Γ3 —^ch2-cJ— cf3 -{ CH2-cf Ό. . ~ (a1-2-27) (a1-2-28) 0, 一〇, °T&gt; —f-CH2-c)- O, (a1 十29) CH3 〇4 o _ (a1-2-30) Hey.

Ch3 icH2-c4-〇4 (a1e2—31)

-49- 200928579 【化2 5】

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

(a1-2-38) (a1-2-39)

-50- 200928579 【化2 6】 ch3 ch3 0==^ 0=1p 0 CH3 ch

ο Ο 〇W^ Q C2H5

(al-3-t)

ο h3c

0 ο ο

C2H5

o h3c o

o O C2H5 〇 (a1-3-2) Ca1-3-3)-fCl^4- -fcH2-C) p p (al-3-4)

(β1-3·5)

(a 1-3-6) 〒 — —^ch2-ch^· —^ch2^ch-0=4

〇

O

O Η3〇Λ2) c2Hs,^0 η3°^^) (al-3-7) Cal-3-8)

0= O

O 0= Ο

O 0

O O (al-3-9) O c2h5-

(at-3-10) h3c^\ ; c2h5-^2) (al-3-11) (al-3-12) ch3 ch3H〇^ fCH〇^ ^CH0^ f〇H^ f CH2a a / / P p 0

〇 &gt;=〇 «5^ 〇h3〇2Q Cat-3-13) (al-3-14)

H3c

0 0

o

o h3c C2H5

o

0

o

Ca1'3-15) (a1-3-i6) (at-3-t7) c2H5-

(af-3-Ιβ) [化 2 7] 十 chJ冬 CH, /0 ,° 0 b

o 6 〇 [ C2H5

(a1-3-19) (al-3-20)

o h3c- 0

(al-3-21)

200928579 【化2 8】

(al-3-27) (βί-3-28)

(al-3-29) (at-3-3D)

(a1 -3-31) (al-3-32)

(a 1-3-34) (a1-3-35) (a 1-3-36) -52- 200928579 [Chem. 2 9]

(al-3-37) (at-3-38) (a 彳-3-39)

Small (a 1-3-40)

(a bu 3-46)

(at-3-46) 200928579 [Chemical 3 0] ch3 ... I VM3 -^CHz-CH)- -(-CH2-C-)- -(-CH2-CH)- -{-CHz-C-}-

〇· ° P 〇 P o ^ o ) O ; o gas u % % gas.

Q (at-4-1) Ca1-4-2) (al-4-3) Ο (a1-4-4) (a 1-4-5)-9H3 _ -^CH2-CH)- -^CH2 -C-^- -fCH2-C^--(ch2-c-}- -^-ch2-ch)- ch3 aoo

) Q 0,

0

o 0 o

o d

O (a1-4-6) (al-4-7)

QO \ /o (a 1 -4-8) (a 1 -4-9) (a1-4-10) ?H3 ❿ -f-CH2-CH)--(-CH2—C-^- -^CH2 —c·)- -^CH2~CH^--3 4 )=〇&gt;=〇&gt;=〇π. ^ ~ O &gt; /o

.0 〇· o'

〇 〇 〇 〇 〇"

Ca1-4-12) Cal-4-13)

Q

O (al-4-14) (at-4-15) (at-4-16) 200928579 【化3 1】卡Η^^Η)&quot; —(CH2j 十-(ch2--ch}- -( *CHz-cy -(oh2-ch-^ -^CH2-C^- -(cHz-CH^-〇〇〇°p 〇&lt;〇〇K〇°p °\

o o

o

o

0

o

o

0 &gt;=0 Q 〇, 03⁄4

(a1-4-18) (al-4-19) (al-4-20) (aW-21) (al-4-22) (a1-4~23) (at-4-24)

Ca1-4-25) (al-4-26) (a1-4-27) (a1-^4-28) (al-4 -29&gt; (dl-4-30) Ο

The structural unit (a 1 ) may be used singly or in combination of two or more. In the above formula, the structural unit represented by the formula (al-1) is preferred. Specifically, at least one selected from the group consisting of the formulas (al-1 to 1) to (al-1 to 6) and the formulas (al-1 to 35) to (al-1 to 41) For better. Further, the structural unit (al) is, in particular, a unit represented by the following general formula (al-1-01) containing a structural unit of the formula (al - 1 - 1 ) to (al - 14 - 4), or an inclusion formula (al-1—35) to (al-1–41) structure -55- 200928579 The unit of the following general formula (al-1 to 〇2) is preferred. [化3 2]

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

c=o

Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R12 is a lower alkyl group, and h is an integer of from 1 to 3. In the general formula (al - 1 - 01), R has the same content as described above. The lower alkyl group of R1 1 is the same as the lower alkyl group represented by R, and a methyl group or an ethyl group is preferred. In the general formula (al - 1 - 02), R has the same content as described above. The lower alkyl group of R12 is the same as the lower alkyl group represented by the above R-56-200928579, and it is preferably a methyl group or an ethyl group, and an ethyl group is preferred. h is preferably 1 or 2, and 2 is the best. The structural unit (al) may be used singly or in combination of two or more. In the component (A 1 ), the ratio of the structural unit (a 1 ) is preferably from 10 to 80 mol%, and from 20 to 70 mol%, based on the entire structural unit constituting the component (A 1 ). For better, 25 to 50 mol% is the best. When it is at least the lower limit 値, it can be easily formed into a pattern when it is a positive resist composition. When it is below the upper limit 値, it can be balanced with other structural units. • Structural unit (a2) The structural unit (a2) is a structural unit derived from an acrylate containing a cyclic group containing a lactone. Among them, the cyclic group containing a lactone is a cyclic group containing a ring (lactone ring) of the -0-C(O)- structure. The lactone ring is counted as a ring unit ,, and the monocyclic group is only a lactone ring. If the fluorene has other ring structures, it is called a polycyclic group regardless of its structure. · The lactone ring group of the structural unit (a2), in the case where the polymer compound (A1*) component is used to form the photoresist film, the adhesion of the photoresist film to the substrate can be effectively improved, and the adhesion can be effectively Increasing the affinity 〇 structural unit (a2) with the developer containing water, any unit can be used without any limitation, specifically, a lactone-containing monocyclic group, for example, 7-butyrolactone removal-57 - 200928579 The basis of 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 structural unit (a2), more specifically, for example, the structural unit shown by the following formulas (a2 - 1) to (a2 - 5). [化3 4]

Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R' is a hydrogen atom, a lower alkyl group, or an alkoxy group having a carbon number of 1 to 5 or a CO OR&quot;, and the aforementioned R&quot; is a hydrogen atom Or a linear, branched or cyclic alkyl group having a carbon number of 1 to 5, m is an integer of 0 or 1, and A&quot; is an alkylene group or an oxygen atom having a carbon number of 1 to 5. R in the general formulae (a2 - 1) to (a2 - 5) has the same content as R in the above structural unit (al). The lower alkyl group of R| has the same content as the lower alkyl group of R in the above structural unit (al). In the case of a linear or branched alkyl group, R&quot; is preferably a carbon number of 1 to 1 Å, and preferably a carbon number of 1 to 5. In the case where R&quot; is a cyclic alkyl group, a carbon number of 3 to 15 is preferable, a carbon number of 4 to 2 is more preferable, and a carbon number of 5 to 10 is most preferable. Specifically, 'for example, -58-200928579 may be substituted by a fluorine atom or a fluorinated alkyl group, or a non-bicycloalkane, a tricycloalkane or a tetracyclic alkane polycyclic chain deuterated monocyclic alkane, and 1 is removed. The base obtained by more than one hydrogen atom, and the like. The specific inner valley is removed by a single ring chain such as Huanyuanyuan and Huanyuanyuan, or a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclodane. The base obtained by the above hydrogen atom and the like. A&quot; an alkylene 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, and the like. In the general formula (a2-l) to (a2-5), R is preferably a hydrogen atom in view of industrial availability. The following are exemplifications of specific structural units of the above general formulae (a2-1) to (a2-5). [化3 5]

-59- 200928579 [Chem. 3 6] ch3 -C-.彳 Ο: ο CH3〇4f CH3 *fcH2—C-}-〇4

o o. ch3

(a2-2-1) 〇(a2-2-2) (a2-2-3) CH3 ch3 Ό 〇(a2-2-4) CH3 ❹ -{CH2—C-)- -fcH2—C-}- ~(CH2—CH)- -fcH2—〇)- 〇=J^ CH3 0=4^ 0==\ 〇=\

(a2-2S)

CH3 (a2-2-6) (a2-2-7) CH3

, i, -(CH2—ch)- . ΐΑ3 -{ch2—ch}- -fcH2-c)- V 〇J -(CH2-Cf- | °=K - o , . loan ^ 10 (32-2- 9) 〇ch3 -fcH2-c4- 〇=J o

-(ch2—ch)- o

(a2-2-14) (a2-2-13) 0 -60- 200928579 [Chem. 3 7]

Ch3 CH2-c)- -{ch2-ch)- i

For 2-3-10) -61 - 200928579 [Chem. 3 8]

-62- 200928579

[化3 9]

In the structural unit (a2), at least one selected from the group consisting of the structural units represented by the above formulas (a2 - 1) to (a2 - 5) is preferred, and the formula (a2 - It is more preferable that at least one selected from the group consisting of structural units shown in (a2 - 3) is preferable. Wherein 'the chemical formula (a2 - 1 - 1 ), ( a2 - 1 - 2 ), ( a2 - 2 - 1 ), ( a2 - 2 - 2 ), (a2 - 3 - 1 ), (a2 - 3 — 2) , (a2—3—9) and at least one selected from the group of structural units shown in (a2 - 3-10) are good structural units (a2), and one type can be used alone or 2 The above group -63- 200928579 can also be used together. In the component (A1), the ratio of the structural unit (a2) is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, based on the total of the structural units constituting the component (A1). 20 to 50% Mo is the best. When the lower limit is above the limit, the effect can be fully achieved when the structural unit (a2) is contained, and the balance with other structural units can be obtained when the upper limit is less than or equal to the upper limit. φ • structural unit (a3) The structural unit (a3) is a structural unit derived from an acrylate having an aliphatic hydrocarbon group containing a polar group. When the component (A3) contains a structural unit (a3), 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 hydroxy group '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 φ aliphatic hydrocarbon group is, for example, a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) or a polycyclic aliphatic hydrocarbon group (polycyclic group)*. The polycyclic group ' can be suitably used, for example, from the resin used for the ArF excimer laser photoresist composition'. The polycyclic group preferably has a carbon number of from 7 to 30. Further, the structural unit derived from an acrylate having a hydroxyl group, a cyano group, a carboxyl group, or an aliphatic polycyclic group containing a hydroxyalkyl group in which one of hydrogen atoms in the alkyl group is substituted by a fluorine atom is more preferable. The polycyclic group is, for example, a group obtained by removing two or more hydrogen atoms -64 - 200928579 from a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, for example, a group obtained by removing two 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 structural unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group containing a polar group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the structural unit derived from hydroxyethyl acrylate is preferred. 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4 0]

OH (a3-3) [wherein R has the same content as described above, j is an integer of 1 to 3, k is an integer of 1 to 3 't' is an integer of 1 to 3, and 1 is an integer of 1 to 5 , 3 is an integer of 1 to 3]. In the formula (a3 - 1), 'j is preferably 1 or 2, and more preferably 1 is more preferable. In the case where j is 2, it is more preferable that the hydroxy group is bonded to the adamantyl group at the 3rd position and the 5th position -65-200928579. 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. Among them, it is preferable that j is 1 or not, and particularly, a hydroxyl group bonded to the adamantyl group is preferred. In the formula (a3-2), it is preferable to use k as one. Further, it is preferred that the cyano group is bonded to the 5- or 6-position of the norbornyl group. In the formula (a3 - 3), it is preferable that t' is one, and that one is 1 is preferable, and s is one. It is preferably a terminal bond of a carboxyl group of acrylic acid 2 - a norbornyl group or a 3-norbornyl group. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the norbornyl group. The structural unit (a3) may be used alone or in combination of two or more. In the component (A1), the ratio of the structural unit (a3) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on the entire structural unit constituting the component (A1). ~25 mol% is the best. When the lower limit is φ, the effect of containing the structural unit (a3) can be sufficiently obtained, and when it is less than the upper limit 可, the balance with other structural units can be obtained. * • Structural unit (a4) (A1) component, which may further contain other structural units (a 4 ) and structural units (a4) other than the above structural units (al) to (a3), without impairing the effects of the present invention (a4) It is not particularly limited as long as it is a structural unit that is not classified into the above structural units (a !) to (a3). It can be used -66- 200928579

A plurality of conventionally known structural units used for resistive resins such as ArF excimer lasers and KrF excimer lasers (preferably for ArF quasi-mineral lasers). The structural unit (a4), for example, a structural unit derived from an acrylate having a non-acid dissociable aliphatic polycyclic group is preferable. The polycyclic group is, for example, the same as exemplified in the above structural unit (al), and can be used for ArF excimer laser or KrF excimer laser (preferably φ ArF excimer laser) Most of the conventionally known structural units used for the resin component of the photoresist composition. In particular, when at least one selected from the group consisting of a tricyclodecylalkyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is industrially preferable, it is preferably obtained. These polycyclic groups may be substituted by a linear or branched alkyl group having 1 to 5 carbon atoms, or a structural unit (a4), specifically, for example, the following formula (a4-1) The structural unit shown in (a4-5). Ο 【化4 1】

[wherein R has the same content as described above]. When the component (a4) is contained in the component (A1), the ratio of the structural unit (a4) in the component (A1) -67 to 200928579 is "to the total of the structural units constituting the component (a1)" to contain 1 ~3 0% of the mole is better, and it is better to contain 10~20 mol%. In the present invention, the component (A1) is preferably a copolymer containing structural units (al), (a2), and (a3). The copolymer is, for example, a copolymer obtained from structural units (al), (a2), and (a3), a copolymer obtained by structural units (al), (a2), (a3), and (a4). The (A1) component can be obtained by polymerization of a monomer derived from each structural unit, for example, a radical polymerization initiator such as azobisisobutyronitrile (AIBN) by a known radical polymerization. Further, in the above-mentioned polymerization, the (A1) component may be, for example, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-?H, and -C(CF3)2- at the end. OH group. Thus, a copolymer into which a hydroxyalkyl group in which one of hydrogen atoms in the alkyl group is substituted by a fluorine atom can be obtained, thereby effectively reducing defects or reducing LER (Line Edge Roughness) effect. The mass average molecular weight (Mw) of the component (A1) (the amount of polystyrene converted by the gel permeation color layer analysis method) is not particularly limited, and is generally preferably -2,000 to 50,000, 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. Also, Μη is the number average -68- 200928579 molecular weight. [(A2) component] (A2) component having a molecular weight of 500 or more and less than 2000. • The acid dissociable dissolving group exemplified in the description of the above (A 1 ) component is preferably a low molecular compound having a hydrophilic group. . Specifically, a compound in which a part of a hydrogen atom of a hydroxyl group of a compound having a phenol skeleton is substituted with the above-mentioned 0-release inhibitory group or the like. (A2) component, for example, a sensitizer in a g-line or photoresist which is known to be non-chemically amplified, or a part of a hydrogen atom of a low molecular weight phenolic hydroxyl group of a heat-resistant enhancer is inhibited by the above-described acid dissociation dissolution The components of the base can be used arbitrarily. The low molecular weight phenol compound, for example, bis(4-hydroxyphenylalkane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxy)-2-(4-hydroxyphenyl) Propane, 2_(2,3,4-trihydroxyindole)-2-(2',3',4--trihydroxyphenyl)propane, tris(4-hydroxy)methane, bis(4-hydroxyl_3, 5_Dimethylphenyl)_2-hydroxy··methane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyxylmethane, bis(4_hydroxy_3,5 — Dimethylphenyl)- 3,4-ylphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-: dihydroxyphenylmethane, bis(4-hydroxy-3-methyl) Phenyl)-: Dihydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-methylphenyl) -3,4 -dihydroxyphenylmethane, 1 -[1 - (4 - substituted with a complex acid-resolving i-line substituted) tolylphenylphenylphenyl phenyl dihydroxy, 4-, 4- Phenyl-6-hydroxy-69- 200928579 Phenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)B , Phenol, m- cresol, P - 2,3,4 core bodies of a phenolic compound of formaldehyde or cresol-xylenol and the like. Of course, it is not limited to this. The acid dissociable dissolution inhibiting group is not particularly limited, and may be, for example, a content. (A) The components may be used alone or in combination of two or more. φ In the photoresist composition of the present invention, the content of the component (A) may be adjusted such as the thickness of the photoresist film to be formed. &lt;(B) Component&gt; (B) The component is an acid generator (B1) (hereinafter also referred to as (B1)) which is formed by the substance represented by the above formula (bl-Ι). The component (B1) is the same as the compound of the present invention (B1). The component (B1) may be used alone or in combination of two or more. In the photoresist composition of the present invention, (B) In the component (the content of B 1 part is preferably 40% by mass or more, and 70% by mass or more * preferably '100% by mass. Most preferably 75% by mass. When used in the range above the limit' The photoresist composition of the present invention forms a photoresist pattern' to improve lithography characteristics such as resolution, mask reproducibility, focal depth of field, exposure, and line width unevenness (LWR). The acid generator other than the component (B1) (hereinafter also referred to as the component (B2)) may be obtained by using the above (B1) group to shrink the above-mentioned hydrazine to make the compounded component) Tolerance (B2 ingredient -70- [Chemical 4 2]

[In the formula, R1&quot; to R3&quot;, R5&quot;, and R6'' 200928579 (B2), as long as the above (] is not particularly limited, it can be used as a component of an acid generator for a photoresist. The acid generator, for example, an acid generator, an oxime sulfonate acid generator, a diazomethane, a poly(disulfonyl) diazonium Q generator, and a nitrobenzyl sulfonate are produced. As the various key salt acid generators such as a reagent and a diterpenoid acid generator, for example, a compound represented by b - 2 ) can be used. In the formula (b-1), R1" to R3&quot; and together with the sulfur atom in the formula form a ring

a cyclic or cyclical base or a fluorinated alkyl group; at least one of R1" to F R5" to R6&quot; is an aryl group. In the formula (b-1), among R1 to R3 in R1&quot; to R3&quot; (b-1), any of the sulfur atoms may form a ring together. In addition, at least one component other than -71 - U in R1&quot; to R3&quot; is proposed as a chemically amplified iodine salt or strontium salt, such as a dialkyl or bisarylsulfonyl methane. A known compound such as a diazomethane-based acid or an iminosulfonate-based acid. The following general formula (b-1) or (R4SO3 (b-2), each independently an aryl group or an alkane, may be bonded to each other'; R4&quot; is a linear, branched-3n at least 1 Each is aryl, independently aryl or alkyl; formula 2 can be bonded to each other and with an aryl group. R1U to R3'' is preferably 2, 2009,579,579 or more aryl, and R1" to R3&quot It is preferred that all are aryl groups. The aryl group of R1 to R3" is not particularly limited, and is, for example, an aryl group having 6 to 20 carbon atoms, and a part or all of hydrogen atoms of the aryl group may be The alkyl group, the alkoxy group, the halogen atom, the hydroxyl group or the like may be substituted or unsubstituted. The aryl group may be inexpensively synthesized, and it is preferred to use an aryl group having 6 to 1 carbon atoms. For example, a phenyl group, a naphthyl group, etc. Q may be substituted for the alkyl group of the hydrogen atom of the above aryl group, preferably an alkyl group having a carbon number of 丨5, and a methyl group, an ethyl group, a propyl group, and a η-butyl group. And tert_butyl is the most preferable. The alkoxy group which can replace the hydrogen atom of the above aryl group is preferably a methoxy group having a carbon number of 1 to 5, and a methoxy group, an ethoxy group, an η-propoxy group, Iso — propoxy η — butoxy group and tert-butoxy group are preferred. The alkoxy group which may replace the hydrogen atom of the above aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and a methoxy group and an ethoxy group. The base is optimal. G may be substituted for the halogen atom of the hydrogen atom of the above aryl group, and the fluorine atom is preferred. *' Rll R3" is not particularly limited, and may be, for example, a carbon number of 1 - 10 A linear, branched or cyclic alkyl group, etc., which has excellent resolution and the like, is preferably 1 to 5 carbon atoms. Specifically, for example, methyl group, ethyl group, η-propyl group, and isopropyl group. Base, η-butyl, isobutyl, n-pentyl, cyclopentyl, hexyl, cyclohexyl, fluorenyl, fluorenyl, etc., in terms of having excellent resolution and being inexpensively synthesized, The basis is better. Among them, R1&quot; to R3&quot; is the best for phenyl or naphthyl group-72-200928579 (R_&quot; to R3&quot; in formula (b_l), any two can be bonded to each other. And in the case of forming a ring together with the sulfur atom in the formula, it is preferable to form a 3~1 member ring containing a sulfur atom, and it is more preferable to form a ring having a 5 to 7 member ring. In the case of R1&quot; to R3" in the formula (b-1), any two of them may be bonded to each other and form a ring together with the sulfur atom in the formula, and the remaining one is preferably an aryl group. The base is, for example, the same as the aryl group of the above R1&quot; to R3&quot;R4&quot; is a linear, branched or cyclic alkyl group, or a linear, branched or cyclic 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 &quot;, 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 Å. good. 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 fluorine atom in the alkyl group) is preferably from 1 〇 to 1 00%, more preferably from 50 to 100%, particularly in the case where all hydrogen atoms are replaced by fluorine atoms. Those having a fluorinated alkyl group (perfluoroalkyl group) are more preferred because their acid strength is stronger. R4&quot; is preferably a linear or cyclic alkyl group or a linear, branched or cyclic fluorinated alkyl group. In the formula (b-2), R5&quot; and R6&quot; are each independently an aryl group or an alkyl group; -73-200928579 at least one of R5'' and R6&quot; is an aryl group, and R5&quot; and R6&quot; The base is the best. The aryl group of R5" and R6" is, for example, the same as the aryl group of R1&quot; to R3&quot;. _ R5&quot; and R6&quot;'s base, for example, the same as R1&quot; to R3&quot;. Among them, R5&quot; and R6'' are all phenyl groups. Q is the same as R4' in (b-2) and R4&quot; in (b-1). Specific examples of the key salt acid generators represented by the formulae (b-1) and (b-2) are, for example, diphenyliodide trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert) -butylphenyl) iodine trifluoromethanesulfonate or nonafluorobutane sulfonate, triphenylsulfonium trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate , tris(4-methylphenyl)phosphonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, dimethyl hydrazine (4-hydroxynaphthyl) fluorene trifluoromethane a sulfonate, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof, a triphenylmethanesulfonate of monophenyldimethylhydrazine, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof, Phenyl monomethyl* fluorene trifluoromethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methylphenyl) diphenyl sulfonium trifluoromethane sulfonate, Its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate Three (4 Tert-butyl)trifluoromethanesulfonate, heptafluoropropanesulfonate or its nonafluorobutanesulfonate, diphenyl-74-200928579 (1 -(4-methoxy)naphthyl) a trifluoromethanesulfonate, a heptafluoropropanesulfonate or a nonafluorobutanesulfonate thereof, a trifluoromethanesulfonate of bis(1-naphthyl)phenylhydrazine, or a heptafluoropropanesulfonate thereof Nonafluorobutane sulfonate, 1-phenyltetrahydrothiophene key trifluoromethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-(4-methylphenyl) four Hydrothienyl trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-(3,5-dimethyl-4-tetrahydroxyphenyl)tetrahydrothiophene φ III Fluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-(4-methoxynaphthalen-1-yl)tetrahydrothiophene iron trifluoromethanesulfonate, and heptafluoropropane sulfonic acid Ester or its nonafluorobutane sulfonate, 1-(4-ethoxynaphthalen-1-yl)tetrahydrothiophene-trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutanesulfonic acid Ester, 1 (4-η-butoxynaphthalene-1-1-yl)tetrahydrothiophene-trifluoromethanesulfonate, heptafluoropropanesulfonate or its nonafluorobutanesulfonate, 1-phenylthiolanate Fluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, trifluoromethanesulfonate of 1-(4 φ-hydroxyphenyl)tetrahydrothiopyran, its heptafluoropropane sulfonate or Its nonafluorobutane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl*-yl)tetrahydrothiocarbamate trifluoromethanesulfonate, its heptafluoropropane sulfonate or Oxybutane sulfonate, trifluoromethanesulfonate of 1-(4-methylphenyl)tetrahydrothiopyran, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, etc. The anion portion of the gun salt is replaced by a methanesulfonate, η-propanesulfonate, η-butanesulfonate or η-octanesulfonate-75-200928579. Further, the above formula ( In the b-1) or (b_2), the anion moiety may be a key salt acid generator obtained by substituting an anion moiety represented by the following formula (b-3) or (b-4) (the cation moiety and the above formula ( b - 1) or ( b - 2) Same). [化4 3]

〇02S—Y&quot; / &quot;N ...(b-4) O^S—Z&quot; [wherein, X&quot; is an alkylene group having 2 to 6 carbon atoms substituted with at least one hydrogen atom replaced by a fluorine atom; Y" And Z" are each independently an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom. X&quot; is a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the carbon number of the alkyl group is preferably from 2 to 6, more preferably from 3 to 5 carbon atoms, most preferably Carbon number 3. Y", Z&quot; each independently is a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the alkyl group preferably has a carbon number of from 1 to 10, more preferably a carbon number of from 1 to 7. The carbon number is preferably from 1 to 3. The carbon number of the alkyl group of X&quot; or the carbon number of the alkyl group of Y&quot;, Z&quot; is in the above range, based on the reason of excellent solubility to the photoresist solvent, etc. The smaller the better, the more the number of hydrogen atoms in the alkyl group of X&quot; or the alkyl group of Υ&quot;, ζ&quot; is replaced by a fluorine atom, the stronger the strength of the acid, and the higher the energy below 200nrn. When the light or the electron beam is used, it is preferable to improve the transparency. The proportion of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate, is preferably -70 to 200928579, 70 to 100%, more Preferably, it is 90 to 100%, preferably a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are replaced by a fluorine atom. Further, it may be represented by the following formula (b_5) or (b-6). The sulfonium salt of the cation portion is used as a gun salt acid generator.

(b-5) (b-6) wherein R41 to R46 are each independently an alkyl group, an ethyl group, an alkoxy group, a carboxyl group, a hydroxyl group or a hydroxyalkyl group; N6 is an integer of 0 to 2]. In the general formulae (b-5) and (b-6), R41 to R46 are the same as those of R41 to R46 in the above formulae (b·5) and (b1-6). When the symbols ～n6 to R41 to R46 are integers of 2 or more, the respective R41 to R46 of the plural number may be the same or different. m is preferably 〇~2' more preferably 0 or 1' is preferably 0. 112 and 113, preferably independent of each other or 1' more preferably n4 is preferably 〇 〜 2, more preferably 0 or 1. N5 is preferably 〇 or 1, more preferably 〇. N6 is preferably 〇 or 1' is more preferably 1. -77-200928579 The anion portion having a sulfonium salt of the cation portion represented by the formula (b-5) or (b_6) is not particularly limited, and an anion portion which is currently proposed as a key salt acid generator can be used. The same anion part. The anion moiety is, for example, a fluorinated alkylsulfonate ion such as an anion moiety (R4 &quot;S03_) of a key salt acid generator represented by the above formula (b-1) or (b-2); 3) or an anion portion represented by (b-4). Among them, a fluorinated alkylsulfonic acid ion is preferred, and a fluorinated alkylsulfonic acid H ion having a carbon number of 1 to 4 is more preferred, and a linear perfluoroalkylsulfonic acid having a carbon number of 1 to 4 is used. The ions are optimal. Specific examples include a trifluoromethanesulfonate ion, a heptafluoro-n-propylsulfonate ion, a nonafluoro-n-butylsulfonate ion, and the like. In the present specification, the oxime sulfonate-based acid generator has, for example, a compound having at least one group represented by the following formula (B-1), which has a property of generating an acid by radiation irradiation. The above-mentioned oxime sulfonate-based acid generator is generally used for a chemically amplified positive-type photoresist composition, and the present invention can be optionally used. ❹ [Chemical 4 5] —C=N—Ο—S02—R31 R32 · · · (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 limited to any -78 to 200928579, and may be, for example, a fluorine atom, a linear one having a carbon number of 1 to 6, a branched chain or a cyclic alkyl group. Here, the "having a substituent" means that at least one of the hydrogen atoms of the alkyl group or the aryl group is substituted with a substituent. The alkyl group is preferably a carbon number of from 1 to 20, preferably a carbon number of from 1 to 1 Torr, more preferably a carbon number of from 1 to 8, more preferably a carbon number of from 1 to 6, and a carbon number of from 1 to 4. Very good. Among them, the alkyl group is particularly preferably an alkyl group (hereinafter, also referred to as a halogenated alkyl group) obtained by partial or complete halogenation. Further, a partially halogenated alkyl group, ^ means a group in which a 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 alkyl group is preferably a fluorinated alkyl group. The aryl group is preferably a carbon number of 4 to 20, preferably a carbon number of 4 to 10, and more preferably a carbon number of 6 to 10. The aryl group is particularly preferably an aryl group obtained by partially or completely halogenating. Further, a partially halogenated aryl group means an aryl group in which a part of a hydrogen atom is substituted by a halogen atom, and an aryl group which is completely halogenated means an aryl group in which a hydrogen atom is completely substituted by a halogen atom. R31 is particularly preferably an alkyl group having 1 to 4 carbon atoms which does not have a substituent, or a fluorinated group having a carbon number of 1 to 4. • The organic group of R32, preferably a linear, branched or cyclic alkyl, aryl or cyano group. The alkyl group or the aryl group of R32 is, for example, the same as the alkyl group or the aryl group exemplified in the above R31. 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 alkyl group having 1 to 8 carbon atoms. The oxime sulfonate-based acid generator is more preferably, for example, a compound represented by the following formula (B-2)-79-200928579 or (B-3). [Chem. 4 6] R34—C=N—Ο—S02—R35 —C=l R33 (B-2) − [In the formula (B_2), R33 is a cyano group, and has no substituents. Halogenated alkyl; R34 is aryl; R35 is a pendant or halogenated alkyl group having no substituent. © [Chem. 4 7] R37--C=N——Ο——S02——R38 R36 &quot; - JP · . . (B-3) [In the formula (B_3), R36 is a cyano group and has no substituent. Or a halogenated alkyl group; R37 is a 2 or 3 valent aromatic hydrocarbon group; R38 is an alkyl group having no substituent or a halogenated alkyl group, and 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 most preferably a carbon number of 1 to 6. Preferably, the fluorinated alkyl group is more preferably. The fluorinated alkyl group in R3 3 is preferably a fluorine atom in the alkyl group which is fluorinated at 50% or more, more preferably 70% or more and 90%. The above is best fluorinated. R34 aryl group, such as phenyl or biphenyl, fluorenyl, naphthyl, anthryl, phenanthryl and other aromatic hydrocarbon ring removal a group of one hydrogen atom and a carbon atom of the ring constituting the aforementioned group -80-200928579 a heteroaryl group obtained by substituting a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, etc. More preferably. R34 aryl group, which may have a carbon number A substituent such as an alkyl group, a halogenated alkyl group or an alkoxy group of 1 to 1 fluorene may be used. The alkyl group or the halogenated alkyl group in the substituent is preferably _ carbon number 1 to 8, and carbon number 1 to 4 is Further, the halogenated alkyl group is more preferably a fluorinated group. The alkyl group or the halogenated alkyl group having no substituent of R35 is preferably a carbon number of 1 to 10, and a carbon number of 1 to 8. Preferably, the carbon number is preferably from 1 to 6. R35 is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group. The fluorinated alkyl group in R35 is fluorinated with a hydrogen atom of an alkyl group of 50% or more. Preferably, it is more preferably 70% or more, and when 90% or more is fluorinated, it is more preferable to increase the acid produced. The best one is a perfluorination in which 1% by mole of hydrogen atoms are replaced by fluorine. In the above formula (B-3), the alkyl group or the halogenated alkyl group having no substituent of R36 is, for example, the same as the alkyl group having no substituent or the halogenated G alkyl group represented by the above R33. The 2 or 3 valent aromatic hydrocarbon group, for example, a group obtained by further removing 1 or 2 hydrogen atoms from the aryl group of the above R34, etc. • an alkyl group having no substituent or a halogenated alkyl group of R38, for example, As shown in the above R3 5 The alkyl group or the halogenated alkyl group having no substituent is the same content 〇p&quot; preferably 2. Specific examples of the oxime sulfonate-based acid generator, such as α-(p-toluenesulfonyloxyimino) Benzyl cyanide 'α — ( ρ -chloro-81 - 200928579 phenylsulfonyloxyimido)-benzyl cyanide, α-(4-nitrophenylsulfonyloxyimido)_ Benzyl cyanide, (4-nitro- 2-trifluoromethylbenzenesulfonyloxyimido)-benzyl cyanide, hydrazine: -(phenylsulfonyloxyimino)_4 monochlorobenzyl cyanide Compound, (phenylsulfonyloxyimido)_2,4 _ _dichlorobenzyl cyanide, α-(phenylsulfonyloxyimino)_2,6-dichlorobenzyl cyanide, α -( Phenylsulfonyloxyimido)-4-methoxybenzyl cyanide, α-(2-chlorophenylsulfonyloxyimino)-1,4-methylsulfonylbenzyl cyanide, (phenylsulfonate) Oxyimido)-thiazol-2-ylacetonitrile, α-(4-dodecylbenzenesulfonyloxyimino)-benzyl cyanide, α-[(ρ-toluenesulfonyloxyimido) ) 4-1,4-methoxyphenyl]acetonitrile, α-[(dodecylbenzenesulfonyloxy) Imino)) 4-methoxyphenyl]acetonitrile, α-(p-toluenesulfonyloxyimido)-4-yl-cyanide, α-(methylsulfonyloxyimino)-1 ring Pentenyl acetonitrile, α-(methylsulfonyloxyimido)_1_cyclohexenylacetonitrile, a-(methylsulfonyloxyimino)- 1 -cycloheptenylacetonitrile, (methyl sulfhydryl) Sulfomethoxyimido)-1 -cyclooctenylacetonitrile, (trifluoromethylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyl) -cyclohexylacetonitrile, α-(ethylsulfonyloxyimido) • _ethylacetonitrile, (propylsulfonyloxyimino)-propyl acetonitrile, α-(cyclohexylsulfonyloxyimido) )-cyclopentylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonate)醯Ominoimido)_1-cyclopentenylacetonitrile, α-(isopropylsulfonyloxyimino)-1,4-cyclopentenylacetonitrile, α-(H-butylsulfonyloxyimino)-1 Cyclopentene-82- 200928579 based acetonitrile, α — ( Alkylsulfonyloxyimido)-1 monocyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(η-butylsulfonyloxyimine (1)-cyclohexenylacetonitrile, α-(methylsulfonyloxyimido)-phenylacetonitrile, (methylsulfonyloxyimido)-fluorenyl-methoxyphenylacetonitrile, α-( Trifluoromethylsulfonyloxyimido)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-fluorenyl-methoxyphenylacetonitrile, α-(ethylsulfonic acid imine a) p-methoxyphenylacetonitrile, α-(propylsulfonyloxyimido)-indole-methylphenylacetonitrile, α-(methylsulfonyloxyimino)-hydrazine-bromo Further, the phenylacetonitrile acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei 9-208554 (paragraphs [〇〇12] to [0014] [Chem. 18] to [Chem. 19]), W02004/ The sulfonate-based acid generator disclosed in 074242A2 (Examples 1 to 40 on pages 65 to 85) may also be used in combination. Further, for example, a compound shown below or the like is suitable. Ο 【化4 8】

H3C—C=N—0S02-(CH2)3CH3 H3C—C=N—-0S02-(CH2)3CH3

C-=N—〇—S〇2—(CF2)6-H

C=N—〇—S〇2—C4p9 {CF2)4-H Diazomethine acid generator, double-base or double-fang (4) __ A specific case of a hospital, such as double (iso-di-base expansion) Diazo A double-83- 200928579 P-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazo Methane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and the like. Further, a diazomethane-based acid generator disclosed in JP-A-H05-035551, JP-A-11-035552, and JP-A-11-035573 is also suitable. Further, poly(disulfonyl)diazomethanes, such as 1,3 -bis(phenylsulfonyldiazomethylsulfonyl)propane, 1, 4 disclosed in JP-A-11-q 322707 _Bis(phenylsulfonyldiazomethylsulfonyl)butane, 1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane, 1,10-bis(phenylsulfonate) Mercaptodiazepinesulfonyl)decane, 1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane, 1,3-bis(cyclohexylsulfonyldiazomethyl) Sulfhydryl)propane, 1,6-bis(cyclohexylsulfonyldiazomethylsulfonyl)hexane, 1,1 〇 bis(cyclohexylsulfonyldiazomethylsulfonyl)hydrazine Alkane, etc. The φ (B2) component may be used alone or in combination of two or more. · When the (B2) component is added, the ratio of the component (B2) in the component (B) is preferably from 10 to 99% by mass, and from 25 to 95% by mass based on the total mass of the component (B). For better, the best is 50 to 95% by mass. When the ratio of the component (B2) is within the above range, the balance with the component (B1) can be obtained, and the lithographic etching property can be improved. In the photoresist composition of the present invention, the content of the component (B) is 0.5 to 30 parts by mass, preferably 1 to 84 to 200928579 to 20 parts by mass, per part by mass of the component (A). In the above range, the pattern can be sufficiently formed. To a homogeneous solution, with good preservation stability. &lt;arbitrary component&gt; _ In the photoresist composition of the present invention, when the post expo sure stability of the latent formed by the pattern — wise exposure of the resis φ , The nitrogen-containing organic compound (D) of any component is also referred to as (D) component). As the component (D), there have been proposals for various compounds, and any of the known components is used, and among them, an aliphatic amine, particularly an aliphatic amine or a tertiary aliphatic amine is preferred. Wherein, the aliphatic amine is an amine of more than one aliphatic group, and the aliphatic group is an aliphatic amine having a carbon number of 1 to 12 Å, for example, an alkyl group or a hydroxyalkane having at least one hydrogen atom of 氨 12 or less in the ammonia nh 3 . The resulting amine (alkylamine or) or cyclic amine is substituted. Specific alkylamines and alkanolamines such as η-hexylamine, n_•, η-octylamine, n-mercaptoamine, n-mercaptoamine, etc. monoalkylaminoamine, di-n-propylamine a dialkylamine such as di-n-heptylamine, di-n- or dicyclohexylamine; trimethylamine, triethylamine, monopropylamine, tris-n-butylamine, tri-n - trialkyl groups such as hexylamine, tris-amine, tri-n-heptylamine, tri-n-octylamine, tri-n-, tri-n-decylamine, tris-n-dodecylamine Amine and available image layer (the following may also be a secondary lipid having a carbon number of alkanolamine heptylamine: diethylene octylamine tri-n η-pentamethyleneamine: di- 85- 200928579 Alkanolamines such as alkanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, and carbon number 5~10 The alkyl group is preferably a trialkylamine having three nitrogen atoms, and is preferably a tri-n-pentylamine. A cyclic amine such as a heterocyclic compound containing a nitrogen atom as a hetero atom. a compound that can be a monocyclic compound (fat) Monocyclic amines, or polycyclic compounds (aliphatic polycyclic amines) may also be φ aliphatic monocyclic amines, specifically, for example, piperidine, piperazine, etc. The amine is preferably a carbon number of 6 to 10, specifically, for example, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4. 0] - 7 - undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, etc. They may be used singly or in combination of two or more. D) 100 parts by mass of the component (A) component, generally in the range of 〇〇.〇1 to 5.0 parts by mass. The photoresist composition of the present invention is used to prevent deterioration (Deterioration *-in sensitivity) or to enhance light. An organic carboxylic acid and a phosphorus oxyacid having an optional composition and the like, and a post exposure stability of the latent image formed by the pattern — wise exposure of the resist layer At least one compound (E) selected from the group consisting of derivatives (hereinafter also referred to as (E) component). Such as acetic acid, malonic acid, citric acid, malic acid, amber -86- 200928579 peric acid, benzoic acid, salicylic acid, etc. Pity oxyacids, such as phosphoric acid, phosphonic acid (Phosphonic acid), phosphinic acid (Phosphinic acid), etc., which is preferably a phosphonic acid. An oxo acid derivative of phosphoric acid, for example, an ester group obtained by substituting a hydrogen atom of the above-mentioned oxo acid with a hydrocarbon group, and the like, for example, a carbon number of 1 to 5 An alkyl group, an aryl group having 6 to 15 carbon atoms, and the like. Phosphoric acid derivatives such as phosphoric acid such as di-n-butyl phosphate or diphenyl phosphate. Phosphonic acid derivatives such as dimethyl phosphonate, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, diphenyl phosphonate, diphenyl phosphonate, and the like. Phosphinic acid derivatives such as phosphinates such as phenylphosphinic acid. (E) The components may be used singly or in combination of two or more. The component (E) is preferably an organic carboxylic acid, particularly preferably salicylic acid. The component (E) is usually used in an amount of from 1 to 5.0 parts by mass based on 1 part by mass of the component (A). • The photoresist composition of the present invention can be further blended with an additive which is suitable for mixing, for example, an additive resin which can improve the properties of the photoresist film, a surfactant for improving coating properties, a dissolution inhibitor, a plasticizer, and stability. Agents, colorants, halo inhibitors, dyes, and the like. &lt;Organic solvent (S) &gt; -87- 200928579 The photoresist composition of the present invention can be produced by dissolving a material in an organic solvent (s) (hereinafter also referred to as (S) component). The component (S) can be used as long as it can dissolve the components to be used in a uniform manner. For example, one or two or more kinds of the above-mentioned conventional solvents can be used as the chemically amplified resist solvent. For example, lactones such as r-butyrolactone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentanone, methyl isoamyl ketone, and 2-heptanone: ethanediol, Polyols such as diethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, etc. a compound; a polyether or a monoalkyl ether or a monophenyl ether such as monomethyl ether, monoethyl ether, monopropyl ether or monobutyl ether having an ester-bonded compound; a derivative of a polyol such as a compound (wherein, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred); a cyclic ether such as dioxane; or a lactate Ester, ethyl lactate (EL), methyl acetate oxime, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate and other esters Anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenylethyl ether, butylbenzene, ethyl ether, ethylbenzene, diethyl Benzene, 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, among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and ethyl lactate (EL) -88 - 200928579 are preferably used. Also, PGMEA can be used to dissolve with the polar agent. The addition ratio (mass ratio) may be appropriately determined depending on the PGMEA property or the like, and is preferably in the range of 1:9:8 to 8:2. More specifically, the polar solvent is preferably used in the form of milk I PGMEA : EL: 1:9 to 8 to 8:2. When the polar solvent is PGME, the mass is preferably from 1:9 to 9:1, more preferably from 3:7 to 7:3. Further, among the (S) components, among the other mixed ratios of at least one selected from E and r-butyrolactone, the former and the latter are superior in quality (S), and the use amount is not particularly limited. The concentration of the substrate or the like, the thickness of the coating film, and the like can be suitably used in the range of the solid content of the photoresist composition of 2 to 5 to 15% by mass. <<Formation Method of Photoresist Pattern>> The method for forming a photoresist pattern of the present invention is a step of exposing a photoresist film to a resist formed on a support, and developing the photoresist film. When the mixed solution of the hydrazine is mixed with the polar solvent to 9:1, more preferably 2 ethyl acrylate (EL), 9:1, more preferably 2:8 PGMEA: PGME: 8 to 8: 2, The best white PGMEA and EL solvent are preferred. At this time, it is 70: 30~95: 5, generally can be matched with the coating selection setting, generally ~20% by mass, preferably including the step of using the above-mentioned hair, forming the photoresist pattern step -89 - 200928579 The method for forming the photoresist pattern of the present invention can be carried out, for example, in the following manner. That is, first, the photoresist composition of the present invention is applied onto a support by a spin coater or the like, and then subjected to a temperature condition of 80 to 150 ° C for 40 to 120 seconds. After 60 to 90 seconds of post-application bake (PAB), and then using an ArF exposure apparatus, the ArF excimer laser light is selectively exposed to 0 by the desired mask pattern. Post-exposure bake (PEB) is carried out for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of 80 to 150 °C. Next, it is subjected to development treatment using an alkali developer, for example, 1.1~1 〇 mass% tetramethylammonium hydroxide (TM AH) aqueous solution, preferably washed with pure water, and then dried. Further, if necessary, baking treatment (post-baking) may be performed after the above development treatment. In this way, a photoresist pattern of a faithful response mask pattern can be obtained. The support is not particularly limited, and a conventionally known article such as a substrate for an electronic component or an article having a specific wiring pattern formed thereon can be used. More specifically, for example, a substrate such as a germanium wafer, copper, chromium, iron, or aluminum, or a glass substrate. For wiring pattern materials, for example, copper, inscription, nickel, gold, etc. can be used. Further, for example, an inorganic or/or organic film may be provided on the substrate. An inorganic film such as an inorganic antireflection film (inorganic BARC). Organic film, such as organic anti-reflective film (organic BARC).

The wavelength used for exposure is not particularly limited, and ArF-90- can be used.

200928579 Excimer laser, KrF excimer laser, F2 excimer f ultraviolet light, VUV (vacuum ultraviolet light) 'EB (electric soft X-ray and other radiation. The above photoresist composition, sub-laser, ArF excimer thunder Shot, ΕΒ or EUV, special-molecule laser is effective. Exposure of photoresist film can be exposed to air or nitrogen, etc. I usually expose (dry exposure), or immersion exposure. Immersion exposure, as mentioned above, It is a state in which a lens of an inert gas such as air or nitrogen is exposed to light and a light Pi on a wafer is filled with a refractive index having a refractive index larger than that of air. More specifically, the immersion exposure is to fill a lens having a refractive index of a large amount (immersion medium) between the lenses at the lowest position of the exposure device of the above-mentioned J, and expose the desired photoresist pattern. (Infiltrating Exposure) The immersion medium is preferably a solvent having a refractive index lower than that of the light-receiving film which is exposed to the immersion exposure. The refractive index of the solvent is not particularly limited as long as it is. A solvent having a refractive index larger than that of air and having a small refractive index is, for example, water, a fluorine-based inert solvent, a hydrocarbon solvent or the like. Specific examples of the fluorine-based inert liquid are, for example, C3HC12F5, c4f90C2h5, c5h3f7 and other fluorine-based compounds, which are mainly composed of "emission, EUV (pole line), X-ray, and KrF, which are respectively used in the ArF quasi-t body". Part of the film between the film (the immersion medium obtained by the photoresist film and the rate of light is in a state of air, by means of a large ratio, and the refractive index is small, the photoresist film in the above range Refractive liquid, lanthanide, liquid of C4F9OCH3', etc., 200928579 is preferably a boiling point of 70 to 180 ° C, more preferably 80 to 160 ° C. In a fluorine-based inert liquid, the boiling point is within the above range. In the case of the substance, after the end of the exposure, the medium used for the wetting type can be removed in a simple manner, and it is preferably a fluorine-based liquid, in particular, a perfluoro group in which all hydrogen atoms in the alkyl group are replaced by fluorine atoms. The alkyl compound is preferably a perfluoroalkyl compound, specifically, for example, a perfluoroalkyl ether compound or a perfluoroalkylamine compound, etc. Q Further, more specifically, the above perfluoroalkyl ether compound, for example, Fluorine (2-butyl-tetrahydrofuran) The boiling point is 10 ° C), the perfluoroalkylamine compound, for example, perfluorotributylamine (boiling point 174 ° C), etc. The above-mentioned photoresist composition of the present invention has a novelty that has not been known in the past. The photoresist composition of the present invention has a perfect circle for improving the reproducibility of the mask when the photoresist pattern is formed (for example, a mask linearity or a mask error factor, and a through hole pattern is formed). And the like, but a photoresist pattern having good lithographic etching characteristics can be formed. The reason for this is still unclear, but it is presumed that it should be the following factors. In the photoresist composition of the present invention, the acid generator is used as described above ( B 1 ) *- Ingredients - The anion portion of the above (B1) component has a polar group on the skeleton of "Y1 - SO," which is based on the "-Q1 - 0 - CO -" bond ring skeleton ( The structure obtained by the ring of high bulk density of X—,—C(=0)—0-). Therefore, it exhibits high polarity when compared with the fluorinated alkylsulfonic acid ion used as an anion in the past, and has a high-dimensional fluffy structure. It is presumed that it has high polarity, so it is based on mutual Function, again, -92- 200928579 Based on its fluffy three-dimensional structure, the anion of the acid generator such as nonafluorobutane sulfonate and the like, regardless of the group having a smaller carbon number of y1 and 1 to 4 When the portion is compared, the diffusion of the anion portion in the photoresist film is chemically or physically inhibited. Therefore, when the (Β 1 ) component is used, the acid diffusion in the exposed region can be suppressed from diffusing to the unexposed region. As a result, the difference in solubility (solubility contrast) between the unexposed area and the exposed area can be improved, and it is presumed that the shape of the resist pattern such as the roundness of the through hole can be improved. For the same reason, You can also expect an increase in exposure latitude (EL Marge) or focus depth of field (DO F ). Exposure latitude (EL Marge) refers to the exposure range that can form a resist pattern when the exposure size is shifted for a certain range, that is, a faithful reaction mask can be obtained. The exposure range of the resist pattern of the mask pattern; the exposure latitude (EL Marge ), the larger the number, the smaller the amount of change in the pattern size caused by the variation of the exposure amount, so that the process can be improved The tolerance is preferred. DOF refers to the range of the focal depth of the resist pattern that can be formed when the focus is shifted up and down for the same exposure amount, that is, the target depth is offset within a certain range. The range of the depth of focus of the resist pattern of the reaction mask pattern is larger, and the larger the number, the better. Further, the alkyl chain of the alkyl group or the fluorinated alkyl group of Y 1 exhibits good decomposability with respect to the hard-to-decompose property of the perfluoroalkyl chain having 6 to 10 carbon atoms, and biodegradability is considered. Views such as processing can also achieve a safer effect. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, and is not limited by the examples. [Example 1] (i) 150 g of methyl fluorosulfonate (difluoro)acetate and pure Z were kept at 1 Torr or less in an ice bath, and 30% of hydroxide was added dropwise to 3 43 · 6 g. After the dropwise addition, the mixture was refluxed at 100 ° C for 3 hours, and neutralized with concentrated hydrochloric acid. The obtained solution was added dropwise to 8888 g of acetone, and filtered and dried to give a white solid compound (I) 1 8 4.5 g 8 8.9 %, yield: 9 5 · 5 % ). [化4 9] © Θ μ* Θ ©

Na O-C—CF2-S-0 Na

L II Ο (I) (ii) 56.2 g of the compound (I), 562.2 g of acetonitrile, 77.4 g of toluenesulfonic acid monohydrate, and refluxed under 3, were filtered, and the filtrate was concentrated and dried. The obtained solid t-butyl methyl ether was stirred at 900 g. Thereafter, the filtrate was filtered to give a white solid compound (π) 22.2 g 9 1 · 〇 %, yield: 4 4 _ 9 % ). However, after the sodium solution of 3 75 g is cooled, the crystallization is carried out (purity: η 9 NaOH CH3-〇-C-CF2-S-F - "tl ο

, add P hours. Among them, added and dried (purity: -94- 200928579 [chemical 5 0]

Oor II II V: HO - 0 - CF2 - swallowing Θ Θ D Na Ο (Π) - (iii) Compound (π1) 5.00g represented by the following formula (ir), compound (II) 3.23g (Purity: 91.0%), 32.2 g of dichloroethane, P-toluenesulfonic acid monohydrate and 328328 g were added, and refluxed at 110 ° C for 21 hours. Thereafter, 49.4 g of methyl ethyl ketone was added to the residue by filtration, followed by stirring. Thereafter, the filtrate was filtered and dried to give a white solid compound (yield: 2.62 g (purity: 43.8%, yield: 21.3%).

(m [Example 1 to 2] The same compound (III) as the compound produced in Example 1 was produced according to the following steps (i') to (iii'). Further, the following steps (Γ)~(iii) The reaction in ') was carried out in the same manner as in the steps (i) to (iii) of Example 1 except that the dichloroethane used in (iii) of Example 1 was changed to toluene. In 192.1 g of methyl fluorosulfonate (difluoro)acetate and 480 g -95 to 200928579 of pure water, it was kept at 10 ° C or less in an ice bath, and 440 g of a 30% aqueous sodium hydroxide solution was added dropwise thereto. After dripping, 10 (TC) was added. After refluxing for 3 hours, after cooling, it was neutralized with 10% hydrochloric acid. The obtained solution was added dropwise to 90 74 g of acetone, and the crystallization was filtered and dried to give a white solid compound (I) 25 7.6 g (purity: 80.7%) , yield: 94.5%). (ii1) In the above compound (I), (5) g of 56.2 g of acetonitrile 562.2 g, add 卩p-toluenesulfonic acid monohydrate and 77.4 g at 110 ° C q After refluxing for 3 hours, the filtrate was concentrated by filtration and dried, and 900 g of t-butyl methyl ether was added to the obtained solid, followed by stirring. The filtrate was dried to give a white solid compound (yield: 25.7 g (purity: 9 1 · 0 %, yield: 5 2.0 %). (iii') The compound (Π) obtained in the above (ii') 5.00 g (Purity: 9 1.0%), 3.69 g of compound (ΙΓ), 25.00 g of toluene, p-toluenesulfonic acid monohydrate (K410g, refluxed at 110 ° C for 20 hours. Thereafter, filtered, residue After adding methyl ketone 7 9.5 0 g, it was stirred and stirred. After that, the filtrate was washed twice with methanol 23·8 6 g, and the obtained precipitate was dried to give Compound (III) 4 as a white solid. · 5 5g •- (purity: 9 7 · 5 %, yield: 5 5.8 %). [Example 1-3] Compound (II) obtained in (ii') of Example 1-2 5.00g (purity : 91.0%), compound (ΙΓ) 3.69 g, toluene 25.00 g, P-toluenesulfonic acid monohydrate and hydrazine 2 1 〇g ' were added and refluxed at 1 1 ° C for 2 6 hours. Thereafter, Filtration, adding methyl ethyl ketone 79.5 0 g to the residue, followed by stirring -96-200928579. After that, 'filtered, the filtrate was washed twice with methanol 23.8 6 g, and the resulting precipitate was obtained. Results dry to give a white solid of compound (III) 3.15g (purity: 99.7 ° /, yield: 39.5%). _ [Example 1 - 4] In the compound (II) obtained in (ii') of Example 1 - 2, 5.00 g (purity: 91.0%), compound (π') 2 - 95 g, toluene 25.00 g, φ added P - Toluenesulfonic acid monohydrate and 0.21 g of water were refluxed at 110 ° C for 24 hours. Thereafter, 6 3.6 g of methyl ethyl ketone was added to the residue by filtration. After that, the filtrate was filtered and the filtrate was washed twice with methanol 19.08 g, and the obtained precipitate was dried to give a white solid compound (III) 4.07 g (purity: 9 9 · 8 %, yield: 6 3 -9 %). When Example 1 was compared with Examples 1-2 to 1_4, Example 1 in which a solvent was used for the reaction of the compound (II) with the compound (π·), and Example 1 to 2_4 in which toluene was used. The purity and yield of the obtained hydrazine compound (πι) are greatly improved. Further, in the case of Example 1-3, when compared with Example 1 - 4, the ratio of the compound (I Γ ) used in the compound (II) was small, and the example 1 - 4' was short. Time to produce high purity compound (III) in good yield. [Example 2] 1.36 g (purity: 43.8%) of the compound (in) was dissolved in 13.6 g of pure water. To the solution, a solution of 5.10 g of dichloromethane dissolved in triphenylsulfonium bromide-97-200928579 〇-5 1 g was added, and the mixture was stirred at room temperature for 3 hours, and then the organic phase was separated by filtration. Further, the organic phase was washed with pure water of 1 8 · 6 g, and the organic phase was concentrated and dried to give a compound (IV) of 0.23 g (yield: 26.8%) of a colorless viscous liquid. [化5 2]

Compound (IV) was analyzed by NMR. H-NMR (DMSO - d6, 400MHz): ¢5 (ppm) = 7.89~7.77 (m, 15H, Ha), 5.48 (m, lH, Hb), 4.98 (s, lH, Hc), 4.73~4.58 (d, 2H, Hd), 2.71 (m, 1 H &gt; He ), 2.1 4 (m, 2H, Hf). 19F - NMR (DMSO - d6 ' 376MHz) : δ (ppm) = -107.1. From the above results, it was confirmed that the compound (IV) had the structure shown below. -98- 200928579 【化5 3】

[Example 3] The compound (V) shown below was produced in the following order. 【化5 4】

(V) Add a small amount of phosphorus oxide (8.53g) and 2,5-dimethylphenol (8.81g) and diphenylarsine in a small amount in methanesulfonic acid (60.75 g) controlled below 20 °C. 12.2g). After the temperature was controlled at 15 to 20 ° C for 30 -99 to 200928579 minutes, the temperature was raised to 40 ° C, and the mixture was aged for 2 hours. After the reaction liquid was poured into pure water (1 〇 9.35 g) cooled to 15 ° C or less, dichloromethane (54.68 g) was added to the methane layer after stirring. After adding another 20 to 25 ° C of hexane in another container, the dichloromethane layer was dropped. After the completion of the dropwise addition, the mixture was aged at 20 minutes for 30 minutes, and the result was filtered to obtain a desired compound of 0.9%. The compound (hereinafter referred to as 'the compound (5 _ 1 咜-NMR) was analyzed, and the results are shown below. !H-NMR (DMSO - d6, 600 MHz): &lt;5 ( 7.61 - 7.72 ( m &gt 10H, phenyl), 714 ( s » 2H 3 -12 ( s ' 3 H, Hb ) 5 2.22 (s - 6Hj Ha). From the above results, it was confirmed that the compound (5 _ 1 ) has a structure. 5] Thereafter, the solution is distilled to recover dichloro (386.86g ~ 2 5 〇C under the product (yield)) in ppm) = , He ), as shown below

The compound (5-1) (4g) was dissolved in dichloromethane. After the dissolution, 'addition of cesium carbonate (6.87g), add -100-79.8g) bromoacetic acid 200928579 methyl adamantane (3.42g) . After refluxing for 24 hours, it was filtered, washed with water and crystallized from hexane. The obtained powder was dried under reduced pressure to give the title compound (yield: 66%). This compound (hereinafter, also referred to as compound (5-2)) was analyzed by 1 Η-NMR. The results are shown below. *H-NMR (CDC13 '600MHz) : δ (ppm) = 7.83 - 7·86 ( m,4Η,phenyl) , 7.69 - 7.78 ( m,6H , phenyl )

, 7.5 1 ( s, 2H, Hd ) , 4.46 ( s, 2H, He) , 2.39 ( s, 6H ' Ha ) ‘ 2.3 3 ( s, 2H, Adamantane ) , 2.17 ( s, 2H,

Adamantane) ' 1.71 — 1.976 ( m,11H,Adamantane), 1 · 6 8 ( s ' 3 H ' Hb ) 5 1.57— 1.61 ( m &gt; 2H &gt; Adamantane) From the above results, confirm the compound (5 - 2) It has the following structure. ❹ -101 - 200928579 【化5 6】

Compound (5-2) (1.798) was dissolved in a mixed solution of water (15.81 lb) and hydrazine methylene chloride (31.62 g), and thereafter, a small amount of compound (III) obtained in Example 1-4 was added in a small amount (purity). 99.8%) ( 1.33g ' ), stirred at 25 ° C for 1 hour. After completion of the reaction, the dichloromethane solution was washed with water and concentrated to dryness. The obtained powder was washed with hexane and then dried under reduced pressure to give the title compound (V) 2 · 3 5 g (yield 8 3 · 3 %). The compound (V) was analyzed by iH-NMR. The results are shown below. NMR ( DMSO — d^, 400 MHz) : δ (ppm) = -102- 200928579 7.76 — 7.8 8 ( m, 10H, Phenyl ) , 7.63 ( s, 2H &gt; 5.51 ( s &gt; 1H, Hd ) , 5.01 ( s, 1H, He), 4.62 - m, 4H, Hc + Hf), 2.75 (m, 1H, Hh), 2.53-m, 1 9 H, Hg + Adamantane ). 19F-NMR (DMS〇-d6, 400MHz): δ (ppm -106.7).

Hb), 4.76 (1.5 1 (The above results show that the compound (V) has a lower structure.

[化5 7]

-103-200928579 [Example 4] The compound (VI) shown below was produced in the following order. 【化5 8】

〇(VI) (i&quot;) in the compound (Π) 17.7g (purity: 91 · 0%), the compound (ΙΓ) 13g, toluene 88.3g, added p-toluenesulfonic acid monohydrate and 5. 5 5 g , reflux at 1 30 ° C for 6 6 hours. Thereafter, the mixture was filtered, and 79.9 g of methyl ethyl ketone was added to the residue, followed by stirring. Thereafter, 84.0 g of methanol was added thereto by filtration, followed by stirring. The filtration was again carried out, and the compound (III) was obtained as a white solid (20.2 g (purity: 99.9% 、, yield: 7 2.1%). [化5 9]

(ii&quot;) 15.0 g (purity: 99.9%) of the compound (III) obtained in the above (i&quot;) was dissolved in 66.4 g of pure water. To the solution, a solution of 132.8 g of dichloromethane in which 13.3 g of 4-methylbromide bromide was dissolved was added, and -104-200928579 was stirred at room temperature for 3 hours, and then the organic phase was separated. The organic phase was washed with pure water (6 6.4 g), and the organic phase was concentrated and dried to give the desired compound (VI) (20.2 g) (yield: 88.1%). [化60]

This compound (VI) was analyzed by NMR. The results are shown below. !H- NMR (DMSO-άβ '600MHz) : δ (ppm)=

7.86 to 7.58 (m, 14H, Ha+Hb), 5.48 (m, lH, Hd), 4.98 (s, 1H, He), 4.73 to 4.58 (d, 2H &gt; Hf) ' 2.71 ( m, 1H, Hg ), 2·43 ( m, 3H, He ), 2.12 ( m, 2 H, Hh ) ° 19F - NMR ( DMSO - d6, 376MHz ) : &lt;5 (ppm) = -1 0 6 · 9 o As a result, it was confirmed that the compound (VI) had the structure shown below. -105- 200928579

【化6 1】

[Example 5] The compound (VII) shown below was produced in the following order.

Ο

Θ (VII) Diphenyl iodide methanesulfonate 2. lg, compound (ΙΠ) (purity: 99.8%) 2.0 g, pure water 1 methane (20.4 g) were added, and the mixture was stirred at room temperature for 2 hours. There will be a compound which is washed with pure water 10.2g, the organic phase is crystallized from hexane, _2g obtained by -106-1_4, dichloro; phase separation liquid, = white solid 200928579 (hereinafter, also referred to as compound ( 7 - 1 ) ) 2 · 1 5 g (yield: 6 7.1 %). 【化6 3】

This compound (7-1) was analyzed by NMR. The results are shown below. - NMR ( DMSO - d6 ' 600MHz ) : δ (ppm) = 8.17 - 8.29 (d, 4H, Ha), 7.64 - 7.68 (t, 2H, Hc), 7.49 - 7.58 (t, 4H, Hb ), 5.46 ( t,1H,Hd) &gt; 4.97 ( s ,1H,He) , 4.57 - 4.70 ( d &gt; 2H,Hf) ' 2.70 - 2.72 ( m ,lH,Hg) ,2.11-2.16 (m,2H,Hh) . 19F - NMR (DMSO - d6, 3 76MHz): δ (ppm) = -107.14 &gt; A 106.98. From the above results, it was confirmed that the compound (7 - 1 ) had the structure shown below. -107 200928579 【化6 4】

A mixed liquid of 0.42 g of dibenzothiophene, 1.5 g of the compound (7-1), 0.019 g of copper (II) benzoate, and 2.25 g of chlorobenzene was stirred at 100 ° C for 1 hour. 13.15 g of hexane was added dropwise to the reaction mixture, and the obtained powder was dissolved in 13.15 g of dichloromethane, washed with 13.1 5 g of a 1% aqueous ammonia solution, and washed three times (13.15 g). The organic phase was crystallized from hexane to give Compound (VII): </ RTI> </ RTI> </ RTI> 5 g (yield: 80.2%). 【化6 5】 ❹

(VII) The obtained compound (VII) is shown below. *H-NMR (DMSO - 8.50 - 8.52 (d &gt; 2H &gt; Ha) was analyzed by NMR. The result was as d6 '600 MHz) · (5 (ppm) = , 8.32 - 8.38 (d, 2H, Hd) -108- 200928579 7.91-7.97 (t,2H,Hb), 7.67-7.70 (t,2H,Hc), 7.52 - 7.63 ( m &gt; 5H,phenyl ) , 5.45 - 5.47 ( t,1H,He ), 4.97 ( s,1H,Hf ) , 4.57 - 4.7 1 ( d,2H,Hg), 2.69-2.72 (m,1H,Hh) , 2.04-2.15 (m,2H,Hi) 19F - NMR ( DMSO - d6, 3 76 MHz) : δ (ppm) = -1 07.20, a 106.99. From the above results, it was confirmed that the compound (VII) has the structure shown below.

[Example 6] The compound (VIII) shown below was produced in the following order.

〇 (VIII) -109- 200928579 After adding 6.50 g of phosphorus pentoxide in a small amount to 33.6 g of methanesulfonic acid, 7.48 g of 2,6-dimethylanisole and 9_17 g of dibenzothiophene oxide were added. After stirring at a temperature of 45 ° C for 2 hours, 90 g of pure water and 150 g of hexane were added. The aqueous layer was obtained by liquid separation. To the 61.02 g of the aqueous solution obtained above, 61.02 g of dichloromethane was added, and the compound (III) obtained in Example 1-4 (purity 9 9.8%) was added, and the mixture was stirred for 1 hour. The organic solvent layer was washed three times with 60 g of pure water, and then crystallized from hexane to give 5.44 g (yield: 75.3%) of Compound ( VIII) as a white solid. Further, in the following chemical formula, Me represents a methyl group. 【化6 8】

One Me-S03

The obtained Compound (VIII) was analyzed by NMR. The results are shown below. 'H-NMR (DMSO-d6 '400MHz): &lt;5 (ppm) = 8.49-8.51 (d &gt; 2H &gt; Ha ) , 8.31 - 8.35 (d, 2H, Hd), 7.9 - 7.96 ( t - 2H , Hb), 7.72 - 7.76 (t &gt; 2H, He), 7.31 (s, 2H, He), 5.45-5.47 (t, lH, Hf), 4.97 (s -110- 200928579

,1H,Hg),4.57 — 4.72 ( d,2H,Hh ) ' 3.67 ( s,3H ,Hk ) ,2.71-2.73 (m,1H,Hi) ,2.08—2.21 (m, 8H &gt; Hj + HI ) . 19F - NMR (DMSO - d6, 376MHz): δ (ppm) = -107.19 &gt; - 106.98. From the above results, it was confirmed that the compound (VIII) had the structure shown below.

[Example 7] In the reaction vessel, the following compound (7-1) 34.10 g, chlorobenzene 51.00 g, pentamethyl sulfide (6.18 g), copper (II) benzoate 0.463 g were added at 100 °. After stirring for 1 hour at C, the reaction solution was cooled to 5 〇t', and 123 g of t-butyl methyl ether was dropped thereinto. The obtained solid was redissolved in 164 g of dichloromethane, washed with 16.5 g of a 1% NH3 aqueous solution, and washed with pure water 16.5 g of water for 4 times, and then 200 g of t-butyl methyl ether was added dropwise to obtain the objective compound (7 — 2) 1 1 · 5 g (yield 47%). -111 - 200928579 【化7 0】

The obtained compound (7-2) was analyzed by NMR. The results are shown below. 1 Η — NMR ( DMS Ο — d 6, 4 0 0 M Hz ) : δ (ppm) = 8.07 ( d 2H &gt; Ph- H ) , 7.81 (d, 2H, Ph-H) &gt; 7.43 ( d ' 2H'PTS) , 7.12 (d, 2H, PTS), 4.10(t, 2H, CH2 ) '3.59 ( d &gt; 2H &gt; CH2 ) , 2.32 (s, 3H, CH3) , 2.20 ( d ' 2H ' CH2 ) , 2.19 - 1_71 ( m, 4H, CH2 ) , 1.23 ( s, 9H' t — Bu ). From the above results, it was confirmed that the compound (7-2) had the structure shown above. Next, 7.66 g of the above compound (7-2) and 23.00 g of pure water were added to the reaction vessel, followed by stirring. 11.15 g of the above compound (III) was added thereto, and 76.6 g of dichloromethane was added and stirred for 24 hours. Then, the reaction liquid was separated, and the obtained organic phase (dichloromethane phase) was recovered, and washed with 73.4 g of a 1% aqueous hydrochloric acid solution. After that, it was washed 4 times with pure water. The organic phase was separated, and methylene chloride was removed under reduced pressure to give the objective compound (X) 2.1 g (yield: 16 6 %). -112- 200928579 【化7 1】

The obtained compound (X) was analyzed by NMR. The results are shown below. H-NMR (DMSO - d6, 400 MHz): δ (ppm) = 7_96 (d, 2H, Ph-H), 7.71 (d, 2H, Ph-H) &gt; 5.49 ( t , 1H, CH) , 4.97 (s, lH, CH), 4.71 (d, lH, CH), 4.58 (s, 1H &gt; CH ) , 3.77 (m, 4H - CH2 ) , 2.72 ( m , 1H, CH) , 2.15 (m, 4H) , CH2), 1.97 (m, 2H, CH2), 1.73 (m, 2H, CH2), 1.30 (s, 9H, t-Bu). From the above results, it was confirmed that the compound (X) had the structure shown above. [Examples 8 to 1 1 and Comparative Example 1] The components shown in Table 1 were mixed and dissolved to prepare a positive resist composition. -113- 200928579 [Table 1] (Α) Ingredients (Β) Ingredients (9) Ingredients (8) Ingredients (S) Ingredient Example 8 (A) -1 [100] (Β) -1 (6.5) (D) -1 [0.50 〕 (Ε) -1 [1.32] (S) -1 [2000] (S) -2 [10] Example 9 (A) -1 [1〇〇] (8) - 2 [14.0] (D) -1 [ 0.50] (Ε) -1 [1.32] (S) -1 [2000] (S) -2 [10] Example 1〇(A) -1 [100] (Β) -3 [6.5] (D) - 1 [0.50 ] (Ε) -1 [1.32] (8) -1 [2000] (S) -2 [10] Example 11 (Α) -2 [100] (Β) -3 [6.5] (D) -1 [0.75] (Ε) -1 [1.32] (8)-1 [2000] (S) -2 [10] Comparative Example 1 (Α) -1 [1〇〇] (Β,)—1 (8.0) (D) -1 [0.50] (Ε) -1 [1.32] (8) - 1 [2000] (S) -2 [1〇] In Table 1, the number 値 in [] is the amount of addition (parts by mass). Further, the symbols in Table 1 indicate the following contents, respectively. (A) — 1: Copolymerization of Mw=7000 and Mw/Mn=1.8 represented by the following chemical formula (A) _1 (where l/m/n = 45/35/20 (mole ratio)) Things. (A) - 2: a copolymer of Mw = 5000 and Mw / Μ = 1.7 represented by the following chemical formula (A) _2 (wherein, = 45/35/20 (mole ratio)). (B) - 1 : the above compound (IV). (B) - 2: the above compound (V). (B) - 3 : the above compound (VI). (B')-1:4-methylphenyldiphenylphosphonium hexafluoro-n-butane sulfonate. (D) — 1: Tri-n-pentylamine. (Ε ) — 1 : Salicylic acid -114- 200928579 (S) — 1 : PGMEA/PGME=6/4 (mass ratio) mixed solvent. (s) — 2: Butyrolactone. [化 7 2]

〇 [Analytical, Sensitivity] - The organic anti-reflective film composition "ARC29A" (trade name, manufactured by Privah Technology Co., Ltd.) was applied to a sand wafer of 8 inches in a spin coater and hot pressed. The plate was baked and dried at 205 t for 60 seconds to form an organic anti-reflection film having a film thickness of 84 nm. Subsequently, the positive-type photoresist composition of the above Table 1 was separately coated on the anti-reflection film using a spin coater, and pre-baked on a hot plate at 120 ° C for 60 seconds (PAB). After the treatment, after drying, a photoresist film having a film thickness of 150 nm was formed. Next, a coating liquid for forming a protective film was formed using a spin coater ^-115-200928579 TSRC_002" (trade name, Tokyo Toka Chemical Co., Ltd. was applied to the above-mentioned photoresist film, and 9 (TC, 60 seconds) The result of the heating of the bell, the top coating layer with a film thickness of 28 nm. Next, using the ArF exposure apparatus NSR-S609B for infiltration (manufactured by the company; NA (number of openings) = 1.07, 2/3 wheel belt illumination, reduction ratio of 1 / 4 times, Infiltrated media: water), ArF excimer Ray 193 nm) selectively irradiates the photoresist film 0 with the top coating layer through a mask. Using a protective film removal solution "TS-Rememover — S" , Tokyo Toka Chemical Co., Ltd.) removes the top coating layer, performs PEB treatment at 110 ° C for 60 seconds, and then uses TMAH aqueous solution NMD-3 at 23 ° C (Tokyo Yinghua Industrial Co., Ltd.) Co., Ltd.) was developed for 60 seconds, and then washed with pure water for 30 seconds, and subjected to vibration drying. As a result, in any of the examples, Q was 65 nm wide on the photoresist film. Line and space pattern with a pitch of 130 nm. At this time, the line width is 65n. m, the line with a pitch of 130 nm, the best exposure amount Eop (mJ/cm2) of the pattern, it is found that the actual 8 is 35.6 mJ/cm2, the embodiment 9 is 30.0 mJ/cm2, and the implementation 1 is 36.0 mJ/cm2. Example 11 is 27.0 mJ/cm 2 and Comparative Example 33.5 mJ / cm 2 . &lt;Mask linear evaluation&gt; In the above Εορ, the LS ratio (line width and space) of the mask pattern is formed into a Ricoh small shot ( The product name is 2.38 finite water into the shape and the empty application can be 1 0 1 for the width -116-200928579 ratio) fixed to 1:1, so that the mask size (line width) in the range of 65~120nm to 5nm Each LS pattern was formed under the change, and the size (line width) of the formed LS pattern was measured. As a result, it was found that in Examples 8 to 11, an LS pattern corresponding to the faithful size of the mask size can be formed, and it is confirmed. The photoresist compositions of Examples 8 to 1 had better mask reproducibility than Comparative Example 1. [Example 1 2 to 1.5, Comparative Example 2] The components shown in Table 2 were mixed. Dissolved to make a positive photoresist composition. [Table 2] (A) Component (B) Component (9) Component (8) Component (S) Component Example 12 (A) -1 1〇〇] (B) -3 [0.8] (B,)—2 [10.4] (D) -1 [1.0] (E) -1 [1.32] (S) -1 [2000] (S) -2 [10] Example 13 (A) -1 [1〇〇] (B) -2 [1.2] (B')-2 [10.4] (D) -1 [1.0] (E) -1 [1_32] ( S) -1 [2000] (S) -2 [10] Example 14 (A) -1 [100] (8) - 2 [2.3] (B,) - 2 [9.2] (D) -1 [1.0] ( E) -1 [1.32] (S) -1 [2000] (8) - 2 [10] Example 15 (A) - 1 [1〇〇] (8) - 2 [11.7] - CD) -1 [1.0] (E ) -1 U.32) (S) -1 (2000 ) (S) -2 [10] Comparative Example 2 (A) -1 [1〇〇] - (B,)-2 [11.7) (D) - 1 Π-0 3 (E) -1 [1.32] (S) -1 [2000] (8) - 2 [10]

In Table 2, the number 値 in [] is the added amount (parts by mass). '

2 中, (A)-1, (B)-2, (B)-3' (D)-1, (E)-1, (S)-1, (S)_2, respectively Similarly, (B')-2 represents a compound of the formula -117-200928579 represented by the following chemical formula (B')-2. 【化7 3】

.0 or

(B,)~2 ❹ ❹ The following evaluation was carried out using the obtained photoresist composition. [Analytical and Sensitivity] The organic anti-reflection film composition "ARC29A" (trade name, manufactured by Privah Technology Co., Ltd.) was applied to a hot platen by a spin coater on a 8 inch wafer. After baking and drying at 205 ° C for 60 seconds, an organic anti-reflection film having a film thickness of 89 nm was formed. Subsequently, the photoresist composition is applied to the anti-reflection film by using a spin coater, and pre-baked (pAB) is performed on a hot plate at 1 l ° C for 60 seconds. After drying, a photoresist film having a film thickness of 150 nm was formed. Then, a coating liquid for forming a protective film "TILC- 03 5" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto the resist film by a spin coater at 90 ° C for 60 seconds. As a result of the bell heating, a top coat layer having a film thickness of 90 nm was formed. Next, using an ArF immersion exposure apparatus NSR-S609B (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 1.07, σ 0.97), an ArF excimer laser (193 nm) was formed with a top view through a through-hole pattern mask pair. The above-mentioned photoresist film of the layer of -118-200928579 was coated for selective irradiation. Thereafter, the PEB treatment was carried out at 105 ° C for 60 seconds, and then, the development was carried out for 60 seconds with a 2.38 mass% aqueous solution NMD-3 (manufactured by Tokyo Ohka Co., Ltd.), and then 3 0. The water was washed with pure water in seconds and subjected to vibration drying. As a result, in any of the examples, a contact hole pattern (hereinafter, also referred to as a Dence CH pattern) having a via hole diameter of 90 nm φ disposed at equal intervals (a pitch of 180 nm) is formed on the photoresist film. : At this time, the best exposure Eop (mJ/cm2) for forming the aforementioned Deuce CH pattern is obtained. The results are shown in Table 3. [Focus Width (DOF)] In the above Eop, the focus is moderately moved up and down. And forming a photoresist pattern according to the same method as the above-mentioned resolution and sensitivity, and obtaining a Dence CH pattern can be formed within a range of ±5% (ie, 85.5 to 94.5 nm) Q-inch change rate of the target size. The depth of focus (DOF, single nm). The results are shown in Table 3. * [Mask defect factor (MEF)] In the above Eop, the diameter of the through hole is used to measure the diameter of 8 6 nm, 8 8 nm, 9 Onm, 92nm, 94nm mask pattern, CH pattern with a distance of 180 nm. At this time, the target size (nm) is used as a shaft to use the through hole pattern formed by each mask pattern on the photoresist film. The inclination of the type (nm) as the vertical axis is plotted as the industrial clock of the 2 3 °C calculated by the MEF. The position of the inch: the inch is the horizontal diameter. -119- 200928579 MEF (the inclination of the line) means that the closer the number is to 1, the better the reproducibility of the mask. The result is as follows. Table 3. [Exposure latitude (EL Marge)] The exposure amount of the Dence CH pattern with a diameter of 90 nm formed with ±5% (85.5 nm, 94.5 nm) of the target size (via diameter 90 nm) The exposure latitude (EL Marge ) (unit: %) is obtained according to the following formula. The results are shown in Table 3. Exposure latitude (EL Marge) (%) = (IE1 - E2! /

Eop) xlOO [wherein, El is an exposure amount (m J / cm 2 ) at the time of forming a CH pattern having a via diameter of 85.5 nm, and E2 represents an exposure amount at the time of forming a CH pattern having a via diameter of 94.5 nm ( Mj/cm2)]. [Table 3] Example 12 Example 13 Example 实施 Example 15 Comparative Example 2 Eop (mJ/cm2) 37.0 38.5 39.9 70.0 43.0 DOF ( //m) 0.12 0.14 0.13 0.15 0.12 MEF 2.80 2.77 2.47 2.33 2.86 EL latitude (%) 11.08 11.06 11.53 10.92 10.43 As shown in Table 3, the photoresist compositions of Examples 1 2 to 15 showed good MEF and exposure latitude compared to the photoresist composition of Comparative Example 2 (ELMarge) ), and the DOF is equal to or above. From the above results, it was confirmed that the photoresist compositions of Examples 8 to 15 have excellent lithographic etching characteristics. -120-200928579 [Example 16] 6.90 g of the compound (11-1) and 28.0 g of water and 68.9 g of dichloromethane were stirred at room temperature, and the compound (III) 8.8 8 g was added thereto. After stirring for 2 hours, the organic layer was recovered by liquid separation, 200 g of methylene chloride was added, and the mixture was washed once with 1% HCl 1 aq 4 8.0 g, and washed 4 times with 48.0 g of pure water. The obtained organic layer was concentrated to dryness to give compound (XI) (yield: 55.3%).

The obtained compound (XI) was analyzed by NMR. The results are shown below. - NMR ( DMSO - d6 ' 400MHz ) : δ (ppm) = O 7.99 ( d,2H,Hd ), 7.76 ( t,1H,Hf ), 7.62 ( t,2H &gt; He ) , 5.46 ( t,1H, Hj ) , 5.30 ( s, 2H, Hc ), 4.96 * (s, lH, Hk), 4.71 (d, lH, Hi), 4.58 (d, lH, Hi ' ), 3.54 ( m, 4H, Hb ), 2.72 ( m, 2H, Hh ), 2.05- 2.28 ( m, 6H, Ha + Hg ). 19F - NMR (DMSO - d6, 3 76MHz) : δ (ppm) = -107.1. From the above results, it was confirmed that the compound (XI) had the structure shown below. -121 - 200928579 【化7 5】

[Example 1 7] 7. After dissolving 7.56 g of the compound (12-1) in 75.64 g of pure water, 10.18 g of a compound (ΠΙ) and 37.82 g of methylene chloride were added thereto, and the mixture was stirred at room temperature for 2 hours. Thereafter, the organic layer was taken out in a liquid separation manner. The organic layer was washed three times with an equal mass of 1% HCl aqueous solution, and then washed four times with an equal mass of pure water, and then the organic layer was concentrated to dryness, and then dried overnight using a vacuum pump. After that, a compound (XII) of 10.21 g (purity = 97.6 mass%, yield: 85.3%) was obtained as white solid.

【化7 6】

Θ

Η - NMR ( DMSO - d6, 400MHz ) shown below : ¢ 5 ( ppm ) 122 200928579 0.87 ( m,3H,Ha ) , 1 · 2 8 ( m,2 Η,H b ) ' 1.54 ( 2H,HC) ' 2.11 ( m &gt; 2H &gt; Hd ) , 2.67 - 2.78 (m, He + Hf ) , 4.58 ( t * 1H, Hg ) , 4.7 1 (m, 1H, Hg 5.00 (m, lH, Hh), 5.47 (m, lH, Hi), 7.72 (m , Hk), 7.74 - 7.85 (m, 12H, H,). 19F - NMR ( DMSO - d6 ' 3 76MHz) : δ ( ppm ) -1 06.1 -- 107.6 ( m, 2F, Fa), wherein hexafluorobenzene is _ 1 60 ppm. From the above results, it was confirmed that the compound (XII) has the following structure. [Chemical 7 7] m , 3H, )' , 2H peak

[Example 1 8] 5.3 g of thioanisole was added to 26.5 g of dibutyl sulfate. After stirring at ° C for 19 hours, the reaction solution was added dropwise to a solution obtained by mixing 53.0 g of butyl methyl ether 3 7.3 g of pure water, and after separating, it was washed twice with butyl methyl ether 3 7.3 g. Dichloro 100, t -t - methane -123- 200928579 3 9 9 g were added to the obtained aqueous layer, and the organic layer was recovered by liquid separation, and washed three times with pure water 4 2.8 g. The obtained organic layer was concentrated to dryness to give Compound (1-8-1) 6.7 g (yield: 4. 1.7%). [化7 8]

(18-1) The obtained compound (18-1) was analyzed by NMR. The results are shown below. 'H-NMR (DMSO-d6 '400MHz): 5 (ppm) = 8.15 (d&gt;2H&gt; Ha), 7.85 - 7.63 (m, 3H, Hb) ' 3.89 - 3_70(m,6H &gt; Hc ) , 1.52 - 1.19 ( m &gt; 12H, Hd ), 0.89 -0.60 ( m, 9H, He ).

From the above results, it was confirmed that the compound (1 8 - 1 ) had the structure shown below. [化7 9]

-124-200928579 4.89 g of the compound (18-1) and 26.5 g of pure water were stirred at room temperature, and 53.0 g of dichloromethane and 5.30 g of the compound (III) were added thereto. After stirring for 1 hour, the organic layer was separated by a liquid separation treatment, washed twice with 2 6.5 g of a 1% aqueous HCl solution and 2 times with 26.5 g of pure water. The obtained organic layer was concentrated to dryness to give Compound (XIII) 4.00 g (yield 57.4%). [化8 0]

The obtained compound (XIII) was analyzed by NMR. The results are shown below. lH - NMR ( DMSO - d6 ' 400MHz ) : δ (ppm) = 8.12 (d - 2H&gt; Ha) , 7.82 - 7.63 (m, 3H, Hb), 5.45 (

〇t,1H,Hc), 4.98 (t,1H,Hd), 4.69 &gt; 4_58 ( m,2H ,He) , 3.89-3.70 (m,4H,Hf) , 2.71 (q,lH,Hg) , 2.12 (t, 2H, Hh), l_52-1.19 (m, 8H, Hi) ' 0.89 % — 0.6 0 ( m, 6 H, Hj ). I9F-NMR (DMSO-d6, 3 76MHz): δ (ppm) = -106.7, a 106.9. From the above results, it was confirmed that the compound (XIII) had the structure shown below. -125- 200928579 【化8 1】

-126-

Claims (1)

200928579 X. Patent Application No. 1 A photoresist composition which is a substrate component (A) containing a change in solubility of an alkali developer via an action of an acid, and an acid generator which generates an acid via exposure. The photoresist composition of the component (B), wherein the acid generator component (B) is an acid generator (B1) formed by a compound represented by the following formula (bl-1); 】 [wherein, X is a 0-, an S-, a 0-R3- or an S-R4-, R3 and R4 are each independently an alkylene group having 1 to 5 carbon atoms; and R2 is a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyalkyl group having 1 to 6 carbon atoms, a hydroxyl group or a cyano group; a is an integer of 0 to 2; Q1 is an alkylene group or a single bond having a carbon number of 1 to 12; Y1 is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4; and A+ is an organic cation]. 2. The photoresist composition according to claim 1, wherein the substrate component (A) is a substrate component which increases the solubility to the alkali developer via the action of an acid. 3. The photoresist composition according to claim 2, wherein the substrate component (A) is a resin component (A1) containing a solubility of -127-200928579 to an alkali developer via an action of an acid. The resin component (A1) is a structural unit derived from an acrylate having an acid dissociable dissolution inhibiting group. 4. The photoresist composition according to claim 3, wherein the resin component (A1) has a content A structural unit derived from propylene containing a lactone ring group (a2). 5. The photoresist composition of claim 3, wherein the resin component (A1) has a structural unit (a3) derived from a polar group-containing aliphatic hydrocarbyl acrylate. 6. The photoresist composition according to claim 1, which comprises the organic compound (D). 7. A method for forming a photoresist pattern, comprising the step of using a photoresist composition according to any one of claims 1 to 6 to form a photoresist film on a support, and exposing the photoresist film Step 'and the step of developing the front barrier film to form a photoresist pattern. 8. A compound characterized by having a compound represented by the above formula (I), wherein the above-mentioned acid ester comprises a nitrogen-containing rh s main methyl δ 上 , and a compound of the above formula (I) -128- 200928579 [wherein, X is a Ο-, a s-, _0-R3- or _S_R4 _, R3 and R4 are each independently an alkylene group having a carbon number of 1 to 5; R2 is a carbon number of 1~ An alkyl group of 6 , an alkoxy group having 1 to 6 carbon atoms, a decantyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyalkyl group having 1 to 6 carbon atoms, a hydroxyl group or a cyano group; a being 0 to 2 An integer; Q1 is an alkylene group or a single bond having a carbon number of 1 to 12; γ ΐ is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4; and Μ + is an alkali metal ion]. A method for producing a compound comprising a compound represented by the following formula (I-3) (I-3) and a compound represented by the following formula (I-4) (I) - 4) a step of dehydration condensation to obtain a compound (:) represented by the following formula (I), [Chemical 3] 〇II + ΗΟ-C-Y1-SO; Μ ... -129- 200928579 A, R3 and R4 are each independently an alkylene group having 1 to 5 carbon atoms; R2 is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number of 1 to 6 Halogenated alkyl group, halogen atom, hydroxyalkyl group having 1 to 6 carbon atoms, hydroxyl group or cyano group; a is an integer of 0 to 2; Q1 is an alkylene group or a single bond having a carbon number of 1 to 12; Y1 is a carbon number of 1 ～4 alkyl or fluorinated alkyl; M + is an alkali metal ion]. 10. A compound represented by the following formula (bl-1), [Chemical 4] [wherein, X is a 〇-, an S-, -0-R3- or -s--R4-, R3 and R4 are each independently an alkylene group having a carbon number of 1 to 5; R2 is a carbon ❹ number 1~ An alkyl group of 6 , an alkoxy group having 1 to 6 carbon atoms, a nationalized alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyalkyl group having 1 to 6 carbon atoms, a hydroxyl group or a cyano group; a is 〇~2 An integer; Q1 is an alkylene group or a single bond having a carbon number of 1 to 12; γ ΐ is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4; and Α + is an organic cation. 11. An acid generator characterized by being formed by a compound of claim 10 of the scope of the patent application. -130- 200928579 VII. Designated representative map: (1) The designated representative figure of this case is: None (2), the representative symbol of the representative figure is simple: No 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 0 ·*· (blβ 1)